KR20130090726A - Nitrogen-containing heterocyclic compound and organic electronic device using the same - Google Patents

Abstract

PURPOSE: A heterocyclic derivative having nitrogen and an organic electronic device using the same are provided to improve the efficiency and stability of the organic solar cell and organic electronic device. CONSTITUTION: A heterocyclic derivative having nitrogen includes at least two of a structure which is represented by chemical formula 1 or a structure of the chemical formula 1. An organic electronic device includes a first electrode, a second electrode, and at least one organic layer arranged between the first and second electrode. At least one of the organic layer contains the heterocyclic derivative having nitrogen. The electronic device is the organic solar cell, an organic light emitting device, an organic photoreceptor, or an organic transistor.

Description

Heterocyclic derivatives containing nitrogen and organic electronic devices using the same {NITROGEN-CONTAINING HETEROCYCLIC COMPOUND AND ORGANIC ELECTRONIC DEVICE USING THE SAME}

The present invention relates to a novel heterocyclic derivative containing a nitrogen element and an organic electronic device using the same, and more particularly to a novel heterocyclic derivative containing a nitrogen element capable of improving the photoelectric conversion efficiency of an organic solar cell.

Recently, the development of organic materials with semiconducting properties and various applications using them have been actively studied. Applications of organic semiconductors such as electromagnetic wave shielding films, capacitors, OLED displays, organic thin film transistors (OTFTs), solar cells, and memory devices using multiphoton absorption phenomena continue to expand.

In particular, the OLED field is in the forefront of commercialization of large-sized displays, and thus acts as a catalyst to activate application research using organic materials. Organic semiconductor thin film transistors (OLEDs), which are expected to be used for applications such as next- Are also emerging. In addition, after the announcement of the electrical power generation characteristics using the organic semiconductor as an active layer, it is also drawing a lot of attention to the application as a laser diode. Compared to non-organic materials, the cost of producing devices is remarkably low, so we are anticipating a future change in the solar cell market.

Solar cells are devices that can convert solar energy directly into electrical energy by applying a photovoltaic effect. Solar cells can be divided into inorganic solar cells and organic solar cells according to the material constituting the thin film.

A typical solar cell is made of p-n junction by doping crystalline silicon (Si), which is an inorganic semiconductor. Electrons and holes generated by absorption of light are diffused to the p-n junction, accelerated by the electric field, and moved to the electrode. The power conversion efficiency of this process is defined as the ratio of the power given to the external circuit to the solar power entering the solar cell, and is achieved up to 24% when measured under the current standardized virtual solar irradiation conditions.

However, since conventional inorganic solar cells have already been limited in terms of economy and supply / demand of materials, organic semiconductor solar cells, which are easy to process, have various functions and are inexpensive, are attracting attention as long-term alternative energy sources.

Organic solar cells use a variety of organic semiconductor materials in small quantities, which can result in cost savings and can be fabricated using an easy method because they can be fabricated using wet processes.

Korean Unexamined Patent Publication 10-2007-0043666

The present invention provides a heterocyclic derivative containing a nitrogen element and an organic electronic device using the same.

The present invention provides a heterocyclic derivative containing a nitrogen element represented by Formula 1 or comprising two or more structures of Formula 1 below:

[Formula 1]

In Formula 1,

Ar ₁ is cyano group (-CN); Ester group (-CO ₂ R); Carbonyl group (-COR); Fluoro groups (-F); Or a chloro group (-Cl), where R is alkyl having 2 to 20 carbon atoms,

X ₁ is N or CR ₁ , X ₂ is N or CR ₂ , X ₃ is N or CR ₃ , X ₄ is N or CR ₄ , X ₁ to X ₄ are not N at the same time,

A ₁ is N or CR ₅ , A ₂ is N or CR ₆ , A ₃ is N or CR ₇ , A ₄ is N or CR ₈ , and at least two of A ₁ to A ₄ are not N,

R ₁ to R ₉ are each independently-(L) p- (Y) q, where p is an integer of 0 to 10, q is an integer of 1 to 10, and two or more adjacent ones of R ₁ to R ₄ Groups can form a monocyclic or polycyclic ring,

L is oxygen; sulfur; Nitrogen substituted or unsubstituted with an alkyl or aryl group; A substituted or unsubstituted arylene group; A substituted or unsubstituted arylamine group; Substituted or unsubstituted triarylamine group; Substituted or unsubstituted triaryl phosphine group; Substituted or unsubstituted triaryl phosphine oxide group; A substituted or unsubstituted alkenylene group; Substituted or unsubstituted alkynylene group; A substituted or unsubstituted fluorenylene group; A substituted or unsubstituted carbazolylene group; Substituted or unsubstituted benzocarbazolylene group; Cyclic ketone groups of an aromatic or aliphatic ring; Aromatic ring groups; Substituted or unsubstituted aromatic or aliphatic heterocyclic group containing one or more of N, O, S atoms; Or a condensed ring group of the aromatic ring and the heterocycle,

Y is hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; Ester group (-CO ₂ R); Carbonyl group (-COR); Ester group (-CO ₂ R); Imide group; An amide 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; Substituted or unsubstituted alkylthioxy group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; Substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted triarylamine group; A substituted or unsubstituted triarylphosphine group; A substituted or unsubstituted triarylphosphine oxide group; Substituted or unsubstituted aryl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted carbazole group; Substituted or unsubstituted benzocarbazole group; Cyclic ketone groups of an aromatic or aliphatic ring; Imide groups of aromatic or aliphatic rings; Aromatic ring groups; A substituted or unsubstituted aromatic or aliphatic heterocyclic group containing at least one of N, O and S atoms; Or a condensed ring group of the aromatic ring and the heterocycle, wherein R is alkyl having 2 to 20 carbon atoms,

When X ₁ to X ₄ are CR ₁ to CR ₄ at the same time, at least one of R ₁ to R ₄ has a substituent other than hydrogen, or at least two of R ₁ to R ₄ are bonded to each other and substituted monocyclic or multi. It may form a cyclic ring.

The present invention also provides an organic electronic device comprising a first electrode, a second electrode, and at least one organic layer disposed between the first and second electrodes, wherein at least one of the organic layers contains the novel nitrogen element. It provides an organic electronic device comprising one heterocyclic derivative.

The nitrogen-containing heterocyclic derivative according to the present invention can be used as a material of an organic material layer of an organic electronic device including an organic solar cell, and the organic electronic device including the organic solar cell using the same exhibits excellent characteristics such as efficiency increase and stability increase. .

In particular, the new nitrogen-containing heterocyclic derivatives according to the present invention exhibited excellent thermal stability, deep HOMO levels, various band gaps, various LUMO level states and electronic stability.

The derivative of Formula 1 according to the present invention can be used purely in organic electronic devices including organic solar cells, or can be used by mixing impurities, and can be applied by vacuum deposition, solution coating, etc. Thermal stability can improve the lifetime characteristics of the device.

1 illustrates an example of an organic solar cell including a substrate 101, a first electrode 102, a hole transport layer 103, a photoactive layer 104, and a second electrode 105.
2 is a diagram showing a mass spectrum of Compound 1-A-1.
3 is a diagram showing a mass spectrum of Compound 1-a-8.
4 is a diagram showing a mass spectrum of Compound 1-a-49.
5 is a diagram showing a mass spectrum of Compound 1-a-50.

Hereinafter, the present invention will be described in detail.

The nitrogen-containing heterocyclic derivative according to the present invention is represented by the formula (1) or includes two or more structures of the formula (1).

In Formula 1, the alkoxy group may be linear or branched chain. Although carbon number of an alkoxy group is not specifically limited, It is preferable that it is 1-40 which is a range which does not give a steric hindrance. For example, in Formula 1, when Y of-(L) p- (Y) q is an alkoxy group, the number of carbon atoms of this alkoxy group does not affect the conjugated length of the compound, The number of carbon atoms in the alkoxy group is not particularly limited since it only affects the application of the method, for example, the vacuum deposition method or the solution coating method.

In the present invention, the alkenyl group may be linear or branched chain, preferably an alkenyl group having 2 to 40 carbon atoms, and specifically, an alkenyl group substituted with an aryl group such as stilbenyl group or styrenyl group Or an alkenyl group substituted with a cycloalkyri or cycloalkenyl group is preferred, but not limited thereto.

In Formula 1, the aryl group may be monocyclic or polycyclic, and the number of carbon atoms is not particularly limited, but is preferably 6 to 60. Examples of the monocyclic aryl group include a phenyl group, a biphenyl group, a terphenyl group, a stilbene group, and the like, and examples of the polycyclic aryl group include a naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, and tetrasenyl group. , Chrysenyl group, fluorenyl group, acenaphthasenyl group, triphenylene group, fluoranthrene group and the like, but the scope of the present invention is not limited only to these examples.

In the general formula (1), the heterocyclic group is a heterocyclic group containing at least one of N, O or S as a hetero atom, carbon number is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furane group, a furyl group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a triazine group, , A quinolinyl group, an isoquinoline group, an indole group, a carbazole group, a benzoxazole group, a benzimidazole group, a benzothiazole group, a benzoxazole group, a benzthiophene group, a dibenzothiophene group, a benzfuranyl group, Naphthyl group, naphthyl group, naphthyl group, naphthyl group, quinacridone group, acridone group and the like.

In the formula (1), the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and particularly preferably a cyclopentyl group and a cyclohexyl group.

In the present invention, examples of the halogen group include fluorine, chlorine, bromine or iodine.

등이 있으나, 이들에 한정되는 것은 아니다.In the present invention, the fluorenyl group includes a structure of a closed fluorenyl group and an open fluorenyl group, wherein the open fluorenyl group has a structure in which two ring organic compounds are linked to each other through a single atom. As a broken structure, for example

And the like, but are not limited thereto.

In the present invention, examples of the aryl amine group include substituted or unsubstituted monocyclic diarylamine groups, substituted or unsubstituted polycyclic diarylamine groups or substituted or unsubstituted monocyclic and polycyclic diaryls. It means an amine group.

등이 있으나, 이들에 한정되는 것은 아니다.In the present invention, examples of the cyclic ketone group of the aromatic or aliphatic ring include

And the like, but are not limited thereto.

등이 있으나, 이에만 한정되는 것은 아니다.In the present invention, the substituted or unsubstituted aromatic or aliphatic heterocyclic group including one or more of N, O, and S atoms may be condensed not only with an aromatic ring, an aliphatic ring, but also with each other or with an aromatic ring and an aliphatic ring. For example

Etc., but is not limited thereto.

등이 있으나, 이들에 한정되는 것은 아니다.In the present invention, examples of the aromatic aryl group include

And the like, but are not limited thereto.

등이 있으나, 이들에 한정되는 것은 아니다. 또한, 방향족 고리와 헤테로고리의 축합고리기들은 화학식 1에 상기 예에서 제시한 아릴기나 다른 방향족 헤테로고리기로 연결될 수 있다. In the present invention, examples of the condensed ring group of the aromatic ring and heterocyclic ring include

And the like, but are not limited thereto. In addition, the condensed ring groups of the aromatic ring and the heterocyclic ring may be linked to the aryl group or other aromatic heterocyclic group shown in the above example in Formula 1.

등이 있으나, 이들에 한정되는 것은 아니다.In the present invention, examples of the imide group of the aromatic or aliphatic ring,

And the like, but are not limited thereto.

According to an exemplary embodiment of the present invention, including two or more structures of Formula 1 means that the compounds having the structure of Formula 1 exist in a directly connected structure without a linking group. In this case, it means that each of the same formula or different formulas of Formula 1 may directly combine to include two or more of the formula structure.

According to yet an embodiment of the present invention, comprising two or more structures of the formula (1), Alkan having a bivalent or more linking group; Cycloalkane having a divalent or higher linking group; Substituted or unsubstituted aryl having a divalent or higher linking group; Substituted or unsubstituted fluorene having a divalent or higher linking group; Cyclic ketones of aromatic or aliphatic rings having a divalent or higher linking group; Substituted or unsubstituted heterocycle having a bivalent or higher linking group containing at least one of N, O, S atoms; Groups having a condensed or non-condensed divalent or higher linking group comprising a heterocycle or an aromatic ring; Oxygen atom; Hwang Wonjae; Substituted or unsubstituted nitrogen atom; Or it means that two or more structures of the formula (1) may be connected to a substituted or unsubstituted phosphorus atom. In this case, it means that the same or different formulas of Formula 1 may be combined to include two or more formula structures.

The heterocyclic derivative containing a nitrogen element according to the present invention includes two or more structures of Formula 1 may be represented by the following Formula 2.

[Formula 2]

In Formula 2, Ar ₁ , X ₁ , X ₂ , X ₃ , X ₄ , A ₁ , A ₂ , A ₃ , A ₄ and R ₉ are the same as defined in claim 1, and Z represents a divalent or higher linking group. Direct binding; Alkanes having a divalent or higher linking group; Cycloalkane having a divalent or higher linking group; Substituted or unsubstituted aryl having a divalent or higher linking group; Substituted or unsubstituted fluorene having a divalent or higher linking group; Cyclic ketones of aromatic or aliphatic rings having a divalent or higher linking group; Substituted or unsubstituted heterocycle having a bivalent or higher linking group containing at least one of N, O, S atoms; Groups having a condensed or non-condensed divalent or higher linking group comprising a heterocycle or an aromatic ring; O; S; NR '; PR ',

Where R 'is hydrogen; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; Selected from the group consisting of a substituted or unsubstituted aryloxy group,

Substituted or unsubstituted Z is connected to any one of X ₁ to X ₄ ,

n is the number of compounds represented by the formula (1) connected by a linking group, n is an integer of 2 to 10, preferably 2 or 3, more preferably n is 2.

In this invention, although the following group is mentioned as a bivalent coupling group, it is not limited to these.

R and R 'are hydrogen; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; It is selected from the group consisting of a substituted or unsubstituted aryloxy group.

In the present invention, "substituted or unsubstituted" means deuterium; A halogen group; A nitrile group; A nitro group; A hydroxy group; An alkyl group; A cycloalkyl group; An alkoxy group; An aryloxy group; Alkyl thioxy group; Arylthioxy group; An alkylsulfoxy group; Arylsulfoxy group; An alkenyl group; Silyl groups; Boron group; An alkylamine group; Aralkyl amine groups; An arylamine group; An aryl group; A fluorenyl group; Carbazole group; And an unsubstituted or substituted with at least one of a heterocyclic group including one or more of N, O, and S atoms, and it is preferable that the substituent is an alkyl group or an aryl group.

In the compound according to the present invention, Ar ₁ is preferably a cyano group (-CN).

In the compounds according to the invention, it is preferred that X ₁ is CR ₁ , X ₂ is CR ₂ , X ₃ is CR ₃ and X ₄ is CR ₄ .

In the compound according to the present invention, N in A ₁ to A ₄ is preferably 2 or less. As one example, it is more preferred that A ₁ is CR ₅ , A ₂ is CR ₆ , A ₃ is CR ₇ , and A ₄ is CR ₈ .

In the compound according to the present invention, p is preferably an integer of 0 to 3, and q is an integer of 1 to 3 in-(L) p- (Y) q.

L is a substituted or unsubstituted arylene group; A substituted or unsubstituted arylamine group; Substituted or unsubstituted triarylamine group; Substituted or unsubstituted triaryl phosphine group; Substituted or unsubstituted triaryl phosphine oxide group; A substituted or unsubstituted alkenylene group;

Substituted or unsubstituted alkynylene group; A substituted or unsubstituted fluorenylene group; A substituted or unsubstituted carbazolylene group; Substituted or unsubstituted benzocarbazolylene group; Cyclic ketone groups of an aromatic or aliphatic ring; Aromatic ring groups; Substituted or unsubstituted aromatic or aliphatic heterocyclic group containing one or more of N, O, S atoms; Or a condensed ring group of the aromatic ring and the heterocycle,

Y is a substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; Substituted or unsubstituted triarylamine group; Substituted or unsubstituted triaryl phosphine group; Substituted or unsubstituted triaryl phosphine oxide group; A substituted or unsubstituted aryl group; A substituted or unsubstituted fluorenyl group; Substituted or unsubstituted carbazole group; A substituted or unsubstituted benzocarbazole group; Cyclic ketone groups of an aromatic or aliphatic ring; Imide groups of aromatic or aliphatic rings; Aromatic ring groups; Substituted or unsubstituted aromatic or aliphatic heterocyclic group containing one or more of N, O, S atoms; Or a condensed ring group of the aromatic ring and the heterocycle.

When p is 2 or more in-(L) p- (Y) q, L is the same or different. When q is 2 or more in-(L) p- (Y) q, Y is the same or different.

In the present invention, the substituted arylene group is a phenyl group, a biphenyl group, a naphthyl group, a fluorenyl group, a pyrenyl group, a phenanthrenyl group, a perylene group, and a tetrasenyl group. It means that an anthracenyl group etc. were substituted by the other substituent.

In the present invention, substituted heteroarylene groups include pyridine, thiophene, triazine, quinoline, phenanthroline, imidazole, thiazole, oxazole, carbazole and their condensed heterocyclic groups such as benzquinoline And benzimidazole, benzoxazole, benzthiazole, benzcarbazole, dibenzothiophenyl, and the like are substituted with other substituents.

Vacuum deposition (Vacuum deposition) of the method of manufacturing an organic solar cell is deposited by sublimation of the material at high vacuum, such as about 10 ^-6 to 10 ^-7 torr and high temperature. Therefore, the property that the compound can be easily sublimed while maintaining its properties without denaturation at high temperatures for a long time is important.

The structure of the general formula (1) has a plate-like core, can be easily sublimated, and by introducing an aryl group, a heteroaryl group, an arylamine group, etc. into a substituent, a compound having desired characteristics can be easily obtained.

On the other hand, the process of proceeding to the solution process method of the manufacturing method of the organic solar cell, the structure of the formula (1) is a core of the plate-like structure, substituents that can increase the solubility, for example, aryl group, heteroaryl group, alkyl group, alkylamine group It can be easily obtained by introducing a substituent such as an alkoxy group.

In addition, the compounds according to the present invention can be used in various applications in organic solar cells according to the type and nature of the substituent. For example, when a substituted or unsubstituted aryl group or a heteroaryl group is substituted, or when two or more structures of Formula 1 are linked, their properties may be deep HOMO due to an increase in electron affinity and electronegativity given by Formula 1. It is advantageous to have a suitable LUMO that can do a good value and electron acceptor, so that it can be used as an electron injection, electron transfer or hold layer.

In an exemplary embodiment of the present invention, Ar ₁ may be a cyano group (-CN).

In another embodiment, R ₉ can be hydrogen.

In another exemplary embodiment, two or less of A ₁ to A ₄ may be nitrogen. Specifically, two of A ₁ to A ₄ may be nitrogen.

In another example, only any one of A ₁ to A ₄ may be nitrogen.

In another example, A ₁ to A ₄ may be CR ₅ to CR ₈ , respectively.

In another example, R ₅ to R ₈ may be hydrogen.

In another exemplary embodiment, one or more of X ₁ to X ₄ may be nitrogen. Specifically, any one of X ₁ to X ₄ may be nitrogen.

In another example, X ₁ to X ₄ may be CR ₁ to CR ₄ , respectively.

In an exemplary embodiment of the present invention, CR ₁ to CR ₉ may be-(L) p- (Y) q.

In one example, p can be an integer from 0 to 10 and q can be an integer from 1 to 10.

In another example, p may be 0 and q may be an integer from 1 to 10. In this case, Y is a substituted or unsubstituted aryl group; A substituted or unsubstituted heterocyclic group; It may be selected from the group consisting of hydrogen.

In another example, p may be 0, q is an integer from 1 to 10, Y is a substituted or unsubstituted anthracene group; Substituted or unsubstituted benzyl group; A substituted or unsubstituted phenyl group; Substituted or unsubstituted naphthalene group; Substituted or unsubstituted pyrene group; Substituted or unsubstituted perylene group; Substituted or unsubstituted isoquinoline group; Substituted or unsubstituted naphthoimidazole group; Substituted or unsubstituted benzoimidazole group; Substituted or unsubstituted naphthothiophene group; A substituted or unsubstituted dibenzotetrafendioene group; It may be selected from the group consisting of a substituted or unsubstituted benzothiazole group.

In another example, p may be 0, q is an integer from 1 to 10, and Y is an anthracene group substituted with naphthalene; Anthracene groups substituted with alkyl groups; Anthracenyl group substituted with a substituted or unsubstituted phenyl group; Anthracenyl group substituted with a phenyl group substituted with an alkyl group; Anthracenyl group substituted with a substituted or unsubstituted triphenylphosphine; Anthracenyl group substituted with a phenyl group substituted with a cyano group; Anthracenyl group substituted with a substituted or unsubstituted thiophene; Anthracenyl group substituted with thiophene substituted with phenyl group; Anthracenyl group substituted with thiophene substituted with alkyl group; Anthracenyl group substituted with a substituted or unsubstituted fluorenyl group; Anthracenyl group substituted with fluorenyl group substituted with alkyl group; Anthracenyl group substituted with a substituted or unsubstituted aryl group; Anthracenyl group substituted with an aryl group substituted with a cyano group; Anthracenyl group substituted with a substituted or unsubstituted carbazole group; Anthracenyl group substituted with a substituted or unsubstituted arylamine group; A phenyl group substituted with an alkyl group; Phenyl group substituted with benzothiazole; Naphthalene group substituted with anthracene; Naphthalene groups substituted with alkyl groups; Naphthalene group; Naphthoimidazole groups substituted with phenyl groups; Naphthoimidazole groups substituted with naphthyl groups; Benzoimidazole group substituted with phenyl group; It may be selected from the group consisting of naphthothiophene group substituted with naphthalene.

; 치환 또는 비치환된

; 치환 또는 비치환된 아릴아민기로 이루어진 군에서 선택될 수 있다.In another exemplary embodiment, p may be an integer of 1 or more. In this case, L is a substituted or unsubstituted heterocyclic group; Substituted or unsubstituted aryl group; Substituted or unsubstituted

; Substituted or unsubstituted

; It may be selected from the group consisting of a substituted or unsubstituted arylamine group.

In another embodiment, p may be an integer of 1 or more, L is a substituted or unsubstituted thiophene group; Substituted or unsubstituted dihydrothienodioxin; Substituted or unsubstituted carbazole group; A substituted or unsubstituted benzocarbazole group; Substituted or unsubstituted benzothiadiazole group; A substituted or unsubstituted pyridine group; Substituted or unsubstituted iso quinoline group; A substituted or unsubstituted phenyl group; Substituted or unsubstituted anthracenyl group; Substituted or unsubstituted perylene group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted naphthyl group; Substituted or unsubstituted biphenyl group; It may be selected from the group consisting of a substituted or unsubstituted imidazole group.

; 플루오르기로 치환된 페닐기; 벤조티아졸기로 치환된 페닐기; 안트라세닐기로 치환된 페닐기; 페닐기로 치환된 안트라세닐기; 알킬기로 치환된 플루오레닐기; 페닐기로 치환된 아릴아민기; 페닐기로 치환된 이미다졸기로 이루어진 군에서 선택될 수 있다.In another exemplary embodiment, p may be an integer of 1 or more, and L is a thiophene group substituted with a phenyl group; Thiophene groups substituted with alkyl groups; A carbazole group substituted with a phenyl group; Pyridine groups substituted with phenyl groups; Isoquinoline group substituted with a phenyl group;

; Phenyl group substituted with fluorine group; Phenyl group substituted with benzothiazole group; Phenyl group substituted with anthracenyl group; Anthracenyl group substituted with a phenyl group; Fluorenyl groups substituted with alkyl groups; An arylamine group substituted with a phenyl group; It may be selected from the group consisting of an imidazole group substituted with a phenyl group.

In another exemplary embodiment, when p is an integer of 1 to 10, q is an integer of 1 to 10, Y is a substituted or unsubstituted aryl group; A substituted or unsubstituted heterocyclic group; It may be selected from the group consisting of hydrogen.

In another example, when p is an integer from 1 to 10, q is an integer from 1 to 10, Y is a substituted or unsubstituted anthracene group; Substituted or unsubstituted benzyl group; A substituted or unsubstituted phenyl group; Substituted or unsubstituted naphthalene group; Substituted or unsubstituted pyrene group; Substituted or unsubstituted perylene group; Substituted or unsubstituted isoquinoline group; Substituted or unsubstituted naphthoimidazole group; Substituted or unsubstituted benzoimidazole group; Substituted or unsubstituted naphthothiophene group; A substituted or unsubstituted dibenzotetrafendioene group; It may be selected from the group consisting of a substituted or unsubstituted benzothiazole group.

In another example, when p is an integer of 1 to 10, q is an integer of 1 to 10, and Y is an anthracene group substituted with naphthalene; Anthracene groups substituted with alkyl groups; Anthracenyl group substituted with a substituted or unsubstituted phenyl group; Anthracenyl group substituted with a phenyl group substituted with an alkyl group; Anthracenyl group substituted with a substituted or unsubstituted triphenylphosphine; Anthracenyl group substituted with a phenyl group substituted with a cyano group; Anthracenyl group substituted with a substituted or unsubstituted thiophene; Anthracenyl group substituted with thiophene substituted with phenyl group; Anthracenyl group substituted with thiophene substituted with alkyl group; Anthracenyl group substituted with a substituted or unsubstituted fluorenyl group; Anthracenyl group substituted with fluorenyl group substituted with alkyl group; Anthracenyl group substituted with a substituted or unsubstituted aryl group; Anthracenyl group substituted with an aryl group substituted with a cyano group; Anthracenyl group substituted with a substituted or unsubstituted carbazole group; Anthracenyl group substituted with a substituted or unsubstituted arylamine group; A phenyl group substituted with an alkyl group; Phenyl group substituted with benzothiazole; Naphthalene group substituted with anthracene; Naphthalene groups substituted with alkyl groups; Naphthalene group; Naphthoimidazole groups substituted with phenyl groups; Naphthoimidazole groups substituted with naphthyl groups; Benzoimidazole group substituted with phenyl group; It may be selected from the group consisting of naphthothiophene group substituted with naphthalene.

In an exemplary embodiment of the present invention, n in Chemical Formula 2 may be 2 to 10.

In one example, n can be two. In this case, Z is a substituted or unsubstituted arylene group; It may be selected from the group consisting of a substituted or unsubstituted heterocyclic group.

In another example, Z is a substituted or unsubstituted anthracene group; A substituted or unsubstituted terphenyl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted naphthyl group; A substituted or unsubstituted dibenzotetrafendioene group; Substituted or unsubstituted biphenyl group; Substituted or unsubstituted perylene group; A substituted or unsubstituted phenyl group; Substituted or unsubstituted pentaxenyl group; A substituted or unsubstituted quinazoline group; Substituted or unsubstituted benzothiadiazole group; Substituted or unsubstituted pyrazine group; A substituted or unsubstituted pyridine group; Substituted or unsubstituted thiophene group; It may be selected from the group consisting of substituted or unsubstituted benzodithiophene.

;

;

; 알킬기로 치환된 플루오레닐기; 페닐기로 치환된 플루오레닐기; 티오펜으로 치환된 나프틸기; 나프틸기;

;

; 티오펜기로 치환된 페닐기; 페닐기로 치환된 퀴나졸린기; 플루오레닐기로 치환된 퀴나졸린기; 페닐기로 치환된 벤조티아다이아졸기; 페닐기로 치환된 피라진기; 페닐기로 치환된 피리딘기; 페닐기로 치환된 티오펜기로 이루어진 군에서 선택될 수 있다. In another exemplary embodiment, Z is an anthracenyl group substituted with a naphthyl group; Anthracene groups substituted with a substituted or unsubstituted phenyl group; Anthracene groups substituted with a phenyl group substituted with an alkyl group; Anthracenyl group substituted with an alkyl group;

;

;

; Fluorenyl groups substituted with alkyl groups; Fluorenyl group substituted with phenyl group; Naphthyl group substituted with thiophene; Naphthyl group;

;

; Phenyl group substituted with thiophene group; A quinazoline group substituted with a phenyl group; A quinazoline group substituted with a fluorenyl group; Benzothiadiazole group substituted with a phenyl group; Pyrazine groups substituted with phenyl groups; Pyridine groups substituted with phenyl groups; It may be selected from the group consisting of a thiophene group substituted with a phenyl group.

Preferred specific examples of the compound represented by Formula 1 include, but are not limited to, those compounds represented by the formula shown in Table 1 below. Table 1 below is a compound containing an anthracene group as a substituent in the structure of formula (1).

[Table 1]

In addition, preferred specific examples of the compound represented by Formula 1 include compounds represented by the formulas shown in Table 2 below, but are not limited thereto.

[Table 2]

In addition, preferred specific examples of the compound represented by Formula 1 include compounds represented by the formulas shown in Table 3 below, but are not limited thereto.

[Table 3]

The present invention also provides a method for preparing the derivative represented by the formula (1).

Methods for preparing compounds according to the invention are described in Chemistry of Heterocyclic Compounds. vol. 40. 8. (2004), p. 1063-1069; Organic Letters. vol. 12. 7 (2010), p. 1500-1503; Chemistry of Heterocyclic Compounds vol. 40. 8. (2004). p. 1063-1069] Compound 1-A having a halogen, a hydroxy group, or the like introduced therein was synthesized by referring to the following Schemes 1-1 and 1-2, and then, a Suzuki-coupling reaction under a palladium catalyst. An aryl group or heteroaryl group was introduced or an arylamine group was introduced under a palladium catalyst.

The compound of Formula 1 is prepared by the following Formula 1-1, Scheme 1-2, and then prepared by the scheme 2-1, Scheme 2-2, but the preparation of the derivative represented by Formula 1 The method is not limited to the following scheme.

[Reaction Scheme 1-1]

[Chemical Formula 1-A]

[Reaction Scheme 1-2]

[Chemical Formula 1-B]

Formulas 1-A and 1-2 of Scheme 1-1 may be easily prepared by heating in a common organic solvent in the presence of triethylamine.

[Reaction Scheme 2-1]

[Formula 1-A] [Formula 1]

[Reaction Scheme 2-2]

[Formula 1-B] [Formula 1]

Scheme 2-1 illustrates a process of introducing substituents R ₁ to R ₄ .

Scheme 2-2 illustrates a process of introducing substituents R ₅ to R ₈ .

In the scheme, X ₀ is a halogen element, such as fluoro (F-), chloro (Cl-), bromo (Br-), and iodo (I-), X ₁ to X ₄ is represented by the formula Same as definition.

In the scheme, X ₁ 'to X ₄ ' and A ₁ 'to A ₄ ' are each or simultaneously halogen elements such as chloro (Cl-), bromo (Br-), and iodo (I-), or

X ₁ to X ₄ , and A ₁ to A ₄ are the same as R ₁ to R ₈ in the formula (1), respectively or simultaneously. This is because the substituent can be easily introduced into the Suzuki bond under the Pd catalyst.

The introduction of such substituents can easily be modified to various R ₁ to R ₈ by methods well known to those skilled in the art. Specific examples thereof will be given in the preparation examples.

The compound of the present invention can act as an electron acceptor material having various LUMO levels because the energy level can be controlled by the core and basically various substituents.

In addition, the present invention is an organic electronic device comprising a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, at least one of the organic layer is a compound of Formula 1 It provides an organic electronic device comprising a.

The organic electronic device of the present invention can be produced by a conventional method and materials for producing an organic electronic device, except that one or more organic material layers are formed using the above-described compounds.

The organic electronic device may be selected from the group consisting of organic solar cells, organic light emitting electrons, organophotoreceptor (OPC) drums, and organic transistors.

Hereinafter, it demonstrates about an organic solar cell.

In one embodiment of the present invention, there is provided an organic solar electron having a structure comprising a first electrode and a second electrode and an organic material layer disposed between the first electrode and the second electrode.

In another embodiment, an organic solar cell including a first electrode, a second electrode, and an organic active layer disposed between the first electrode and the second electrode and containing a heterocyclic derivative containing the nitrogen element. To provide.

In another embodiment, the organic solar cell may be an organic solar cell having a structure in which an anode, one or more organic layers, and a cathode are sequentially stacked on a substrate. In another embodiment, the organic solar cell may be an organic solar cell having a reverse structure in which a cathode, at least one organic layer, and an anode are sequentially stacked on a substrate.

In addition, the present invention is an organic solar cell according to the structure of the photoactive layer, an organic solar cell comprising a photoactive layer consisting of two layers of p-type semiconductor film and n-type semiconductor thin film, that is, bi-layer pn junction type Provide an organic solar cell.

The present invention provides an organic solar cell including a photoactive layer in which an n-type semiconductor and a p-type semiconductor are blended, that is, a bulk heterojunction (BHJ) junction organic solar cell.

A bi-layer p-n junction type organic solar cell is shown in Fig.

Referring to FIG. 1, an organic solar cell includes a substrate 101, a first electrode 102, a hole transport layer 103, a photoactive layer 104, and a second electrode 105, and the photoactive layer 104. The silver may include a p-type semiconductor thin film and an n-type semiconductor thin film.

Photoexcitation causes the p-type semiconductor to form an exciton paired with electrons and holes, and the exciton is separated into electrons and holes at the p-n junction. The separated electrons and holes migrate to the n-type semiconductor thin film and the p-type semiconductor thin film, respectively, and they are collected in the first electrode and the second electrode, respectively, so that they can be used as electric energy from the outside.

In another exemplary embodiment, the heterocyclic derivative containing a nitrogen element of Chemical Formula 1 is an electron acceptor material, and the organic active layer further provides an electron donor material.

In another exemplary embodiment, the derivative of Chemical Formula 1 provides an organic solar cell having an LUMO energy level of −3 to −5 eV.

In another exemplary embodiment, the derivative of Formula 1 provides an organic solar cell having a LUMO energy level of −5 eV or less. That is, the derivative of Formula 1 provides an organic solar cell having an LUMO energy level of 5 eV or more as an absolute value.

It is suitable for application to the electron acceptor of organic solar cell.

Specifically, the derivative of Formula 1 provides an organic solar cell having a LUMO energy level of -3.3 to -4.5 eV.

In particular, in order to use the aromatic heterocyclic derivative including the nitrogen atom of Chemical Formula 1 as an electron acceptor of an organic solar cell, the LUMO level of compounds such as P3HT, which is generally used as an electron donor, and one metal Considering the work function, the level of LUMO of the e-acceptor should be adjusted. HOMO and LUMO can be controlled by introducing various substituents to the substituents and R ₁ to R ₉ to attract electrons of Ar ₁ .

When the compound of Formula 1 is used as the electron acceptor material in the photoactive layer of the organic solar cell, LUMO can be adjusted to expect higher open voltage than the conventional organic solar cell using PCBM as the electron acceptor material in the photoactive layer. HOMO adjustment may also be possible to enable a blocking role.

Solar cells are important to increase efficiency so that they can output as much electrical energy as possible from solar energy. In order to increase the efficiency of such a solar cell, it is also important to generate as much excitons as possible in the semiconductor, but it is also important to draw out generated charges without loss. Therefore, the organic solar cell by the heterocyclic derivative containing a nitrogen element represented by the formula (1) of the present invention can improve the energy efficiency by controlling LUMO and HOMO.

The organic solar cell according to the present invention may be manufactured using a conventional method and material for manufacturing an organic solar cell, except that the compound of Formula 1 is used in at least one layer of the organic material layer of the organic solar cell.

For example, the organic solar cell according to the present invention can be manufactured by using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation to form a metal or conductive metal oxide or an alloy thereof To form an anode, then forming an organic material layer on the organic material layer by vacuum deposition or solution coating thereon, and then depositing a material usable as a cathode on the organic material layer.

The organic solar cell provides an organic solar cell having a reverse structure in addition to the sequentially stacked structure.

In addition to the sequentially stacked structure as described above, in order to manufacture an organic solar cell of the reverse structure, the organic solar cell may be made by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

The organic layers of the respective layers may be formed by using a variety of monomolecular or polymeric materials, not a vapor deposition method, but a solvent process such as roll to roll, spin coating, dip coating, casting, roll court, Coating, flow coating, doctor blading, screen printing, inkjet printing, or thermal transfer.

A dry film formation method such as an organic layer of each of the above layers, vacuum deposition, sputtering, plasma, ion plating, or the like.

As the anode material, a material having a large work function is preferably used so as to smoothly inject holes, which are usually formed in the organic material layer. Specific examples of the cathode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SnO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline.

The negative electrode material is preferably a material having a small work function to facilitate injection of electrons from the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; Layer structure materials such as LiF / Al or LiO ₂ / Al, but are not limited thereto.

The hole transport material is a material capable of well injecting holes from the active layer, and the highest occupied molecular orbital (HOMO) of the hole transport material is preferably between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of the hole transferring material include metal porphyrine, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, perylene , Anthraquinone, polyaniline and polythiophene-based conductive polymers, but the present invention is not limited thereto.

In addition, several hole transport layers may be used. At this time, a compound having high mobility to holes is suitable. Specific examples thereof include arylamine-based compounds; Carbazole-based compounds; Anthracene-based compounds; Pyrene-based compounds; A conductive polymer, a block copolymer having a conjugated portion and a non-conjugated portion together, but the present invention is not limited thereto.

The photoactive layer of the organic solar cell according to the present invention may include a bulk heterojunction.

Bulk heterojunction means that the electron donor material and the electron acceptor material are mixed in the photoactive layer. The photoactive layer of the organic solar cell of the present invention may be an electron donor material or a mixture layer (bulk heterojunction layer) of an electron donor material and an electron acceptor material.

Representative electron donor materials include the following structures, including PPV (poly (phenylene vinylene)) polymer or P3HT (poly (3-hexylthiophene)) polymer.

The electron donor materials are preferably substances having a small band gap so as to absorb the entire visible light region of sunlight, and polymer compounds are generally used, but the present invention is not limited thereto.

The most widely used electron acceptor material is the {6} -1- (3- (methoxycarbonyl) propyl) - {5} - methanofullerene derivative as disclosed in the Fred Wudl group in 1995 } -1-phenyl [5,6] C61 ({6} -1- (3- (methoxycarbonyl) propyl) Chem. 1995. 60532). PCBM is mixed with representative materials such as MDMO-PPV (poly (2-methoxy-5- (3 ', 7'-dimethyl-octyloxy))-p-phenylene vinylene) and P3HT (poly (3-hexylthiophene)). It is introduced into solar cells, and the energy conversion efficiency varies depending on the mixing ratio, annealing conditions, and the lamination structure, and the organic solar cell is reported to have a maximum efficiency of 6%, but the manufacturing process is complicated, which causes problems in mass production. many.

The aromatic heterocyclic derivative including the nitrogen atom of Chemical Formula 1 prepared by the present invention may be manufactured in a suitable structure so that it may be used as an organic solar cell.

In addition, the derivative of Formula 1 is advantageous to improve various solubility compared with the conventional PCBM series, and has an advantage in reproducibility and productivity.

Therefore, when the compound of Formula 1 of the present invention is used as the photoactive layer of the organic solar cell, the energy conversion efficiency can be further improved, and in the case of a compound having low solubility, the device can be manufactured by vacuum deposition, In the case of an excellent compound, a low cost and high efficiency organic solar cell can be manufactured as a material suitable for a low cost printing process.

The compound according to the present invention may act on a principle similar to that applied to organic solar cells in organic electronic devices including organic light emitting devices, organophotoreceptors, organic transistors, and the like.

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

In another embodiment, the present invention provides an organic transistor including a source, a drain, a gate, and an organic material layer containing at least one heterocyclic derivative represented by the above formula (1).

In another exemplary embodiment, the organic transistor includes a charge generating layer including a heterocyclic derivative represented by Chemical Formula 1.

In another embodiment, the organic transistor may further include the insulating layer. The insulating layer may be positioned on the substrate and the gate.

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

In another embodiment, the first electrode; A second electrode opposed to the first electrode; And at least one organic material layer provided between the first electrode and the second electrode and including an organic photosensitive layer, wherein at least one of the organic material layers includes a heterocyclic derivative represented by Chemical Formula 1. .

In another exemplary embodiment, the organic photoconductor includes a charge generating layer including a heterocyclic derivative represented by Chemical Formula 1.

In another exemplary embodiment, the organic material layer further includes an ultraviolet light stabilizer including a heterocyclic derivative represented by Formula 1.

In another embodiment, the organophotoreceptor may be in the form of, for example, a plate, a flexible belt, a disk, a rigid drum, a sheet around a rigid or flexible drum, and a rigid drum generally used for commercial purposes.

In another embodiment, the organophotoreceptor may comprise an electrically conductive substrate and a photoconductive element, for example, in the form of one or more layers. The organophotoreceptor is poly and may contain both a charge transport compound and a charge generating compound in the binder, which may or may not be in the same layer.

Similarly, the electron transport compound may or may not be the same layer as the charge generating compound. If the electron transport compound is present in a layer other than the charge generating compound, then the electron transport compound may be an overcoat, i.e., on the opposite side of the electrically conductive substrate, or may be in the form of an undercoat, Can be on the side.

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

In another embodiment, the first electrode; A second electrode opposed to the first electrode; And at least one organic material layer provided between the first electrode and the second electrode and including a light emitting layer, wherein at least one of the organic material layers includes a heterocyclic derivative represented by Chemical Formula 1. to be.

In another exemplary embodiment, the organic material layer further includes at least one selected from the group consisting of a hole injection layer, a hole transport layer, a hole blocking layer, an electron blocking layer, a charge generating layer, an electron transport layer, and an electron injection layer.

In another embodiment, when the organic light emitting element includes a plurality of organic layers, the organic layers may be formed of the same material or another material.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. The following examples are intended to be illustrative and not limiting.

[Production Example 1]

Preparation of Compound 1-A-1

[Compound 1-A-1]

The reaction is described in Chemistry of Heterocyclic Compounds. vol. 40. 8. (2004), p. Proceed as described in 1063-1069 to prepare Compound 1-A-1.

(2-Benzimidazolyl) acetonitrile [(2-Benzimidazolyl) acetonitrile] (15.2 g, 96.6 mmol) and 4-bromo-2-fluorobenzaldehyde (19.6 g, 96.6 mmol) and 80 mL of dimethylaldehyde (DMF). Triethylamine (20 mL) was added to the reaction mixture, and the reaction temperature was raised to 100 ° C. and stirred for 12 hours. After the reaction was cooled to room temperature, the solid formed was filtered and washed well with ethanol. Drying in a vacuum oven afforded the desired compound 1-A-1 (23.3 g, yield 75%). MS: [M] ⁺ = 322

The mass spectrum of Compound 1-A-1 is shown in FIG. 2.

[Production Example 2]

Preparation of Compound 1-A-2

[Compound 1-A-2]

The compound 1-A-1 (6.33 g, 19.64 mmol), bis (pinacolato) diboron (5.5 g, 21.8 mmol) and potassium acetate (5.78 g, 58.8 mmol) were suspended in dioxane (160 mL). . Palladium (diphenylphosphinoferrocene) chloride (0.48 g, 3 mol%) was added to the suspension. The mixture was stirred at 80 ° C. for about 8 hours and cooled to room temperature. The mixture was diluted with water (140 mL) and extracted with dichloromethane (100 mL). The organic extract was dried over magnesium sulfate and concentrated in vacuo. The product was washed with ethanol and dried in vacuo to yield the compound 1-A-2 (6.3 g, 87%).

MS: [M + H] ⁺ = 368

[Table 4-1]

[Table 4-2]

Among the intermediates, 1-B-16 and 1-B-17 compounds according to the preparation method of Intermediate 3 of Example 1 shown in Korean Patent No. 10-0765078, the following intermediate 10C-1 (1-B-16 in the present invention) ), And the compounds of Formula 10D and Formula 1-10 may be prepared according to the preparation method.

[10-C] [10D] [Compound 1-B-17]

In addition, Compound 1-B-18 to Compound 1-B-19 of the intermediate may be prepared according to the method of Example 1 shown in Korean Patent No. 0813385 (US Patent No. 7678474).

Scheme 3 below is a general method for preparing the anthracenyl-2-boron ester compounds used in the present invention. This method was prepared according to the method of Compound 120 of Preparation Example 20 of WO 03/095445 (Domestic Publication 2003-0087522 '(2003.11.14)). It is also a general method for preparing other anthracene boron ester compounds and other aryl compounds with aryl boron ester compounds.

Scheme 3 [Compound 1-B-1]

2-bromo-9,10-dinaphthylanthracene (10.0 g, 19.6 mmol), bis (pinacolato) diboron (5.5 g, 21.8 mmol) and potassium acetate (5.78 g, 58.8 mmol) were converted to dioxane ( 120 mL). Palladium (diphenylphosphinoferrocene) chloride (0.48 g, 3 mol%) was added to the suspension. The mixture was stirred at 80 ° C. for about 6 hours and cooled to room temperature. The mixture was diluted with water (100 mL) and extracted with dichloromethane (3 x 100 mL). The organic extract was dried over magnesium sulfate and concentrated in vacuo. The crude product was washed with ethanol and dried in vacuo to give 9,10-dinaphthylanthracenyl-2-borate compound 1-B-1 (10.92 g, 92%).

MS: [M + H] ⁺ = 557

Preparation of Compound 1-a-8

[Compound 1-A-1] [1-B-1] [Compound 1-a-8]

Dissolve Compound 1-A-1 (3.22 g, 10.0 mmol) and Compound 1-B-1 (5.56 g, 10.0 mmol) in tetrahydrofuran (100 mL), then add 2M aqueous potassium carbonate solution (100 mL). Tetrakistriphenylphosphinopalladium (231 mg, 2 mol%) was added thereto, followed by stirring under reflux for 5 hours. The temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was recrystallized with chloroform and ethanol, filtered and dried to give compound 1-a-8 (4.57 g, 68%). MS: [M + H] < ⁺ > = 672

Preparation of Compound 1-a-10

[Compound 1-A-1] [Compound 1-B-2] [Compound 1-a-10]

Except for using Compound 1-B-2 (4.56 g, 10.0 mmol) in place of Compound 1-B-1 in Example 1, the compound was prepared in the same manner as in Example 1 and the compound 1-a-10 (3.26 g, 57%) was prepared. MS: [M + H] < ⁺ > = 572

Preparation of Compound 1-a-14

[Compound 1-A-1] [Compound 1-B-3] [Compound 1-a-14]

Except for using Compound 1-B-3 (4.48 g, 10.0 mmol) in place of Compound 1-B-1 in Example 1, the compound 1-a-14 (3.73) was prepared in the same manner as in Example 1 g, 65%) was prepared. MS: [M + H] < ⁺ > = 648

Preparation of Compound 1-a-9

[Compound 1-A-1] [Compound 1-B-4] [Compound 1-a-9]

Except for using Compound 1-B-4 (5.40 g, 10.0 mmol) instead of Compound 1-B-1 in Example 1, the compound 1-a-9 (4.66) was prepared in the same manner as in Example 1 g, 71%) was prepared. MS: [M + H] ⁺ = 656

Preparation of Compound 1-a-22

[Compound 1-A-1] [Compound 1-B-5] [Compound 1-a-22]

Except for using Compound 1-B-5 (7.9 g, 10.0 mmol) in place of Compound 1-B-1 in Example 1, the compound was prepared in the same manner as in Example 1 Compound 1-a-22 (5.29 g, 54%) was prepared. MS: [M + H] ⁺ = 812

Preparation of Compound 1-c-1

[Compound 1-A-2] [Compound 1-B-10] [Compound 1-a-20]

Example 1 was prepared in the same manner as in Example 1, except that Compound 1-A-2 instead of Compound 1-A-1, Compound 1-B-10 instead of Compound 1-B-1 was used Compound 1-c-1 (3.94 g, 82%) was prepared. MS: [M + H] ⁺ = 481

Preparation of Compound 1-a-23

[Compound 1-A-1] [Compound 1-B-38] [Compound 1-a-23]

Compound 1-a-23 (6.13 g, 82%) was prepared by the same method as Example 1 except that Compound 1-B-4 was used instead of Compound 1-B-1 in Example 1 It was. MS: [M + H] < ⁺ > = 748

Preparation of Compound 1-a-24

[Compound 1-A-1] [Compound 1-B-6] [Compound 1-a-24]

Compound 1-a-24 (5.19 g, 59%) was prepared by the same method as Example 1 except for using the compound 1-B-6 instead of the compound 1-B-1 in Example 1 It was. MS: [M + H] ⁺ = 880

Preparation of Compound 1-c-2

[Compound 1-A-2] [Compound 1-B-11] [Compound 1-c-2]

Example 1 was prepared in the same manner as in Example 1, except that Compound 1-A-2 instead of Compound 1-A-1, Compound 1-B-11 instead of Compound 1-B-1 was used Compound 1-c-2 (3.54 g, 67%) was prepared. MS: [M + H] ⁺ = 529

Preparation of Compound 1-c-5

[Compound 1-A-2] [Compound 1-B-14] [Compound 1-c-5]

Example 1 was prepared in the same manner as in Example 1, except that Compound 1-A-2 instead of Compound 1-A-1, Compound 1-B-14 instead of Compound 1-B-1 was used Compound 1-c-5 (3.54 g, 67%) was prepared. MS: [M + H] ⁺ = 529

Preparation of Compound 1-c-6

[Compound 1-A-2] [Compound 1-B-15] [Compound 1-c-6]

Example 1 was prepared in the same manner as in Example 1, except that Compound 1-A-2 instead of Compound 1-A-1, Compound 1-B-9 instead of Compound 1-B-1 was used Compound 1-C-2 (3.54 g, 67%) was prepared. MS: [M + H] < ⁺ > = 707

Preparation of Compound 1-c-7

[Compound 1-A-2] [Compound 1-B-27] [Compound 1-c-7]

In Example 1 except that Compound 1-A-2 instead of Compound 1-A-1, Compound 1-B-27 instead of Compound 1-B-1 was prepared in the same manner as in Example 1 Compound 1-c-7 (3.54 g, 67%) was prepared. MS: [M + H] ⁺ = 570

Preparation of Compound 1-c-8

[Compound 1-A-2] [Compound 1-B-12] [Compound 1-c-8]

Example 1 was prepared in the same manner as in Example 1, except that Compound 1-A-2 instead of Compound 1-A-1, Compound 1-B-12 instead of Compound 1-B-1 was used Compound 1-c-8 (3.54 g, 67%) was prepared. MS: [M + H] ⁺ = 529

Preparation of Compound 1-c-9

The intermediate was proceeded according to the preparation method of Example 1 3 of the Republic of Korea Patent Registration 10-0765078 to obtain a compound 10C-2 intermediate.

[Compound 1-B-16] [Compound 10C-2]

[Compound 1-A-2] [Compound 10C-2] [Compound 1-c-9]

Compound 1 was prepared in the same manner as in Example 1, except that Compound 1-A-2 instead of Compound 1-A-1 and Compound 10C-2 instead of Compound 1-B-1 were used in Example 1 -c-9 (3.54 g, 67%) was prepared. MS: [M + H] ⁺ = 529

Preparation of Compound 1-c-10

[Compound 1-A-2] [Compound 1-B-17] [Compound 1-c-10]

Example 1 was prepared in the same manner as in Example 1, except that Compound 1-A-2 instead of Compound 1-A-1, Compound 1-B-17 instead of Compound 1-B-1 was used Compound 1-c-10 (2.1 g, 77%) was prepared. MS: [M + H] ⁺ = 814

Preparation of Compound 1-c-11

The following intermediate obtained Intermediate Compound 1-B-19, which was obtained by referring to the experimental example of Korean Patent No. 10-0813385.

                      [Compound 1-B-19]

[Compound 1-B-20]

[Compound 1-A-2] [Compound 1-B-20] [Compound 1-c-11]

Example 1 was prepared in the same manner as in Example 1, except that Compound 1-A-2 instead of Compound 1-A-1, Compound 1-B-20 instead of Compound 1-B-1 was used Compound 1-c-11 (3.54 g, 67%) was prepared. MS: [M + H] ⁺ = 612

Preparation of Compound 1-c-12

[Compound 1-B-19] [Compound 1-B-21]

[Compound 1-A-2] [Compound 1-B-21] [Compound 1-c-12]

Example 1 was prepared in the same manner as in Example 1, except that Compound 1-A-2 instead of Compound 1-A-1, Compound 1-B-21 instead of Compound 1-B-1 was used Compound 1-c-12 (3.54 g, 67%) was prepared. MS: [M + H] ⁺ = 712

Preparation of Compound 1-b-9

[Compound 1-A-2] [Compound 1-b-9]

In Example 1 Compound 1-A-2 instead of Compound 1-A-1, Compound 2,7-dibromo-9,9-dimethylfluorene (2,7-dibromo- instead of Compound 1-B-1 9,9-dimethylfluorene) was prepared in the same manner as in Example 1, except that Compound 1-b-9 was prepared. MS: [M + H] ⁺ = 677

Preparation of Compound 1-b-25

[Compound 1-A-2] [1-b-25]

Compound 1-A-2 instead of compound 1-A-1 in Example 1, and compound 2,7-dibromo-9,9-dioctylfluorene (2,7-dibromo instead of compound 1-B-1 -9,9-dioctylfluorene) was prepared in the same manner as in Example 1 except that Compound 1-b-25 was prepared. MS: [M + H] ⁺ = 873

Preparation of Compound 1-a-48

[Compound 1-A-2] [Compound 1-B-31] [Compound 1-B-33] [Compound 1-B-34]

[Compound 1-B-1] [Compound 1-B-34] [Compound 1-a-48]

Compound 1-A-2 instead of compound 1-A-1 and Compound 1-B-31 instead of Compound 1-B-1 were prepared in the same manner as in Example 1, except that Compound 1-A-1 was used in Example 1 1-B-33 was prepared.

Compound 1-B-34 was prepared by mixing trifluoroacetic anhydride and 2M potassium carbonate (K ₂ CO ₃ ) in compound 1-B-33, followed by heating in an acetonitrile solvent. .

Compound 1-B-1 instead of compound 1-A-1 and Compound 1-B-1 instead of Compound 1-B-1 in Example 1 were prepared in the same manner as in Example 1 except that Compound 1-B-1 was used. 1-a-48 was prepared. MS: [M + H] ⁺ = 1060

Preparation of Compound 1-a-49

[Compound 1-B-1] [Compound 1-B-35] [Compound 1-B-36] [Compound 1-B-37]

[Compound 1-A-2] [Compound 1-B-37] [Compound 1-a-49]

Compound 1-B-1 instead of compound 1-A-1 and Compound 1-B-1 instead of Compound 1-B-1 in Example 1 were prepared in the same manner as in Example 1 except that Compound 1-B-1 was used. 1-B-36 was prepared.

Compound 1-B-36 was mixed with trifluoroacetic anhydride and 2 M potassium carbonate to heat and react in an acetonitrile solvent to prepare compound 1-B-37.

Compound 1-A-2 instead of compound 1-A-1 and Compound 1-B-137 instead of Compound 1-B-1 in Example 1 were prepared in the same manner as in Example 1, except that the compound was prepared. 1-a-49 was prepared. MS: [M + H] ⁺ = 1042

Preparation of Compound 1-a-50

Compound 1-a-50 was prepared by the same method as Example 21, except that Compound 1-B-32 was used instead of Compound 1-B-35 in Example 21. MS: [M + H] ⁺ = 1060

Preparation of Compound 1-b-27

Compound 1-b-27 was prepared in the same manner as in Example 21 except that Compound 1-B-32 was used instead of Compound 1-B-35 in Example 21. MS: [M + H] ⁺ = 1060

Experimental Example 1-1-1 Electrochemical Properties of the Chemical Formula 1 Compounds

In order to observe the electrochemical properties of the compounds prepared in Examples 1 to 5, 9 and 19 to 22, the oxidation / reduction properties using a cyclovoltameter (CV) were observed. CV equipment was used Autolab PGSTAT128N cyclovoltametry, 0.1M tetrabutylammonium tetrafluoroborate (Bu ₄ NBF ₄ (Tetrabutylammonium tetrafluoroborate)) and acetonitrile (Acetonitrile) solvent was used as an electrolyte, the sample was 10 ^-3 M It was dissolved in 1,2-dichlorobenzene at the concentration. Measured at a scanning speed of 100 mV / s under Ar at room temperature, a glass carbon electrode (0.3 mm in diameter) was used as a working electrode, Pt and Ag / AgCl electrode as a counter electrode and a reference electrode the results are shown in the following table 5 is shown.

Table 5 Electrochemistry of the Compounds

* The HOMO and LUMO are calculated by calculating the energy level of ferrocene (Ferrocene) to -4.5 eV.

In general, the open-circuit voltage (Voc) of an organic solar cell is known to be caused by the difference between the HOMO energy level of the donor material and the LUMO energy level of the donor material (CJ Brabec et al., Adv. Func. 374).

Experimental Example 1-1-2 An organic solar cell using P3HT and compound 1-a-8 as a photoactive layer

After spin-coating PEDOT-PSS (Heraeus, CLEVIOS P) about 40 nm on an indium tin oxide (ITO) glass substrate (surface resistance 7 Ω / sq), poly (3-hexylthiophene) [Poly-3- (hexylthiophene), P3HT, Rieke Metal Co., Ltd.] and the compound 1-a-8 prepared in the present invention are spin-coated by dissolving 1,2-dichlorobenzene, chlorobenzene, chloroform alone or a mixed solvent thereof in a weight ratio of 1: 0.6. An organic thin film having a thickness of 80 nm was formed by the method described above. LiF / Al was deposited on the thus formed organic film under the vacuum of 0.7 nm and 120 nm, respectively, and sealed with a glass cap with a moisture absorbent.

The encapsulated device was annealed at 150 ° C. for 10 minutes and then measured IV characteristics under a light source of AM 1.5G 100 mW / cm ² using a-bet b class artificial solar simulator.

As a result, the electrochemical characteristics of the organic solar cell are shown in Table 6 below.

<Experimental Example 1-1-3> Organic solar cell using 1-a-8 as the photoactive layer

A glass substrate coated with indium tin oxide (ITO) coated with a thickness of about 1000 mm 3 (Corning 7059 glass) was placed in distilled water in which detergent (Fischer Co., Ltd.) was dissolved, and washed for 30 minutes with ultrasonic waves. Subsequently, the glass substrate was placed in distilled water and the ultrasonic cleaning performed for 5 minutes was repeated twice.

After the distilled water was washed, the glass substrate was ultrasonically cleaned once in this order and dried in isopropyl alcohol, acetone, and methanol solvent. Subsequently, the ITO coated glass substrate was plasma treated for 5 minutes in a plasma cleaner using nitrogen plasma at a pressure of 14 mtorr and a 50 W power condition. The work function of the surface treated ITO anode was about 4.8 eV.

About 200 kW thick HAT was thermally vacuum deposited on the ITO transparent electrode to form an anode having an ITO conductive layer and a HAT n-type organic compound layer. Subsequently, CuPc (Copper Phthalocyanine) (HOMO level = about 5.20 eV) was vacuum deposited to a thickness of about 400 kV to form a p-type electron donor layer.

Compound 1-a-8 prepared in Example 1 was vacuum-deposited to a thickness of about 400 kPa on the electron donor layer to form an electron acceptor layer. Subsequently, an LiF thin film having a thickness of about 5 mW and aluminum having a thickness of about 2500 mW were sequentially vacuum-deposited on the electron acceptor layer to form a cathode, thereby completing an organic solar cell. In the above process, the deposition rate of the organic material was maintained at about 0.4 ~ 0.7 Å / sec, LiF was about 0.3 Å / sec, aluminum was about 2 Å / sec deposition rate, the vacuum degree in the deposition chamber during deposition is 2 × 10 -7 to 5 x 10 ^-8 torr was maintained.

As a result, the electrochemical characteristics of the organic solar cell are shown in Table 6 below.

Experimental Example 1-1-4 An organic solar cell using P3HT and compound 1-a-10 as a photoactive layer

As in Example 1-1-2, except that Compound 1-a-10 was used instead of Compound 1-a-8 as the photoactive layer receiving material. As a result, the electrochemical characteristics of the organic solar cell are shown in Table 6 below.

Experimental Example 1-1-5 An organic solar cell using P3HT and compound 1-b-25 as a photoactive layer

As in Example 1-1-3, except that Compound 1-b-25 was used instead of Compound 1-a-8 as the photoactive layer receiving material. As a result, the electrochemical characteristics of the organic solar cell are shown in Table 6 below.

Experimental Example 1-1-6 Organic Solar Cell Using P3HT and Compound 1-a-48 as Photoactive Layers

 Except for using the compound 1-a-48 instead of compound 1-a-8 as the photoactive layer receiving material as in Example 1-1-2. As a result, the electrochemical characteristics of the organic solar cell are shown in Table 6 below.

Experimental Example 1-1-7 An organic solar cell using P3HT and compound 1-a-49 as photoactive layers

Except for using the compound 1-a-49 instead of compound 1-a-8 as the photoactive layer receiving material as in Example 1-1-2. As a result, the electrochemical characteristics of the organic solar cell are shown in Table 6 below.

TABLE 6

The solar cell manufactured as shown in Table 6 showed a relatively high value of V _oc . This is due to an increase in the difference between HOMO and LUMO of P3HT, the compound of formula (I). On the other hand, the low J _sc value occurs because of poor solubility of the compounds of Formula 1, resulting in poor morphology in solution coating or vacuum deposition.

By introducing a substituent that can improve the electron donor material and morphology of the compounds of the general formula (1) is expected to overcome this problem.

The following is an example of manufacturing an organic solar cell by a deposition process among the compounds having the structure of Formula 1. This was carried out in the same manner as in Example 11 to Example 12 of the Republic of Korea Patent Registration 10-0690348.

Experimental Example 2 Organic Solar Cell Using P3HT and Compound 1-a-8 as Photoactive Layers

A glass substrate coated with indium tin oxide (ITO) having a thickness of about 1000 mm 3 was ultrasonically cleaned once in this order in a detergent solution, distilled water, isopropyl alcohol, acetone, and a methanol solvent, and then ultrasonically cleaned and dried. Subsequently, the ITO coated glass substrate was plasma treated for 5 minutes in a plasma cleaner using nitrogen plasma at a pressure of 14 mtorr and a 50 W power condition. The work function of the surface treated ITO anode was about 4.8 eV. About 200 μs thick HAT (hexanitrile hexaazatriphenylene) was thermally vacuum deposited on the ITO transparent electrode to form an anode having an ITO conductive layer and a HAT n-type organic compound layer. Subsequently, CuPc (Copper Phthalocyanine) (HOMO level = about 5.20 eV) was vacuum deposited to a thickness of about 400 kV to form a p-type electron donor layer.

[LINE]

Compound 1-a-8 was vacuum deposited to a thickness of about 400 kPa on the electron donor layer to form an electron acceptor layer. An organic solar cell was completed by sequentially vacuum depositing a LiF thin film having a thickness of about 5 mW and aluminum having a thickness of about 2500 mW on the electron donor layer to form a cathode. In the above process, the deposition rate of the organic material was maintained at about 0.4 ~ 0.7 Å / sec, LiF was about 0.3 Å / sec, aluminum was maintained at the deposition rate of about 2 Å / sec, the vacuum degree in the deposition chamber during deposition is 2 × 10 ⁻⁷ to 5 × 10 ⁻⁸ torr was maintained. The efficiency of the organic solar cell was calculated by irradiating the organic solar cell with light emitted from a xenon lamp and measuring the IV curve of the solar cell. The efficiency of the organic solar cell can be obtained by dividing the maximum value of the product of the measured voltage and current by the irradiated light energy. The efficiency of about 0.72% was obtained using this solar cell.

Claims (20)

Heterocyclic derivatives containing a nitrogen element represented by the following formula (1) or comprising two or more structures of formula (1):
[Formula 1]

In Formula 1,
Ar ₁ is cyano group (-CN); Ester group (-CO ₂ R); Carbonyl group (-COR); Fluoro groups (-F); Or a chloro group (-Cl), where R is alkyl having 2 to 20 carbon atoms,
X ₁ is N or CR ₁ , X ₂ is N or CR ₂ , X ₃ is N or CR ₃ , X ₄ is N or CR ₄ , X ₁ to X ₄ are not N at the same time,
A ₁ is N or CR ₅ , A ₂ is N or CR ₆ , A ₃ is N or CR ₇ , A ₄ is N or CR ₈ , and at least two of A ₁ to A ₄ are not N,
R ₁ to R ₉ are each independently-(L) p- (Y) q, where p is an integer of 0 to 10, q is an integer of 1 to 10, and two or more adjacent ones of R ₁ to R ₄ Groups can form a monocyclic or polycyclic ring,
L is oxygen; sulfur; Nitrogen substituted or unsubstituted with an alkyl or aryl group; A substituted or unsubstituted arylene group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted triarylamine group; A substituted or unsubstituted triarylphosphine group; A substituted or unsubstituted triarylphosphine oxide group; A substituted or unsubstituted alkenylene group; Substituted or unsubstituted alkynylene group; A substituted or unsubstituted fluorenylene group; Substituted or unsubstituted carbazolylene group; Substituted or unsubstituted benzocarbazolylene group; Cyclic ketone groups of an aromatic or aliphatic ring; Aromatic ring groups; A substituted or unsubstituted aromatic or aliphatic heterocyclic group containing at least one of N, O and S atoms; Or a condensed ring group of said aromatic ring and said heterocycle,
Y is hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; Ester group (-CO ₂ R); Carbonyl group (-COR); Ester group (-CO ₂ R); Imide group; An amide 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; Substituted or unsubstituted alkylthioxy group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; Substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted triarylamine group; A substituted or unsubstituted triarylphosphine group; A substituted or unsubstituted triarylphosphine oxide group; Substituted or unsubstituted aryl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted carbazole group; Substituted or unsubstituted benzocarbazole group; Cyclic ketone groups of an aromatic or aliphatic ring; Imide groups of aromatic or aliphatic rings; Aromatic ring groups; A substituted or unsubstituted aromatic or aliphatic heterocyclic group containing at least one of N, O and S atoms; Or a condensed ring group of the aromatic ring and the heterocycle, wherein R is alkyl having 2 to 20 carbon atoms,
When X ₁ to X ₄ are CR ₁ to CR ₄ at the same time, at least one of R ₁ to R ₄ has a substituent other than hydrogen, or at least two of R ₁ to R ₄ are bonded to each other and substituted monocyclic or multi. To form a cyclic ring. The nitrogen-containing heterocyclic derivative of claim 1, wherein the nitrogen-containing heterocyclic derivative including two or more structures represented by Chemical Formula 1 is represented by the following Chemical Formula 2:
(2)

Ar ₁ , X ₁ , X ₂ , X ₃ , X ₄ , A ₁ , A ₂ , A ₃ , A ₄ and R ₉ in Chemical Formula 2 are as defined in claim 1,
Z represents a divalent or higher linking group and is a direct bond; Alkanes having a divalent or higher linking group; Cycloalkane having a divalent or higher linking group; Substituted or unsubstituted aryl having a divalent or higher linking group; Substituted or unsubstituted fluorene having a divalent or higher linking group; Cyclic ketones of aromatic or aliphatic rings having a divalent or higher linking group; Substituted or unsubstituted heterocycle having a bivalent or higher linking group containing at least one of N, O, S atoms; Groups having a condensed or non-condensed divalent or higher linking group comprising a heterocycle or an aromatic ring; O; S; NR '; PR ',
R 'is hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; Selected from the group consisting of a substituted or unsubstituted aryloxy group,
Substituted or unsubstituted Z is connected to any one of X ₁ to X ₄ ,
n is an integer from 2 to 10. The nitrogen-containing heterocyclic derivative of claim 1, wherein Ar ₁ is a cyano group (-CN). The nitrogen-containing heterocyclic derivative of claim 1, wherein X ₁ is CR ₁ , X ₂ is CR ₂ , X ₃ is CR ₃ , and X ₄ is CR ₄ . The nitrogen-containing heterocyclic derivative according to claim 1, wherein the number of N in A ₁ to A ₄ is 0 to 2. The nitrogen-containing heterocyclic derivative of claim 1, wherein p is an integer of 0 to 3 and q is an integer of 1 to 3. The method according to claim 1, wherein L is a substituted or unsubstituted arylene group; A substituted or unsubstituted arylamine group; Substituted or unsubstituted triarylamine group; Substituted or unsubstituted triaryl phosphine group; Substituted or unsubstituted triaryl phosphine oxide group; A substituted or unsubstituted alkenylene group; Substituted or unsubstituted alkynylene group; A substituted or unsubstituted fluorenylene group; A substituted or unsubstituted carbazolylene group; Substituted or unsubstituted benzocarbazolylene group; Cyclic ketone groups of an aromatic or aliphatic ring; Aromatic ring groups; Substituted or unsubstituted aromatic or aliphatic heterocyclic group containing one or more of N, O, S atoms; Or a nitrogen-containing heterocyclic derivative which is a condensed ring group of the aromatic ring and the heterocycle. The method according to claim 1, wherein Y is a substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; Substituted or unsubstituted triarylamine group; Substituted or unsubstituted triaryl phosphine group; Substituted or unsubstituted triaryl phosphine oxide group; A substituted or unsubstituted aryl group; A substituted or unsubstituted fluorenyl group; Substituted or unsubstituted carbazole group; A substituted or unsubstituted benzocarbazole group; Cyclic ketone groups of an aromatic or aliphatic ring; Imide groups of aromatic or aliphatic rings; Aromatic ring groups; Substituted or unsubstituted aromatic or aliphatic heterocyclic group containing one or more of N, O, S atoms; Or a heterocyclic derivative containing nitrogen that is a condensed ring group of the aromatic ring and the heterocycle. The nitrogen-containing heterocyclic derivative according to claim 2, wherein Z is a group having the following divalent linking group:

R and R 'are hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; It is selected from the group consisting of a substituted or unsubstituted aryloxy group. The nitrogen-containing heterocyclic derivative of claim 2, wherein n is 2. The method according to claim 1, wherein Formula 1 is a nitrogen element-containing heterocyclic derivative is selected from the formula shown in Table 1 below:
[Table 1]

. The method according to claim 1, wherein Formula 1 is a nitrogen element-containing heterocyclic derivative is selected from the formula shown in Table 2 below:
[Table 2]

. The method according to claim 1, wherein Formula 1 is a nitrogen element-containing heterocyclic derivative is selected from the formula shown in Table 3 below:
[Table 3]

. An organic electronic device comprising a first electrode, a second electrode, and at least one organic material layer disposed between the first electrode and the second electrode, wherein at least one of the organic material layers is a heterocyclic derivative containing nitrogen. An organic electronic device comprising. The organic electronic device of claim 14, wherein the organic electronic device is an organic solar cell, an organic light emitting device, an organic photoconductor, or an organic transistor. The method according to claim 15, wherein the organic solar cell,
A first electrode; A second electrode opposed to the first electrode; An organic electronic device comprising an organic active layer disposed between the first electrode and the second electrode, the organic active layer containing a heterocyclic derivative containing the nitrogen element. The organic electronic device of claim 16, wherein the organic solar cell is a bilayer p-n junction type. The organic electronic device of claim 16, wherein the organic solar cell is a bulk heterojunction (BHJ) junction type. The organic electronic device according to claim 16, wherein the nitrogen-containing heterocyclic derivative is an electron acceptor material, and the organic active layer further contains an electron donor material. The organic electronic device according to claim 16, wherein the nitrogen-containing heterocyclic derivative has a LUMO energy level of -3 to -5 eV.

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