KR101732220B1 - Heterocyclic compound and organic solar cell comprising the same - Google Patents

Abstract

The present invention provides heterocyclic compounds and organic solar cells containing the same.

Description

HETEROCYCLIC COMPOUND AND ORGANIC SOLAR CELL COMPRISING THE SAME [0002]

The present invention relates to heterocyclic compounds and organic solar cells comprising the same.

Organic solar cells are devices that can convert solar energy directly into electric energy by applying photovoltaic effect. Solar cells can be divided into inorganic solar cells and organic solar cells depending on 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 economic efficiency and supply / demand of materials, organic semiconductor solar cells, which are easy to process, have various functions and are inexpensive, are seen as long-term alternative energy sources.

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. One of the causes of loss of charge is that the generated electrons and holes are destroyed by recombination. Various methods have been proposed as methods for transferring generated electrons and holes to electrodes without loss, but most of them require additional processing, which may increase the manufacturing cost.

Thomas S. van der Poll, John A. Love, Thuc-Quyen Nguyen, and Guillermo C. Bazan, Adv. Mater. 24, 2012, 3646-3649 Gregory C. Welch1, Louis A. Perez1,4, Corey V. Hoven1, Yuan Zhang1, Xuan-Dung Dang1, Alexander Sharenko1, Michael F. Toney6, Edward J. Kramer4,5, Thuc-Quyen Nguyen 1,2,3, and Guillermo C. Bazan, J. Mater. Chem. 21, 2011, 12700-12709 Jiaoyan Zhou, Xiangjian Wan, Yongsheng Liu, Guankui Long, Fei Wang, Zhi Li, Yi Zuo, Chenxi Li, and Yongsheng Chen, Chem. Mater. 23, 2011, 4666-4668

It is an object of the present invention to provide a heterocyclic compound and an organic solar cell containing the heterocyclic compound.

The present invention relates to a composition comprising an A unit represented by the following formula (1): And

A heterocyclic compound comprising at least one B unit acting as an electron acceptor.

[Chemical Formula 1]

In formula (1)

R1 to R4 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; Ester group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; And a substituted or unsubstituted heterocyclic group containing at least one of N, O and S atoms.

Also, the present specification discloses a plasma display panel comprising a first electrode; A second electrode facing the first electrode; And at least one organic layer disposed between the first electrode and the second electrode and including a photoactive layer,

Wherein at least one of the organic material layers comprises the above-described heterocyclic compound.

The heterocyclic compound of the present invention can be used as a material for an organic solar cell organic material layer, and an organic solar cell including the heterocyclic compound can exhibit excellent characteristics in terms of increase in open circuit voltage and short circuit current and / or increase in efficiency.

Heterocyclic compounds according to one embodiment of the present disclosure may exhibit excellent properties due to their deep HOMO level, small band gap, and high charge mobility. The polymer according to one embodiment of the present invention can be used alone or in combination with other materials in an organic solar cell, and can improve the efficiency and improve the lifetime characteristics of the device by the thermal stability of the compound.

Fig. 1 shows the mass spectrum of the compound A prepared in Example 1. Fig.
Fig. 2 shows the NMR spectrum of the compound A prepared in Example 1. Fig.
Fig. 3 shows the NMR spectrum of the compound B prepared in Example 2. Fig.
4 shows the mass spectrum of the compound of the formula 1-1-1 produced by Example 3. Fig.
5 shows the NMR spectrum of the compound of formula (1-1-1) prepared in example 3.
6 shows a solution of the compound of the formula 1-1-1 prepared in Example 3 and a UV absorption spectrum on a film.
FIG. 7 shows the cyclic voltammetry of the compound of Formula 1-1-1 prepared in Example 3. FIG.
Fig. 8 shows the mass spectrum of the compound C prepared in Example 4. Fig.
9 shows the mass spectrum of the compound of the formula 1-1-2 prepared in Example 5. Fig.
10 shows the NMR spectrum of the compound of Formula 1-1-2 prepared in Example 5. Fig.
Fig. 11 shows the mass spectrum of the compound D prepared in Example 6. Fig.
Fig. 12 shows the mass spectrum of the formula 1-1-3 prepared in Example 7. Fig.
Fig. 13 shows the mass spectrum of the formula 1-1-4 prepared in Example 8. Fig.
14 is a view showing an organic solar cell according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

As used herein, the term "unit" means a structure contained in a heterocyclic compound, wherein a monomer is bonded to a heterocyclic compound by polymerization.

In one embodiment of the present invention, the heterocyclic compound includes an A unit represented by the formula (1) and at least one B unit serving as an electron acceptor.

When the B unit is 2 or more, the B units are the same or different from each other.

In one embodiment of the present invention, the heterocyclic compound includes a structure represented by the following formula (2) as a terminal.

(2)

In formula (2)

a is an integer of 1 to 5,

X is CRR ', NR, O, SiRR', PR, S, GeRR ', Se or Te,

R, R 'and R5 to R7 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; Aldehyde group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; And a substituted or unsubstituted heterocyclic group containing at least one of N, O and S atoms.

In one embodiment of the present specification, the B unit is a monocyclic or polycyclic substituted or unsubstituted divalent heterocyclic group containing at least one of N, O and S atoms; A monocyclic or polycyclic substituted or unsubstituted divalent aromatic ring group; And a divalent substituted or unsubstituted condensed ring group in which a monocyclic or polycyclic heterocyclic group containing at least one of N, O and S atoms is condensed with a monocyclic or polycyclic aromatic ring, .

In one embodiment of the present invention, the absolute value of the highest occupied molecular orbital (HOMO) energy of B units is greater than the absolute value of HOMO energy of A units.

In this case, the B unit functions as an electron acceptor in the heterocyclic compound, and the A unit represented by the formula (1) can serve as an electron donor. An electron acceptor and an electron donor may be contained in the heterocyclic compound to increase the electron transfer capability. The difference in HOMO values can be adjusted as needed.

In one embodiment of the present specification, the B unit includes one ring.

In another embodiment, the heterocyclic compound includes two or more B units, and the two or more B units are not directly connected to each other. For example, two B units are not directly connected to each other but are connected through A units.

In the present specification, the B unit is a bivalent ring group, and the B unit is composed of one ring.

In the present specification, "one ring" means a structure formed by a ring, and does not include structures such as a biphenyl group in which rings and rings are connected. When the B unit is composed of one ring, the ring may be a monocyclic ring or a polycyclic ring, and may be a ring condensed with a hydrocarbon ring, a heterocyclic group or a hydrocarbon ring and a heterocyclic ring, but is not limited thereto.

When the A unit acts as an electron donor and the B unit contains one ring, the band gap of the heterocyclic compound is lowered and the absorption rate can be excellent.

In one embodiment of the present specification, the B unit includes any one of the following structures.

In the above structure,

NRa, O, SiRaRb, PRa, S, GeRaRb, Se or Te, and X1 to X12 are the same or different from each other,

Y1 to Y21 are the same or different from each other and each independently represents CRc, N, SiRc, P or GeRc,

R10 to R26, Ra, Rb and Rc are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; Ester group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; And a substituted or unsubstituted heterocyclic group containing at least one of N, O and S atoms.

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

는 다른 치환기 또는 헤테로환 화합물 내의 단위와의 연결되는 부위를 의미한다.In the present specification,

Quot; refers to a moiety that is linked to a unit in another substituent or heterocyclic compound.

As used herein, the term " substituted or unsubstituted " A halogen group; An alkyl group; An alkenyl group; An alkoxy group; A cycloalkyl group; Silyl group; An arylalkenyl group; An aryloxy group; An alkyloxy group; An alkylsulfoxy group; Arylsulfoxy group; Boron group; An alkylamine group; An aralkylamine group; An arylamine group; A heteroaryl group; An arylamine group; An aryl group; A nitrile group; A nitro group; Means a group substituted with at least one substituent selected from the group consisting of a hydroxyl group and a heterocyclic group containing at least one of N, O and S atoms, or has no substituent, and the substituent may be further substituted.

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

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

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 50. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec- N-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, n-hexyl, N-octyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl Heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl and the like.

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

In the present specification, the alkoxy group may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20 carbon atoms. Specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, N-hexyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, But is not limited thereto.

In the present specification, the alkenyl group may be straight-chain 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, Butenyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, (Diphenyl-1-yl) vinyl-1-yl, stilbenyl, stilenyl, and the like.

In the present specification, the aryl group may be a monocyclic aryl group or a polycyclic aryl group, and the number of carbon atoms is not limited, but may be 6 to 50. [ When the aryl group is a monocyclic aryl group, it may be a phenyl group, a biphenyl group, a terphenyl group, or the like, but is not limited thereto. When the aryl group is a polycyclic aryl group, it may specifically be a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a klycenyl group, a fluorenyl group, and the like, but is not limited thereto.

An aryl group as used herein may mean an aromatic ring.

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

The fluorenyl group includes a structure of an open fluorenyl group, wherein the open fluorenyl group is a structure in which one ring compound is disconnected in a structure in which two ring organic compounds are connected via one atom.

,

,

및

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

,

,

And

And the like. However, the present invention is not limited thereto.

In the present specification, the silyl group specifically includes a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, But are not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group containing at least one of O, N and S as a heteroatom. The number of carbon atoms 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 pyrimidyl group, A pyridazinyl group, a pyrazinopyrazinyl group, an isoquinoline group, an isoquinolinyl group, an isoquinolinyl group, an isoquinolinyl group, an isoquinolinyl group, an isoquinolyl group, A benzothiazole group, a benzothiazole group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, a phenanthroline group, a thiazolyl group, a thiazolyl group, An isoxazolyl group, an oxadiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but is not limited thereto.

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 having at least two aryl groups may contain 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 arylamine group include phenylamine, naphthylamine, biphenylamine, anthracenylamine, 3-methylphenylamine, 4-methyl-naphthylamine, 2-methyl- But are not limited to, cenylamine, diphenylamine, phenylnaphthylamine, ditolylamine, phenyltolylamine and triphenylamine groups.

In the present specification, the aryl group in the aryloxy group, arylthioxy group, arylsulfoxy group and aralkylamine group is the same as the aforementioned aryl group. Specific examples of the aryloxy group include phenoxy, p-tolyloxy, m-tolyloxy, 3,5-dimethyl-phenoxy, 2,4,6-trimethylphenoxy, Naphthyloxy, 4-methyl-1-naphthyloxy, 5-methyl-2-naphthyloxy, 1-anthryloxy, 2-anthryl Phenanthryloxy, 9-phenanthryloxy and the like. Examples of the arylthioxy group include phenylthio group, 2-methylphenylthio group, 4-tert-butylphenyl And the like. Examples of the aryl sulfoxy group include a benzene sulfoxy group and a p-toluenesulfoxy group, but the present invention is not limited thereto.

In the present specification, the heteroaryl group in the heteroarylamine group can be selected from the examples of the above-mentioned heterocyclic group.

In the present specification, the alkyl group in the alkylthio group and the alkylsulfoxy group is the same as the alkyl group described above. Specific examples of the alkyloxy group include a methylthio group, an ethylthio group, a tert-butylthio group, a hexylthio group and an octylthio group. Examples of the alkylsulfoxy group include a mesyl group, an ethylsulfoxy group, a propylsulfoxy group, But are not limited thereto.

In one embodiment of the present invention, R 1 and R 2 are the same or different from each other, and each independently is a substituted or unsubstituted, linear or branched alkyl group having 1 to 30 carbon atoms. Heterocyclic compounds containing an alkyl group of the above-mentioned carbon number within the above range are suitable in solubility, so that it is easy to manufacture the device. In addition, the morphology can be appropriately controlled by controlling the straight or branched chain of the alkyl group and the carbon number of the alkyl group.

In one embodiment of the present invention, R 1 is a substituted or unsubstituted alkyl group.

In one embodiment, R < 1 > is a linear or branched alkyl group.

In another embodiment, R1 is a 2-ethylhexyl group.

In one embodiment of the present invention, R 2 is a substituted or unsubstituted alkyl group.

In one embodiment, R 2 is a linear or branched alkyl group.

In another embodiment, R 2 is a 2-ethylhexyl group.

이다. In one embodiment of the present disclosure, the B unit is

to be.

이다. In another embodiment, the B unit is

to be.

In one embodiment of the present invention, the heterocyclic compound includes a unit represented by the following formula (3) or (4).

(3)

[Chemical Formula 4]

In formulas (3) and (4)

b is an integer of 1 to 3,

R1 to R4 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; And a substituted or unsubstituted heterocyclic group containing at least one of N, O and S atoms,

NRa, O, SiRaRb, PRa, S, GeRaRb, Se, or Te, wherein each of X5, X5 ', X7 and X7' is the same or different,

Y4 to Y7 and Y4 'to Y7' are the same or different from each other and each independently CRc, N, SiRc, P or GeRc,

R21, R22, R21 ', R22', Ra, Rb and Rc are the same or different from each other and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; Ester group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; And a substituted or unsubstituted heterocyclic group containing at least one of N, O and S atoms.

In one embodiment of the present disclosure, X5 is S.

In another embodiment, Y4 is N.

In another embodiment, Y5 is N.

In one embodiment of the present disclosure, Y6 is CRc.

In another embodiment, Y6 is N.

In one embodiment of the present disclosure, Y7 is CRc.

In one embodiment of the present disclosure, Y7 is N.

In one embodiment of the present disclosure, X5 'is S.

In another embodiment, Y4 'is N.

In another embodiment, Y5 'is N.

In one embodiment of the present disclosure, Y6 'is CRc.

In another embodiment, Y6 'is N.

In one embodiment of the present disclosure, Y7 'is CRc.

In one embodiment of the present disclosure, Y7 'is N.

In one embodiment of the present disclosure, X is S.

In one embodiment of the present disclosure, X7 is S.

In another embodiment, X7 'is S.

In one embodiment of the present invention, the heterocyclic compound is represented by any one of the following formulas (1-1) to (1-4).

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Formulas 1-1 to 1-4,

a and a 'are each an integer of 1 to 5,

b is an integer of 1 to 3,

R1 to R4, R21 to R26, R21 'and R22' are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; Ester group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; And a substituted or unsubstituted heterocyclic group containing at least one of N, O and S atoms,

R5 to R7 and R5 'to R7' are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; Aldehyde group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; And a substituted or unsubstituted heterocyclic group containing at least one of N, O and S atoms.

In one embodiment of the present disclosure, R5 is hydrogen.

In another embodiment, R5 is a substituted or unsubstituted alkyl group.

In another embodiment, R5 is an octyl group.

In one embodiment of the present disclosure, R6 is hydrogen.

In another embodiment, R6 is a substituted or unsubstituted alkyl group.

In another embodiment, R6 is an octyl group.

In one embodiment of the present disclosure, R21 is hydrogen.

In another embodiment, R21 is a substituted or unsubstituted alkyl group.

In one embodiment of the present specification, R21 is an octyl group.

In one embodiment of the present disclosure, R22 is hydrogen.

In another embodiment, R22 is a substituted or unsubstituted alkyl group.

In another embodiment, R22 is an octyl group.

In one embodiment of the present disclosure, R21 'is hydrogen.

In another embodiment, R21 'is a substituted or unsubstituted alkyl group.

In one embodiment of the present specification, R21 'is an octyl group.

In one embodiment of the present disclosure, R22 'is hydrogen.

In another embodiment, R22 'is a substituted or unsubstituted alkyl group.

In another embodiment, R22 'is an octyl group.

In one embodiment of the present specification, R23 is hydrogen.

In another embodiment, R23 is a halogen group.

In another embodiment, R23 is fluorine.

In one embodiment of the present disclosure, R24 is hydrogen.

In another embodiment, R24 is a halogen group.

In another embodiment, R24 is fluorine.

In one embodiment of the present specification, R25 is hydrogen.

In another embodiment, R25 is a halogen group.

In another embodiment, R25 is fluorine.

In one embodiment of the present specification, R 26 is hydrogen.

In another embodiment, R26 is a halogen group.

In another embodiment, R < 26 > is fluorine.

In one embodiment of the present disclosure, b is one.

In another implementation, c is one.

In one embodiment of the present disclosure, d is one.

In one embodiment of the present disclosure, a is 2.

In one embodiment of the present disclosure, a is 3.

In one embodiment of the present specification, when a is 2 or more, the structures in parentheses are the same or different.

In one embodiment of the present disclosure, a 'is 2.

In another embodiment, a 'is 3.

In one embodiment of the present specification, when a 'is 2 or more, the structures in () are the same or different.

In one embodiment of the present specification, R7 is a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted alkenyl group.

In one embodiment, R7 is a substituted or unsubstituted alkyl group.

In another embodiment, R7 is a hexyl group.

In one embodiment of the present specification, R7 is a substituted or unsubstituted alkenyl group.

In one embodiment, R7 is an alkenyl group substituted with a heterocyclic group.

In another embodiment, R7 is an alkenyl group substituted with a substituted or unsubstituted rhodanine group.

In another embodiment, R7 is an alkenyl group substituted with 3-ethylundanine.

In another embodiment, R7 is 3-ethyl-5-methylene-2-thioxothiazolidin-4-one.

In one embodiment of the present invention, the heterocyclic compound is represented by any one of the following formulas 1-1-1 to 1-1-5.

[Formula 1-1-1]

[Formula 1-1-2]

[Formula 1-1-3]

[Formula 1-1-4]

[Formula 1-1-5]

The above heterocyclic compound can be produced based on the following production example.

In the present specification, R1 to R4 are substituted in the cyclopentadithiophene group represented by the formula (1), and the stannyl group is substituted. A B unit substituted with a halogen group may be bonded to a cyclopentadithiophene group substituted with a stilyl group, and then a terminal group may be bonded to prepare a heterocyclic compound according to one embodiment of the present invention.

In the present specification, R1 to R4 are substituted in the cyclopentadithiophene group represented by the formula (1), and the stannyl group is substituted. A heterocyclic compound according to one embodiment of the present specification can be prepared by bonding a B unit substituted with a terminal group and a halogen group to a cyclopentadithiophene group substituted with a stannyl group.

The heterocyclic compounds according to the present disclosure can be prepared by a multistage chemical reaction. After the monomers are prepared through alkylation, Grignard reaction, Suzuki coupling reaction, and Stille coupling reaction, the monomers are reacted through a carbon-carbon coupling reaction such as a steel coupling reaction, Can be prepared. When the substituent to be introduced is a boronic acid or a boronic ester compound, it can be prepared through a Suzuki coupling reaction. When the substituent to be introduced is a tributyltin compound, But it is not limited thereto.

In one embodiment of the present disclosure, the first electrode; A second electrode facing the first electrode; And at least one organic compound layer including a photoactive layer disposed between the first electrode and the second electrode, wherein at least one of the organic compound layers includes the heterocyclic compound.

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

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

In one embodiment of the present invention, the organic material layer includes a hole transport layer, a hole injection layer, or a layer that simultaneously transports holes and holes, and the hole transport layer, the hole injection layer, And the above heterocyclic compound.

In another embodiment, the organic material layer may include an electron injection layer, an electron transport layer, or a layer that simultaneously performs electron injection and electron transport, and the electron injection layer, the electron transport layer, And the above heterocyclic compound.

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

In one embodiment of the present invention, the organic solar cell includes one or more organic layers selected from the group consisting of a hole injecting layer, a hole transporting layer, a hole blocking layer, a charge generating layer, an electron blocking layer, As shown in FIG.

In one embodiment of the present disclosure, the organic solar cell may further include an additional organic layer. The organic solar cell can reduce the number of organic layers by using organic materials having various functions at the same time.

In one embodiment of the present disclosure, the organic solar cell may be arranged in the order of the cathode, the photoactive layer, and the anode, and may be arranged in the order of the anode, the photoactive layer, and the cathode, but is not limited thereto.

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

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

In one embodiment of the present invention, the photoactive layer includes one or two or more selected from the group consisting of an electron donor and a donor, and the electron donor includes the heterocyclic compound.

In one embodiment of the present disclosure, the electron acceptor material may be selected from the group consisting of fullerene, fullerene derivatives, vicoprofoins, semiconducting elements, semiconducting compounds, and combinations thereof. Specifically, there can be a _{PC 61 BM (phenyl C 61 -butyric} acid methyl ester) or _{PC 71 BM (phenyl C 71 -butyric} acid methyl ester).

In one embodiment of the present disclosure, the electron donor and the electron acceptor constitute a bulk heterojunction (BHJ). The electron donor material and the electron acceptor material are mixed in a ratio (w / w) of 1:10 to 10: 1.

In one embodiment of the present invention, the photoactive layer is a bilayer structure including an n-type organic layer and a p-type organic layer, and the p-type organic layer includes the heterocyclic compound.

In this 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 as long as it is a substrate commonly used in organic solar cells. Specific examples include glass or polyethylene terephthalate, polyethylene naphthalate (PEN), polypropylene (PP), polyimide (PI), and triacetyl cellulose (TAC) But is not limited thereto.

The anode electrode may be a transparent material having excellent conductivity, but is not limited thereto. Metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), 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 method of forming the anode electrode is not particularly limited and may be applied to one surface of the substrate or may be coated in a film form using, for example, sputtering, E-beam, thermal evaporation, spin coating, screen printing, inkjet printing, doctor blade or gravure printing . ≪ / RTI >

When the anode electrode is formed on a substrate, it may undergo cleaning, moisture removal and hydrophilic reforming 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 120 ° C for 10 minutes , And the substrate surface is hydrophilically reformed when the substrate is completely cleaned.

Through such surface modification, the junction surface potential can be maintained at a level suitable for the surface potential of the photoactive layer. Further, in the modification, the formation of the polymer thin film on the anode electrode is facilitated, and the quality of the thin film may be improved.

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

One of the above methods can be selected depending on the state of the anode electrode or the substrate. However, whichever method is used, it is preferable to prevent oxygen from escaping from 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 substantial effect of the preprocessing can be maximized.

As a specific example, a method of oxidizing the surface through ozone generated using UV can be used. At this time, the ITO substrate patterned after the ultrasonic cleaning is dried by baking on a hot plate, and then put into a chamber. Then, by the action of a UV lamp, ozone generated by reaction of oxygen gas with UV light The patterned ITO substrate can be cleaned.

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

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

The cathode electrode may be formed by depositing in a thermal evaporator having a degree of vacuum of 5 x 10 < ^-7 > torr or less, but the method is not limited thereto.

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

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

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

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

The production method of the heterocyclic compound and the production of the organic solar cell including the heterocyclic compound 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 thereto.

Example  1. Synthesis of Compound A

[Compound A]

Cyclopenta [2,1-b: 3,4-b '] dithiophene (1.5 g, 8.14 mmol) was dissolved in tetrahydrofuran was dissolved in THF (tetrahydrofuran, 25ml), sodium-tert-butoxide were added to (sodium tert-butoxide, 1.78g, 18.5mmol) and carbon disulfide _{(CS 2) (1.41g, 18.5mmol} ) slowly. After 10 minutes, 2-ethylhexyl bromide (2.90 g, 20.2 mmol) was added thereto and stirred for 24 hours. NH ₄ OH was added to terminate the reaction, 200 ml of water was added, and the mixture was extracted three times with dichloromethane and washed three times with water. Purification by column chromatography gave a red oil. (yield: 72%)

Fig. 1 shows the mass spectrum of the compound A prepared in Example 1. Fig.

Fig. 2 shows the NMR spectrum of the compound A prepared in Example 1. Fig.

Example  2. Synthesis of Compound B

[Compound B]

Compound A (6 g, 12.5 mmol) was dissolved in tetrahydrofuran (200 ml), and the temperature was lowered to -78 ° C. At this temperature, 2.5 M n-BuLi (2.5 M n-Butyllithium in hexane, 13.5 ml, 33.6 mmol) dissolved in hexane was slowly added and stirred for 1 hour. After that, 1M trimethyltinchloride in THF (37.5 ml, 37.5 mmol) dissolved in tetrahydrofuran was added in one portion, the temperature was raised to room temperature, and the mixture was stirred for 12 hours. The solution was poured into ice, extracted three times with diethyl ether, washed three times with water, and the residue was removed with magnesium sulfate (MgSO ₄ ). The remaining solution was removed under reduced pressure to obtain a red liquid. (yield: 95%)

Fig. 3 shows the NMR spectrum of the compound B prepared in Example 2. Fig.

Example  3. Synthesis of Formula 1-1-1

[Formula 1-1-1]

(5'-hexyl- [2,2'-bithiophen] -5-yl) benzo [c] [1,2,5] thiadiazole 5-fluoro-7- (5'-hexyl- [2,2'-bithiophene] -5-yl) benzo [c] [1,2,5] thiadiazole) . (Thomas S. van der Poll, John A. Love, Thuc-Quyen Nguyen, and Guillermo C. Bazan, Adv. Mater. 24, 2012, 3646-3649)

To a Microwave reactor vial were added 18 ml of chlorobenzene, 2.56 g (3.18 mmol) of compound B, 4-bromo-5-fluoro-7- (5'- -Bisthiophen-5-yl) benzo [c] [1,2,5] thiadiazole (4-Bromo-5-fluoro-7- (5'-hexyl- [2,2'-bithiophene ] -5-yl) benzo [c] [1,2,5] thiadiazole, 3.37 g, 6.91 mmol) and tetrakis (triphenylphosophine) palladium (0) And allowed to react for 1 hour at 130 ° C. The mixture was cooled to room temperature and poured into methanol. The solid was filtered and purified by column chromatography and recrystallization to obtain a blue solid. (yield: 32%)

4 shows the mass spectrum of the compound of the formula 1-1-1 produced by Example 3. Fig.

5 shows the NMR spectrum of the compound of formula (1-1-1) prepared in example 3.

6 shows a solution of the compound of the formula 1-1-1 prepared in Example 3 and a UV absorption spectrum on a film.

The film-based UV absorption spectrum of the film in FIG. 6 was obtained by dissolving the compound of formula (1-1-1) in chlorobenzene at a concentration of 1 wt%, dropping the solution on a glass substrate, spin-coating it at 1000 rpm for 60 seconds, spectrometer. The solution-state UV absorption spectrum of FIG. 6 was obtained by dissolving the compound of formula (1-1-1) in toluene at a concentration of 0.01 wt% and analyzing it by using a UV-Vis spectrometer.

FIG. 7 shows the cyclic voltammetry of the compound of Formula 1-1-1 prepared in Example 3. FIG.

The cyclic voltametry of FIG. 7 was performed by using a glassy carbonworking electrode and an Ag / Agcl reference electrode in an electrolyte solution prepared by dissolving Bu ₄ NBF ₄ in acetonitrile at 0.1 M, Pt electrodes were loaded and analyzed by three electrode method. The compound of Formula 1-1-1 was coated on a working electrode by a drop casting method.

Example  4. Compound Of C  synthesis

[Compound C]

In the present specification, 4,7-dibromo-5-fluorobenzo [c] [1,2,5] thiadiazole (4,7-dibromo-5-fluorobenzo [c] ) Were prepared by referring to the prior literature. (Thomas S. van der Poll, John A. Love, Thuc-Quyen Nguyen, and Guillermo C. Bazan, Adv. Mater. 24, 2012, 3646-3649)

To a microwave reactor vial were added 15 ml of chlorobenzene, 2.3 g of compound B (2.86 mmol), 4,7-dibromo-5-fluorobenzo [c] (4,7-dibromo-5-fluorobenzo [c] [1,2,5] thiadiazole, 1.87 g, 6.00 mmol), tetrakis (triphenylphosophine) palladium 0), 0.100 g), and the reaction was carried out at 130 캜 for 1 hour. The mixture was cooled to room temperature and poured into methanol. The solid was filtered and purified by column chromatography and recrystallization to obtain a purple solid. (yield: 46%)

Fig. 8 shows the mass spectrum of the compound C prepared in Example 4. Fig.

Example  5. A compound of the formula 1-1- 2 of  synthesis

[Formula 1-1-2]

A microwave reactor vial was charged with 18 ml of chlorobenzene, 1.49 g (1.58 mmol) of C, 5'-hexyl-2,2'-bithiophene-5-trimethylstyrene (5 '-hexyl-2,2'-bithiophene-5- trimethylstannane, 2.14g, 3.96mmol), Pd (PPh 3) 4 (tetrakis (triphenylphosphine) palladium (0), 54 mg) and the mixture reacted for one hour at 130 ℃ conditions . The mixture was cooled to room temperature and poured into methanol. The solid was filtered and purified by column chromatography and recrystallization to obtain a purple solid. (yield: 28%)

9 shows the mass spectrum of the compound of the formula 1-1-2 prepared in Example 5. Fig.

10 shows the NMR spectrum of the compound of Formula 1-1-2 prepared in Example 5. Fig.

Example  6. Compound Of D  synthesis

[Compound D]

A microwave reactor vial was charged with 5 ml of chlorobenzene, compound B (0.9482 g, 1.18 mmol), 4,7-dibromo [1,2,5] thiadiazole [ -c] pyridine (4,7-dibromo- [1,2,5] thiadiazolo [3,4-c] pyridine, 0.869g, 2.94mmol), Pd (PPh 3) 4 (tetrakis (triphenylphosphine) palladium (0) , 40 mg), and the mixture was reacted at 130 캜 for 1 hour. The mixture was cooled to room temperature and poured into methanol. The solid was filtered and purified by column chromatography and recrystallization to obtain a purple solid. (yield: 38%)

Fig. 11 shows the mass spectrum of the compound D prepared in Example 6. Fig.

Example  7. A compound of the formula 1-1- 3 of  synthesis

[Formula 1-1-3]

A microwave reactor vial was charged with 10 ml of chlorobenzene, compound D (1.31 g, 1.44 mmol), 5'-hexyl-2,2'-bithiophene-5-trimethylstyrene (5 ' Pd (PPh ₃ ) ₄ (tetrakis (triphenylphosphine) palladium (0), 50 mg) was added to the reaction mixture and the reaction was carried out at 130 ° C. for 1 hour . The mixture was cooled to room temperature and poured into methanol. The solid was filtered and purified by column chromatography and recrystallization to obtain a bluish green solid. (yield: 62%)

Fig. 12 shows the mass spectrum of the compound of formula 1-1-3 prepared in Example 7. Fig.

Example  8. Synthesis of Formula 1-1-4

[Formula 1-1-4]

(5-hexylthiophen-2-yl) thiophen-2-yl) - [1,2,5] thiadiazolo [3,4- c] 2-yl) - [l, 2,5] thiadiazolo [3,4-c] pyridine) . (Gregory C. Welch1, Louis A. Perez1,4, Corey V. Hoven1, Yuan Zhang1, Xuan-Dung Dang1, Alexander Sharenko1, Michael F. Toney6, Edward J. Kramer4,5, Thuc-Quyen Nguyen 1,2,3 , and Guillermo C. Bazan, J. Mater. Chem. 21, 2011, 12700-12709)

To a microwave reactor vial were added 15 ml of chlorobenzene, 2 g of compound B (2.49 mmol), 5'-hexyl-2,2'-bithiophene-5-trimethylstyrene (5'- hexyl-2,2'-bithiophene-5- trimethylstannane, 2.89g, 6.22mmol), Pd (PPh 3) 4 (tetrakis (triphenylphosphine) into a palladium (0), 100mg) and the reaction was carried out for one hour at 130 ℃ conditions. The mixture was cooled to room temperature and poured into methanol. The solid was filtered and purified by column chromatography and recrystallization to obtain a bluish green solid. (yield: 60%)

13 shows the mass spectrum of the compound of Formula 1-1-4 prepared in Example 8. Fig.

Example  9. Compound Of E  synthesis

[Compound E]

5-bromo-3,3-dioctyl- [2,2: 5] thiophene-5-carboxaldehyde , 2-terthiophene] -5-carbaldehyde) was prepared by referring to the previous literatures. (Jiaoyan Zhou, Xiangjian Wan, Yongsheng Liu, Guankui Long, Fei Wang, Zhi Li, Yi Zuo, Chenxi Li, and Yongsheng Chen, Chem. 23, 2011, 4666-4668)

A microwave reactor vial was charged with 15 ml of chlorobenzene, compound B (2 g, 2.49 mmol), 5-bromo-3,3-dioctyl- [2,2: thiophene] -5-carbazol aldehyde (5-bromo-3,3-dioctyl- [2,2: 5,2-terthiophene] -5-carbaldehyde, 3.60g, 6.22mmol), Pd (PPh 3) 4 (tetrakis ( triphenylphosphine) palladium (0), 100 mg), and the reaction was carried out at 130 ° C for 1 hour. The mixture was cooled to room temperature and poured into methanol. The solid was filtered and purified by column chromatography and recrystallization to obtain a solid. (yield: 72%)

Example  10. The compound of formula 1-1-5

[Formula 1-1-5]

Compound E (1 g, 0.677 mmol), two drops of piperidine and 3-ethylrhodanine (1.09 g, 6.77 mmol) were added to 20 ml of anhydrous chloroform, Was refluxed in a nitrogen atmosphere. The reaction mixture was extracted three times with dichloromethane, washed three times with water, and the remaining water was removed with magnesium sulfate (MgSO ₄ ), the solvent was removed, and the residue was purified by column chromatography. (yield: 54%)

Preparation and characterization of organic solar cell

Experimental Example  1. Manufacture of organic solar cell -1

The heterocyclic compound of Formula 1-1-1 prepared in Example 3 and PC71BM were dissolved in chlorobenzene (CB) at a ratio of 1: 1 to prepare a composite solution. At this time, the concentration was adjusted to 4.0 wt%, and the organic solar cell had the structure of ITO / PEDOT: PSS / photoactive layer / Al. The glass substrate coated with ITO was ultrasonically cleaned using distilled water, acetone, and 2-propanol, and the ITO surface was ozone-treated for 10 minutes and spin coated with PEDOT: PSS (baytrom P) Min. For the coating of the photoactive layer, the compound-PC71BM complex solution of Formula 1-1-1 was filtered with a 0.45 μm PP syringe filter, then spin-coated, and dried using a thermal evaporator under a vacuum of 3 × 10 ^-8 torr And Al was deposited to a thickness of 200 nm to produce an organic solar cell.

Experimental Example  2. Manufacture of organic solar cell -2

The heterocyclic compound of Formula 1-1-2 prepared in Example 5 and PC71BM were dissolved in chlorobenzene (CB) at a ratio of 1: 1 to prepare a composite solution. At this time, the concentration was adjusted to 4.0 wt%, and the organic solar cell had the structure of ITO / PEDOT: PSS / photoactive layer / Al. The glass substrate coated with ITO was ultrasonically cleaned using distilled water, acetone, and 2-propanol, and the ITO surface was ozone-treated for 10 minutes and spin coated with PEDOT: PSS (baytrom P) Min. For the coating of the photoactive layer, the compound-PC71BM complex solution of formula 1-1-2 was filtered with a 0.45 μm PP syringe filter, and then spin-coated. Using a thermal evaporator under a vacuum of 3 × 10 ^-8 torr And Al was deposited to a thickness of 200 nm to produce an organic solar cell.

Experimental Example  3. Manufacturing of Organic Solar Cells -3

A heterocyclic compound of Formula 1-1-3 and PC71BM prepared in Example 7 were dissolved in chlorobenzene (CB) at a ratio of 1: 1 to prepare a composite solution. At this time, the concentration was adjusted to 4.0 wt%, and the organic solar cell had the structure of ITO / PEDOT: PSS / photoactive layer / Al. The glass substrate coated with ITO was ultrasonically cleaned using distilled water, acetone, and 2-propanol, and the ITO surface was ozone-treated for 10 minutes and spin coated with PEDOT: PSS (baytrom P) Min. For the coating of the photoactive layer, the compound-PC71BM complex solution of Formula 1-1-3 was filtered with a 0.45 μm PP syringe filter, and then spin-coated, and then dried using a thermal evaporator under a vacuum of 3 × 10 ^-8 torr And Al was deposited to a thickness of 200 nm to produce an organic solar cell.

Experimental Example  4. Manufacture of organic solar cell -4

A heterocyclic compound of Formula 1-1-4 prepared in Example 8 and PC71BM were dissolved in chlorobenzene (CB) at a ratio of 1: 1 to prepare a composite solution. At this time, the concentration was adjusted to 4.0 wt%, and the organic solar cell had the structure of ITO / PEDOT: PSS / photoactive layer / Al. The glass substrate coated with ITO was ultrasonically cleaned using distilled water, acetone, and 2-propanol, and the ITO surface was ozone-treated for 10 minutes and spin coated with PEDOT: PSS (baytrom P) Min. For the coating of the photoactive layer, the compound-PC71BM complex solution of Formula 1-1-4 was filtered with a 0.45 μm PP syringe filter, then spin-coated, and then dried using a thermal evaporator under a vacuum of 3 × 10 ^-8 torr And Al was deposited to a thickness of 200 nm to produce an organic solar cell.

Experimental Example  5. Manufacture of organic solar cell -5

The compound of Formula 1-1-5 prepared in Example 10 and PC71BM were dissolved in chlorobenzene (CB) at a ratio of 1: 1 to prepare a composite solution. At this time, the concentration was adjusted to 4.0 wt%, and the organic solar cell had the structure of ITO / PEDOT: PSS / photoactive layer / Al. The glass substrate coated with ITO was ultrasonically cleaned using distilled water, acetone, and 2-propanol, and the ITO surface was ozone-treated for 10 minutes and spin coated with PEDOT: PSS (baytrom P) Min. For the coating of the photoactive layer, the compound-PC71BM complex solution of Formula 1-1-5 was filtered with a 0.45 μm PP syringe filter, followed by spin coating, using a thermal evaporator under a vacuum of 3 × 10 ^-8 torr And Al was deposited to a thickness of 200 nm to produce an organic solar cell.

The photoelectric conversion characteristics of the organic solar cells prepared in Experimental Examples 1 to 5 were measured under the conditions of 100 mW / cm ² (AM 1.5), and the results are shown in Table 1 below.

Active layer VOC (V) JSC (mA / cm 2) FF (%) PCE (%) Experimental Example 1 Formula 1-1-1 / PC71BM = 1: 1 0.85 8.3 60.4 4.26 Experimental Example 2 Formula 1-1-2 / PC71BM = 1: 1 0.84 3.2 48.2 1.30 Experimental Example 3 Formula 1-1-3 / PC71BM = 1: 1 0.80 5.4 50.0 2.16 Experimental Example 4 Formula 1-1-4 / PC71BM = 1: 1 0.79 7.6 61.0 3.66 Experimental Example 5 Formula 1-1-5 / PC71BM = 1: 1 0.69 9.1 52.6 3.30

In Table 1, the total thickness means the thickness of the active layer in the organic solar cell, Voc means open voltage, Jsc means short-circuit current, FF means fill factor, and PCE means energy conversion efficiency. The open-circuit voltage and the short-circuit current are the X-axis and Y-axis intercepts in the fourth quadrant of the voltage-current density curve, respectively. The higher the two values, the higher the efficiency of the solar cell is. The fill factor is the width of the rectangle that can be drawn inside the curve divided by the product of the short-circuit current and the open-circuit voltage. The energy conversion efficiency can be obtained by dividing these three values by the intensity of the irradiated light, and a higher value is preferable.

101: substrate
102: first electrode
103: Hole transport layer
104: photoactive layer
105: second electrode

Claims (17)

An A unit represented by the following formula (1); And
At least one B unit,
The B unit is a monocyclic or polycyclic substituted or unsubstituted divalent heterocyclic group containing at least one of N, O and S atoms; A monocyclic or polycyclic substituted or unsubstituted divalent aromatic ring group; And a divalent substituted or unsubstituted fused ring group in which a monocyclic or polycyclic heterocyclic group containing at least one of N, O, and S atoms is condensed with a monocyclic or polycyclic aromatic ring, and a heterocyclic compound :
[Chemical Formula 1]

In formula (1)
R1 to R4 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; Ester group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; And a substituted or unsubstituted heterocyclic group containing at least one of N, O and S atoms,

Is a moiety connected to a unit in another substituent or a heterocyclic compound. The method according to claim 1,
Wherein the heterocyclic compound comprises a structure represented by the following formula (2) as a terminal:
(2)

In formula (2)
a is an integer of 1 to 5,
X is CRR ', NR, O, SiRR', PR, S, GeRR ', Se or Te,
R, R 'and R5 to R7 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; Aldehyde group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; And a substituted or unsubstituted heterocyclic group containing at least one of N, O and S atoms. delete delete The method according to claim 1,
Wherein the absolute value of the HOMO energy of the B unit is larger than the absolute value of the HOMO energy of the A unit. The method according to claim 1,
Wherein said B unit comprises any one of the following structures:

In the above structure,
NRa, O, SiRaRb, PRa, S, GeRaRb, Se or Te, and X1 to X12 are the same or different from each other,
Y1 to Y21 are the same or different from each other and each independently represents CRc, N, SiRc, P or GeRc,
R10 to R26, Ra, Rb and Rc are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; Ester group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; And a substituted or unsubstituted heterocyclic group containing at least one of N, O and S atoms. The method according to claim 1,
And R < 2 > are the same or different from each other, and each independently is a substituted or unsubstituted linear or branched alkyl group having 3 to 20 carbon atoms. The method according to claim 1,
Wherein the heterocyclic compound comprises a unit represented by the following general formula (3) or (4):
(3)

[Chemical Formula 4]

In formulas (3) and (4)
b is an integer of 1 to 3,
R1 to R4 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; Ester group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; And a substituted or unsubstituted heterocyclic group containing at least one of N, O and S atoms,
NRa, O, SiRaRb, PRa, S, GeRaRb, Se, or Te, wherein each of X5, X5 ', X7 and X7' is the same or different,
Y4 to Y7 and Y4 'to Y7' are the same or different from each other and each independently CRc, N, SiRc, P or GeRc,
R21, R22, R21 ', R22', Ra, Rb and Rc are the same or different from each other and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; Ester group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; And a substituted or unsubstituted heterocyclic group containing at least one of N, O and S atoms. The method of claim 2,
R7 is a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted alkenyl group. The method according to claim 1,
Wherein said heterocyclic compound is represented by any one of the following formulas (1-1) to (1-4):
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Formulas 1-1 to 1-4,
a and a 'are each an integer of 1 to 5,
b is an integer of 1 to 3,
R1 to R4, R21 to R26, R21 'and R22' are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; Ester group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; And a substituted or unsubstituted heterocyclic group containing at least one of N, O and S atoms,
R5 to R7 and R5 'to R7' are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; Aldehyde group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; And a substituted or unsubstituted heterocyclic group containing at least one of N, O and S atoms. A first electrode; A second electrode facing the first electrode; And at least one organic layer disposed between the first electrode and the second electrode and including a photoactive layer,
Wherein at least one of the organic material layers contains the heterocyclic compound according to any one of claims 1, 2, and 5 to 10. The method of claim 11,
Wherein the organic material layer includes a hole transporting layer, a hole injecting layer, or a layer simultaneously transporting holes and injecting holes,
Wherein the hole transporting layer, the hole injecting layer, or the layer simultaneously transporting the holes and the hole injecting layer comprises the heterocyclic compound. The method of claim 11,
Wherein the organic material layer includes an electron injection layer, an electron transport layer, or a layer that simultaneously performs electron injection and electron transport,
Wherein the electron injecting layer, the electron transporting layer, or the layer which simultaneously injects electrons and transports electrons comprises the heterocyclic compound. The method of claim 11,
Wherein the photoactive layer comprises one or more selected from the group consisting of an electron donor and an electron donor,
Wherein the electron donor comprises the heterocyclic compound. 15. The method of claim 14,
Wherein the electron acceptor is selected from the group consisting of fullerene, a fullerene derivative, a heterocyclic compound, a semiconductor element, a semiconducting compound, and a combination thereof. 15. The method of claim 14,
Wherein the electron donor and the electron acceptor constitute bulk heterojunction (BHJ). The method of claim 11,
The photoactive layer is a bilayer structure including an n-type organic layer and a p-type organic layer,
Wherein the p-type organic compound layer comprises the heterocyclic compound.

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