KR20200112028A - Heterocyclic compound and organic electronic device comprising the same - Google Patents

Abstract

The present specification relates to a heterocyclic compound, a composition for forming an organic active layer of an organic electronic device including the same, and an organic electronic device. The heterocyclic compound of the present invention is represented by a chemical formula 1.

Description

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

The present specification relates to a heterocyclic compound, a composition for forming an organic active layer of an organic electronic device including the same, and an organic electronic device.

In the present specification, an organic electronic device is an electronic device using an organic semiconductor material, and requires an exchange of holes and/or electrons between an electrode and an organic semiconductor material. Organic electronic devices can be largely divided into two as follows according to the operating principle. First, excitons are formed in the organic material layer by photons introduced into the device from an external light source, and the excitons are separated into electrons and holes, and these electrons and holes are transferred to different electrodes, and used as a current source (voltage source). It is a type of electronic device. The second is an electronic device in which holes and/or electrons are injected into an organic semiconductor material layer that forms an interface with the electrode by applying voltage or current to two or more electrodes, and operates by the injected electrons and holes.

Examples of organic electronic devices include organic solar cells, organic photoelectric devices, organic light-emitting devices, organic photoreceptors (OPC), and organic transistors, all of which are electron/hole injection materials, electron/hole extraction materials, and electrons for driving devices. /Requires a hole transport material or a luminescent material. Hereinafter, an organic solar cell will be mainly described in detail, but in the organic electronic devices, an electron/hole injection material, an electron/hole extraction material, an electron/hole transport material, or a light-emitting material all act on a similar principle.

A solar cell is a cell that changes electrical energy directly from sunlight, and research is being actively conducted because it is a clean alternative energy source to solve the global environmental problems caused by the depletion of fossil energy and its use. Here, the solar cell refers to a cell that generates a current-voltage by using a photovoltaic effect in which electrons and holes are generated by absorbing light energy from sunlight.

A solar cell is a device that can directly convert solar energy into electrical energy by applying a photovoltaic effect. Solar cells can be divided into inorganic solar cells and organic solar cells depending on the material constituting the thin film.

A number of studies are being conducted to increase energy conversion efficiency through changes in various layers and electrodes according to the design of a solar cell.

Two-layer organic photovoltaic cell (C.W.Tang, Appl. Phys. Lett., 48, 183. (1986)) Efficiencies via Network of Internal Donor-Acceptor Heterojunctions (G. Yu, J. Gao, J. C. Hummelen, F. Wudl, A. J. Heeger, Science, 270, 1789. (1995))

An object of the present invention is to provide a heterocyclic compound, a composition for forming an organic active layer of an organic electronic device including the same, and an organic electronic device.

An exemplary embodiment of the present specification provides a heterocyclic compound represented by Formula 1 below.

[Formula 1]

In Formula 1,

R1 to R8 are each hydrogen; Or a substituted or unsubstituted alkyl group,

X1 and X2 are each a substituted or unsubstituted alkyl group,

X3 to X6 are each a substituted or unsubstituted alkyl group; A substituted or unsubstituted alkoxy group; Or a substituted or unsubstituted alkylthio group,

Ar1 and Ar2 are each a substituted or unsubstituted aromatic hydrocarbon ring; Or a substituted or unsubstituted heterocycle,

Y1 and Y2 are each a halogen group; Or a substituted or unsubstituted alkyl group,

o to r are each an integer of 0 to 4,

n and m are each an integer of 0-6.

In addition, an exemplary embodiment of the present specification

It provides a composition for forming an organic active layer of an organic electronic device comprising the heterocyclic compound.

In addition, an exemplary embodiment of the present specification

A first electrode;

A second electrode provided to face the first electrode; And

It is provided between the first electrode and the second electrode, and includes one or more organic material layers including an organic active layer,

The organic active layer provides an organic electronic device comprising the heterocyclic compound.

In the exemplary embodiment of the present specification, since the heterocyclic compound has excellent electron mobility, when it is used in an organic active layer of an organic electronic device, it has an effect of improving the charge balance between holes and electrons. The current (J _sc ) and the charging rate (FF) are improved, and ultimately, a high level of photo-electric conversion efficiency can be obtained.

1 is a diagram showing an organic solar cell according to an exemplary embodiment of the present specification.
2 is a diagram showing the NMR spectrum of Compound A synthesized in Preparation Example.
3 is a diagram showing the NMR spectrum of Compound C synthesized in Preparation Example.
4 and 5 are diagrams showing NMR spectra of each of compounds 2 and 3 synthesized in Preparation Example.
6 is a diagram showing a UV-Vis spectrum of a film state of Comparative Compound 1 used in Comparative Example.
7 to 36 are diagrams showing UV-Vis spectra of each film state of Compounds 1 to 30 synthesized in Preparation Example.

Hereinafter, the present specification will be described in more detail.

An exemplary embodiment of the present specification provides a heterocyclic compound represented by Formula 1 below.

[Formula 1]

In Formula 1,

R1 to R8 are each hydrogen; Or a substituted or unsubstituted alkyl group,

X1 and X2 are each a substituted or unsubstituted alkyl group,

X3 to X6 are each a substituted or unsubstituted alkyl group; A substituted or unsubstituted alkoxy group; Or a substituted or unsubstituted alkylthio group,

Ar1 and Ar2 are each a substituted or unsubstituted aromatic hydrocarbon ring; Or a substituted or unsubstituted heterocycle,

Y1 and Y2 are each a halogen group; Or a substituted or unsubstituted alkyl group,

o to r are each an integer of 0 to 4,

n and m are each an integer of 0-6.

Research on conventional organic electronic devices has focused on finding an electron donor material that exhibits high efficiency when the electron acceptor of the organic active layer is a fullerene compound such as PCBM. However, the organic electronic device including the fullerene compound has an absorption region, an open circuit voltage, and Due to the limitations in performance such as device life, researches on utilizing non-fullerene compounds such as ITIC as electron acceptors are increasing.

The inventors of the present invention improved the solubility of the compound by introducing an alkyl group, an alkoxy group, or an alkylthio group as a side chain to the phenyl group at the orthogonal position as shown in Chemical Formula 1, and among them, the alkyl group, the alkoxy group or the alkylthio group at the para position It was confirmed that the solubility and electron mobility were improved when substituted at the meta position (each position of X3 to X6 in Formula 1) compared to the substitution. In addition, by introducing an alkyl group to the conjugation backbone (X1 and X2 in Formula 1), it was found that there is an effect of improving the solubility. Based on these characteristics, it was confirmed through an experiment that excellent photo-electric conversion efficiency can be obtained when the heterocyclic compound represented by Formula 1 is used as an electron acceptor material for an organic electronic device.

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

In the present specification, when a member is positioned'on' another member, this includes not only a case where a member is in contact with another member, but also a case where another member exists between the two members.

In the present specification, the energy level means the amount of energy. Therefore, even when the energy level is displayed in the negative (-) direction from the vacuum level, the energy level is interpreted to mean the absolute value of the energy value. For example, the HOMO energy level means the distance from the vacuum level to the highest occupied molecular orbital. In addition, the LUMO energy level refers to the distance from the vacuum level to the lowest unoccupied molecular orbital.

In the present specification, the term'substitution' means that the hydrogen atom bonded to the carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited as long as the position at which the hydrogen atom is substituted, that is, the position where the substituent can be substituted, and 2 When substituted for more than one, two or more substituents may be the same as or different from each other.

In the present specification, the term'substituted or unsubstituted' refers to deuterium; Halogen group; Hydroxy group; Alkyl group; Cycloalkyl group; Alkoxy group; Aryloxy group; Alkenyl group; Aryl group; And it means that it is substituted with one or more substituents selected from the group consisting of a heterocyclic group, or is substituted with a substituent to which two or more substituents are connected among the aforementioned substituents, or does not have any substituents.

In the present specification, the number of carbon atoms of the substituent having a branched chain includes the number of carbon atoms of the branched chain. For example, in the'alkyl group having 3 to 20 carbon atoms having one or more methyl groups as branched chains', the '3 to 20' is a numerical value including the number of carbon atoms of the'one or more methyl groups'.

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-butyl, 1-methylbutyl, 1-ethylbutyl, pentyl, n-pentyl, iso Pentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl , 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylhexyl, 4-methylhexyl, 5-methylhexyl, and the like, but are not limited thereto.

In the present specification, the alkylthio group may be linear, branched or cyclic. Although the number of carbon atoms of the alkylthio group is not particularly limited, it is preferably 1 to 20 carbon atoms. Specifically, methylthio, ethylthio, n-propylthio, isopropylthio, i-propylthio, n-butylthio, isobutylthio, tert-butylthio, sec-butylthio, n-pentylthio, neopentylthio , Isopentylthio, n-hexylthio, 3,3-dimethylbutylthio, 2-ethylbutylthio, n-octylthio, n-nonylthio, n-decylthio, benzylthio and p-methylbenzylthio, etc. , But is not limited thereto.

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 it is preferably 1 to 20 carbon atoms. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, Isopentyloxy, n-hexyloxy, (3,3-dimethylbutyl)oxy, (2-ethylbutyl)oxy, (2-hexyldecyl)oxy, n-octyloxy, n-nonyloxy and n-decyloxy Poems, but are not limited thereto.

In the present specification, the aryl group may be monocyclic or polycyclic.

In the present specification, when the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but it is preferably 6 to 30 carbon atoms. Specifically, the monocyclic aryl group includes a phenyl group, a biphenyl group, and a terphenyl group, but is not limited thereto.

In the present specification, when the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. It is preferable that it has 10 to 30 carbon atoms. Specifically, the polycyclic aryl group includes a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, and a fluorenyl group, but is not limited thereto. The fluorenyl group may be substituted, and adjacent substituents may be bonded to each other to form a ring.

In the present specification, the heterocyclic group includes at least one atom or hetero atom other than carbon, and specifically, the hetero atom may include at least one atom selected from the group consisting of O, N, Se, and S. The number of carbon atoms of the heterocyclic group is not particularly limited, but it is preferably 2 to 60 carbon atoms. Examples of heterocyclic groups include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, triazole group, Acridyl group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, isoquinoline group, indole group, carbazole group, benzoxazole group, benzimidazole group, benzothiazole group, benzocarbazole group , Benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, thiazolyl group, isoxazolyl group, oxadiazolyl group, thiadiazolyl group, phenothiazinyl group and dibenzo There are furanyl groups and the like, but are not limited thereto.

The heterocyclic group may be monocyclic or polycyclic, and may be aromatic, aliphatic, or condensed rings of aromatic and aliphatic.

In the present specification, the description of the aforementioned heterocyclic group may be applied except that the heteroaryl group is aromatic.

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

The aromatic hydrocarbon ring and heterocycle positioned at Ar1 and Ar2 are monovalent, and may be, for example, a divalent or higher aryl or a divalent or higher heterocyclic ring.

In the exemplary embodiment of the present specification, Ar1 and Ar2 are monocyclic or polycyclic aromatic hydrocarbon rings.

In the exemplary embodiment of the present specification, Ar1 and Ar2 are a substituted or unsubstituted benzene ring.

In the exemplary embodiment of the present specification, Ar1 and Ar2 are a substituted or unsubstituted naphthalene ring.

In the exemplary embodiment of the present specification, Ar1 and Ar2 are substituted or unsubstituted thiophene.

In the exemplary embodiment of the present specification, Y1 and Y2 are each hydrogen.

In the exemplary embodiment of the present specification, Y1 and Y2 are each a linear alkyl group having 1 to 10 carbon atoms.

In the exemplary embodiment of the present specification, Y1 and Y2 are each a linear alkyl group having 1 to 5 carbon atoms.

In the exemplary embodiment of the present specification, Y1 and Y2 are each a methyl group.

In the exemplary embodiment of the present specification, Y1 and Y2 are each fluorine, chlorine, or bromine. In the case where Y1 and Y2 are halogen groups, the ability to attract electrons is improved and absorption of a wider area becomes possible, thereby exhibiting a high short-circuit current value. Therefore, it may be more preferable than an alkyl group in which the absorption region is shortened and the energy level is increased by the effect of giving electrons.

In the exemplary embodiment of the present specification, n and m are each an integer of 0 to 2.

In the exemplary embodiment of the present specification, n and m are each 1.

In the exemplary embodiment of the present specification, n and m are each 2.

In the exemplary embodiment of the present specification, Chemical Formula 1 is represented by any one of the following 2-1 to 2-4.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

In Formulas 2-1 to 2-4,

R1 to R8, X1 to X6, Y1, Y2 and m to r are the same as defined in Formula 1,

Each of R9 to R16 is hydrogen; Or a substituted or unsubstituted alkyl group.

In an exemplary embodiment of the present specification, R3 to R6 are each hydrogen.

In the exemplary embodiment of the present specification, R7 and R8 are each hydrogen.

In the exemplary embodiment of the present specification, R9 to R16 are each hydrogen.

In the exemplary embodiment of the present specification, R1 to R8 are each hydrogen.

In the exemplary embodiment of the present specification, o, p, q, and r are each an integer of 0 to 4.

In an exemplary embodiment of the present specification, Formula 1 is represented by the following Formula 3.

[Formula 3]

In Chemical Formula 3,

X1 to X6, Ar1, Ar2, Y1, Y2, n and m are the same as defined in Chemical Formula 1.

In the exemplary embodiment of the present specification, X3 to X6 are each a substituted or unsubstituted alkyl group.

In the exemplary embodiment of the present specification, X3 to X6 are each a linear or branched alkyl group having 1 to 20 carbon atoms.

In the exemplary embodiment of the present specification, X3 to X6 are each a linear or branched alkyl group having 3 to 10 carbon atoms.

In the exemplary embodiment of the present specification, X3 to X6 are each a linear alkyl group having 3 to 10 carbon atoms.

In the exemplary embodiment of the present specification, each of X3 to X6 is a hexyl group.

In the exemplary embodiment of the present specification, X3 to X6 are each a substituted or unsubstituted alkoxy group.

In the exemplary embodiment of the present specification, X3 to X6 are each a linear or branched alkoxy group having 1 to 20 carbon atoms.

In the exemplary embodiment of the present specification, X3 to X6 are each a linear or branched alkoxy group having 3 to 10 carbon atoms.

In the exemplary embodiment of the present specification, X3 to X6 are each a linear alkoxy group having 3 to 10 carbon atoms.

In the exemplary embodiment of the present specification, each of X3 to X6 is a hexyloxy group.

In the exemplary embodiment of the present specification, X3 to X6 are each a substituted or unsubstituted alkylthio group.

In the exemplary embodiment of the present specification, X3 to X6 are each a linear or branched alkylthio group having 1 to 20 carbon atoms.

In the exemplary embodiment of the present specification, X3 to X6 are each a linear or branched alkylthio group having 3 to 10 carbon atoms.

In the exemplary embodiment of the present specification, X3 to X6 are each a linear alkylthio group having 3 to 10 carbon atoms.

In the exemplary embodiment of the present specification, X3 to X6 are each a hexylthio group.

In an exemplary embodiment of the present specification, Formula 1 is represented by any one of the following Formulas 3-1 to 3-12.

[Formula 3-1]

[Chemical Formula 3-2]

[Chemical Formula 3-3]

[Formula 3-4]

[Formula 3-5]

[Formula 3-6]

[Formula 3-7]

[Formula 3-8]

[Chemical Formula 3-9]

[Chemical Formula 3-10]

[Chemical Formula 3-11]

[Formula 3-12]

In Formulas 3-1 to 3-12,

X1, X2, Y1, Y2, m and n are the same as defined in Formula 1,

Each of R9 to R16 is hydrogen; Or a substituted or unsubstituted alkyl group,

R103 to R106 are each a substituted or unsubstituted alkyl group.

In the exemplary embodiment of the present specification, X1 and X2 are each a linear or branched alkyl group having 1 to 30 carbon atoms.

In the exemplary embodiment of the present specification, X1 and X2 are each a linear or branched alkyl group having 3 to 20 carbon atoms.

In the exemplary embodiment of the present specification, X1 and X2 are each a linear or branched alkyl group having 3 to 15 carbon atoms.

In the exemplary embodiment of the present specification, X1 and X2 are each a linear alkyl group having 3 to 15 carbon atoms.

In the exemplary embodiment of the present specification, X1 and X2 are each an octyl group.

In the exemplary embodiment of the present specification, R103 to R106 are each a linear or branched alkyl group having 1 to 20 carbon atoms.

In the exemplary embodiment of the present specification, R103 to R106 are each a linear or branched alkyl group having 3 to 10 carbon atoms.

In the exemplary embodiment of the present specification, R103 to R106 are each a linear alkyl group having 3 to 10 carbon atoms.

In the exemplary embodiment of the present specification, R103 to R106 are each a hexyl group.

In the exemplary embodiment of the present specification, Formula 1 is any one selected from the following compounds 4-1 to 4-30.

[Formula 4-1]

[Formula 4-2]

[Chemical Formula 4-3]

[Formula 4-4]

[Formula 4-5]

[Formula 4-6]

[Formula 4-7]

[Formula 4-8]

[Formula 4-9]

[Formula 4-10]

[Formula 4-11]

[Formula 4-12]

[Formula 4-13]

[Formula 4-14]

[Formula 4-15]

[Formula 4-16]

[Formula 4-17]

[Formula 4-18]

[Chemical Formula 4-19]

[Formula 4-20]

[Formula 4-21]

[Formula 4-22]

[Formula 4-23]

[Formula 4-24]

[Formula 4-25]

[Formula 4-26]

[Formula 4-27]

[Formula 4-28]

[Formula 4-29]

[Formula 4-30]

와 같이 표시된 구조를 포함하는 경우, Y1이 5번 위치에 치환된 화합물과 6번 위치에 치환된 화합물이 혼합되어 있음을 의미하며, Y1이 5번 위치에 치환된 화합물과 Y1이 6번 위치에 치환된 화합물의 질량비는 1:9 내지 9:1, 구체적으로 7:3일 수 있다.In Formulas 4-1 to 4-30,

In the case of including the structure indicated as, Y1 means that the compound substituted at the 5th position and the compound substituted at the 6th position are mixed, and the compound where Y1 is substituted at the 5th position and Y1 are at the 6th position. The mass ratio of the substituted compound may be 1:9 to 9:1, specifically 7:3.

In an exemplary embodiment of the present specification, the The heterocyclic compound exhibits an absorption region of 300 nm to 1,000 nm, and preferably has a maximum absorption wavelength at 700 nm to 800 nm.

Accordingly, when applied to an organic electronic device, it exhibits complementary absorption with an absorption region (300 nm to 700 nm) of an electron donor, and thus a high short-circuit current may be exhibited when applied to an organic electronic device.

In the exemplary embodiment of the present specification, the hetero-cyclic compound may absorb light in a visible light wavelength region and absorb light in an infrared region. Accordingly, the absorption wavelength range of the device can exhibit a wide effect.

An exemplary embodiment of the present specification provides a composition for forming an organic active layer of an organic electronic device including the heterocyclic compound.

In the exemplary embodiment of the present specification, the heterocyclic compound is included in an amount of 0.5wt% to 3wt%, preferably 1wt% to 1.5wt% based on 100wt% of the composition.

When the polymer content exceeds 3wt%, it is difficult to form a clean thin film due to a solubility problem.

In an exemplary embodiment of the present specification, the composition may further include an electron donor material to be described later, and the content of the electron donor material is 1wt% to 3wt% based on 100wt% of the composition.

In the exemplary embodiment of the present specification, the composition may further include one or more selected from toluene and xylene as a solvent, but is not limited thereto, and the heterocyclic compound and Except for electron donor substances, the balance is all solvents.

An exemplary embodiment of the present specification is a first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode and including an organic active layer, wherein the organic active layer includes the heterocyclic compound.

In addition, an exemplary embodiment of the present specification includes forming a first electrode on a substrate; Forming one or more organic material layers including an organic active layer on the first electrode; And forming a second electrode on the organic material layer, wherein the organic active layer includes the heterocyclic compound.

In the exemplary embodiment of the present specification, the method of manufacturing the organic electronic device may further include forming an electron transport layer on the first electrode.

In the exemplary embodiment of the present specification, the forming of the organic material layer may be performed by spin-coating, slot die, blade coating, or roll-to-roll coating.

The organic electronic device of the present invention may be manufactured by a conventional method and material for manufacturing an organic electronic device, except that the heterocyclic compound represented by Formula 1 is included in the organic active layer.

In the exemplary embodiment of the present specification, the organic active layer includes an electron donor and an electron acceptor, and the electron acceptor includes the heterocyclic compound.

In the present specification, the organic active layer may be a photoactive layer or a light emitting layer.

In the present specification, the organic electronic device may be an organic solar cell, an organic photoelectric device, an organic light emitting device, an organic photoconductor (OPC), or an organic transistor.

Hereinafter, an organic solar cell is illustrated. In the organic solar cell, the organic active layer is a photoactive layer, and the above-described organic electronic device may refer to a description of an organic solar cell to be described later.

An exemplary embodiment of the present specification is a first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode and including a photoactive layer, wherein the photoactive layer includes the heterocyclic compound.

The organic solar cell may further include a substrate, a hole transport layer, a hole injection layer, an electron injection layer and/or an electron transport layer.

In the exemplary embodiment of the present specification, the organic solar cell may further include an additional organic material layer. The organic solar cell may reduce the number of organic material layers by using organic materials having several functions at the same time.

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

In the exemplary embodiment of the present specification, the electron donor may use a material applied in the art, for example, poly 3-hexyl thiophene (P3HT), PCDTBT (poly[N-9 '-heptadecanyl-2,7-carbazole-alt-5,5-(4'-7'-di-2-thienyl-2',1',3'-benzothiadiazole)]), PCPDTBT(poly[2,6 -(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] ), PFO-DBT(poly[2,7-(9,9-dioctylfluorene)-alt-5,5-(4,7-bis(thiophene-2-yl)benzo-2,1,3-thiadiazole)] ), PTB7(Poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2- [(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl]]), PSiF-DBT(Poly[2,7-(9,9-dioctyl-dibenzosilole)-alt-4,7-bis(thiophen -2-yl)benzo-2,1,3-thiadiazole]), PTB7-Th(Poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b; 4,5-b']dithiophene-2,6-diyl-alt-(4-(2-ethylhexyl)-3-fluorothieno[3,4-b]thiophene-)-2-carboxylate-2-6-diyl) ]) and PBDB-T (poly(benzodithiophene-benzotriazole)) and at least one material selected from the group consisting of.

In the exemplary embodiment of the present specification, the electron donor is a PBDB-T. The mass ratio of the electron donor and the electron acceptor may be 1:2 to 2:1, preferably 1:1.5 to 1.5:1, more preferably 1:1.

In the exemplary embodiment of the present specification, the electron donor and the electron acceptor may constitute a bulk hetero junction (BHJ). Bulk heterojunction means that an electron donor material and an electron acceptor material are mixed with each other in a photoactive layer.

In the exemplary embodiment of the present specification, the electron donor is a p-type organic material layer, and the electron acceptor is an n-type organic material layer.

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

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

In the exemplary embodiment of the present specification, the organic solar cell has a normal structure. In the normal structure, a substrate, a first electrode, a hole transport layer, an organic material layer including a photoactive layer, an electron transport layer, and a second electrode may be sequentially stacked.

In the exemplary embodiment of the present specification, the organic solar cell has an inverted structure. In the inverted structure, a substrate, a first electrode, an electron transport layer, an organic material layer including a photoactive layer, a hole transport layer, and a second electrode may be sequentially stacked.

1 is a diagram showing an organic solar cell according to an exemplary embodiment of the present specification, an electron transport layer 102, a photoactive layer 103 and a hole transport layer 104 and a second electrode 105 on the first electrode 101 The structure stacked in this order, but the structure of the organic solar cell of the present specification is not limited thereto.

According to FIG. 1, in the organic solar cell, when light is incident from the side of the first electrode 101 and/or the second electrode 105 and the photoactive layer 103 absorbs light in the entire wavelength range, excitons are generated inside. I can. The excitons are separated into holes and electrons in the photoactive layer 103, the separated holes move to the anode side, which is one of the first electrode 101 and the second electrode 105, and the separated electrons are separated from the first electrode 101 The second electrode 105 moves to the other of the cathode, so that current can flow through the organic solar cell.

In the exemplary embodiment of the present specification, the organic solar cell has a tandem structure. In this case, the organic solar cell may include two or more photoactive layers.

The organic solar cell according to the exemplary embodiment of the present specification may have one or two or more photoactive layers.

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

In the exemplary embodiment of the present specification, the substrate may be a glass substrate or a transparent plastic substrate having excellent transparency, surface smoothness, ease of handling, and waterproofness, but is not limited thereto, and any substrate commonly used for organic solar cells is limited. It doesn't work. Specifically, there are glass, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polypropylene (PP), polyimide (PI), and triacetyl cellulose (TAC). It is not limited thereto.

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

The method of forming the first electrode is not particularly limited, but for example, sputtering, E-beam, thermal evaporation, spin coating, screen printing, inkjet printing, doctor blade or gravure printing may be used.

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

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

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

The first electrode pretreatment techniques include a) a surface oxidation method using parallel plate type discharge, b) a method of oxidizing the surface through ozone generated using UV ultraviolet rays in a vacuum state, and c) oxygen generated by plasma. There is a method of oxidizing using radicals.

One of the above methods can be selected according to the state of the first electrode or the substrate. However, regardless of which method is used, it is generally preferable to prevent the oxygen from leaving the surface of the first electrode or the substrate and to minimize the residual moisture and organic matter. At this time, it is possible to maximize the practical effect of the pre-treatment.

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

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

The second electrode may be deposited and formed inside a thermal evaporator showing a vacuum degree of 5 × 10 ^-7 torr or less, but is not limited to this method.

The material of the hole transport layer and/or the electron transport layer plays a role of efficiently transferring electrons and holes separated in the photoactive layer to an electrode, and the material is not particularly limited.

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

The electron transport layer material may be bathocuproine (BCP) or electron-extracting metal oxides, and specifically, bathocuproine (BCP); Metal complexes 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 are not limited thereto.

In one embodiment of the present specification, a vacuum deposition method or a solution coating method may be used as a method of forming the photoactive layer, and the solution coating method refers to a photoactive material such as an electron donor and/or an electron acceptor in an organic solvent. After dissolving, it refers to a method of applying the solution by spin coating, dip coating, screen printing, spray coating, doctor blade and brush painting, etc., but is not limited to these methods.

The compound according to an exemplary embodiment of the present specification may be prepared by a manufacturing method described below. In the preparation examples described below, representative examples are described, but if necessary, a substituent may be added or excluded, and the position of the substituent may be changed. In addition, starting materials, reactants, reaction conditions, and the like can be changed based on techniques known in the art.

In addition, examples will be described in detail in order to describe the present specification in detail. However, the embodiments according to the present specification may be modified in various forms, and the scope of the present specification is not construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more completely describe the present specification to those of ordinary skill in the art.

<Production Example: Preparation of compounds 1 to 30>

Preparation Example 1. Preparation of compounds 1 to 10

(1) Preparation of compound A

In a round flask equipped with a condenser, 10 g of compound A-2 (diethyl 2,5-dibromoterephthalate) was added to 0.43 g of Pd ₂ (dba) ₃ and 0.57 g of tri(o-tolyl)phosphine. Together, they were dissolved in 150 mL of toluene and then refluxed. When the temperature reached 100℃, 35.6g (2.5eq) of compound A-1 (tributyl(6-octylthieno[3,2-b]thiophen-2-yl)stannane) was dissolved in 5 mL of toluene and slowly injected for 12 hours. Refluxed. After the reaction was completed, the compound A (diethyl 2,5-bis(6-octylthieno[3,2-b]thiophen-2-yl)terephthalate) was obtained through column chromatography. Fig. 2 shows the NMR spectrum of Compound A.

(2) Preparation of compound B

In a round flask, 8.16g (5.3eq) of 1-bromo-3-hexylbenzene was dissolved in 200mL of THF, and 13.5mL of n-BuLi was slowly added at -78℃ for 1 hour. After stirring at the same temperature, compound A prepared in (1) was dissolved in 50 mL of THF, slowly poured into a stirring round flask, and stirred at room temperature for 12 hours. After extracting the organic layer through chloroform, the solvent was removed, dissolved in 100 mL of octane, 10 mL of acetic acid and 1 mL of sulfuric acid, and refluxed at 65° C. for 4 hours. The reaction was terminated with distilled water, and the compound B was obtained through column chromatography.

(3) Preparation of compound C

In a round flask, 1 g of Compound B prepared in (2) was dissolved in 100 mL of THF, and 0.76 mL of n-BuLi was slowly injected at -78°C. After stirring at the same temperature for 1 hour, 0.5 mL of DMF was slowly injected and stirred for 12 hours. After the reaction was terminated with distilled water, the organic layer was extracted, and the compound C was obtained through column chromatography. Fig. 3 shows the NMR spectrum of Compound C.

(4) Preparation of compound 1

In a round flask equipped with a condenser, compound C 1g prepared in (3) above and 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (2-(3- 0.7 g of oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile) was dissolved in 10 mL of chloroform, and 1 mL of pyridine was injected, followed by refluxing at 60° C. for 12 hours. After filtration through methanol, the compound 1 was obtained through column chromatography.

(5) Preparation of compounds 2 to 10

In (4) above, 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (2-(3-oxo-2,3-dihydro-1H-inden-1) -ylidene)malononitrile) was carried out in the same manner as in (4), except that the materials of Table 1 were used instead of, respectively, to prepare the following compounds 2 to 10. 4 and 5 show NMR spectra of compounds 2 and 3, respectively.

Target compound Material used Compound 2 2-(6-fluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile and 2-(5-fluoro-3-oxo-2,3-dihydro-1H-inden-1- A compound in which ylidene)malononitrile is mixed in a mass ratio of 3:7 Compound 3 (2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile) Compound 4 2-(6-methyl-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile and 2-(5-methyl-3-oxo-2,3-dihydro-1H-inden-1- A compound in which ylidene)malononitrile is mixed in a mass ratio of 3:7 Compound 5 2-(5,6-dimethyl-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile Compound 6 2-(6-bromo-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile and 2-(5-bromo-3-oxo-2,3-dihydro-1H-inden-1- a compound of ylidene)malononitrile in a mass ratio of 3:7 Compound 7 2-(6-chloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile2-(5-chloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene) A compound in which malononitrile and 2-(5-chloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile are mixed in a mass ratio of 3:7 Compound 8 2-(3-oxo-2,3-dihydro-1H-cyclopenta[b]naphthalen-1-ylidene)malononitrile Compound 9 2-(6-oxo-5,6-dihydro-4H-cyclopenta[c]thiophen-4-ylidene)malononitrile Compound 10 2-(6-oxo-5,6-dihydro-4H-cyclopenta[b]thiophen-4-ylidene)malononitrile

[Compound 2]

[Compound 3]

[Compound 4]

[Compound 5]

[Compound 6]

[Compound 7]

[Compound 8]

[Compound 9]

[Compound 10]

Preparation Example 2. Preparation of compounds 11 to 20

(1) Preparation of compound B2

In (2) of Preparation Example 1, 1-bromo-3-(hexyloxy)benzene (1-bromo-3-(hexyloxy) instead of 1-bromo-3-hexylbenzene) ) benzene) was used, and the compound B2 was prepared in the same manner as in Preparation Example 1 (2).

(2) Preparation of compound C2

Compound C2 was prepared in the same manner as in Preparation Example 1 (3), except that Compound B2 was used instead of Compound B in Preparation Example 1 (3).

(3) Preparation of compound 11

Compound 11 was prepared in the same manner as in Preparation Example 1 (4), except that Compound C2 was used instead of Compound C in Preparation Example 1 (4).

(4) Preparation of compounds 12 to 20

In Preparation Example 2 (3), 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (2-(3-oxo-2,3-dihydro-1H) -Inden-1-ylidene)malononitrile), except that the material of Table 2 was used instead of each of the following compounds 12 to 20 was prepared by performing the same procedure as in (3) of Preparation Example 2 above.

Target compound Material used Compound 12 2-(6-fluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile and 2-(5-fluoro-3-oxo-2,3-dihydro-1H-inden-1- A compound in which ylidene)malononitrile is mixed in a mass ratio of 3:7 Compound 13 (2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile) Compound 14 2-(6-methyl-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile and 2-(5-methyl-3-oxo-2,3-dihydro-1H-inden-1- A compound in which ylidene)malononitrile is mixed in a mass ratio of 3:7 Compound 15 2-(5,6-dimethyl-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile Compound 16 2-(6-bromo-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile and 2-(5-bromo-3-oxo-2,3-dihydro-1H-inden-1- a compound of ylidene)malononitrile in a mass ratio of 3:7 Compound 17 2-(6-chloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile2-(5-chloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene) A compound in which malononitrile and 2-(5-chloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile are mixed in a mass ratio of 3:7 Compound 18 2-(3-oxo-2,3-dihydro-1H-cyclopenta[b]naphthalen-1-ylidene)malononitrile Compound 19 2-(6-oxo-5,6-dihydro-4H-cyclopenta[c]thiophen-4-ylidene)malononitrile Compound 20 2-(6-oxo-5,6-dihydro-4H-cyclopenta[b]thiophen-4-ylidene)malononitrile

[Compound 12]

[Compound 13]

[Compound 14]

[Compound 15]

[Compound 16]

[Compound 17]

[Compound 18]

[Compound 19]

[Compound 20]

Preparation Example 3. Preparation of compounds 21 to 30

(1) Preparation of compound B3

Instead of 1-bromo-3-hexylbenzene (1-bromo-4-hexylbenzene) in (2) of Preparation Example 1, 3-bromophenyl (hexyl) sulfane ((3-bromophenyl) (hexyl) sulfane) was used. Compound B3 was prepared in the same manner as in Preparation Example 1 (2) except that it was used.

(2) Preparation of compound C3

Compound C3 was prepared in the same manner as in Preparation Example 1 (3), except that Compound B3 was used instead of Compound B in Preparation Example 1 (3).

(3) Preparation of compound 21

Compound 21 was prepared in the same manner as in Preparation Example 1 (4), except that Compound C3 was used instead of Compound C in Preparation Example 1 (4).

(4) Preparation of compounds 22 to 30

2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (2-(3-oxo-2,3-dihydro-1H) in (3) of Preparation Example 3 -Inden-1-ylidene)malononitrile), except that the material of Table 3 was used instead of each, and compounds 22 to 30 were prepared by performing the same procedure as in Preparation Example 3 (3).

7 to 36 show the UV-Vis spectrum of each of the compounds 1 to 30 in the film state.

Target compound Material used Compound 22 2-(6-fluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile and 2-(5-fluoro-3-oxo-2,3-dihydro-1H-inden-1- A compound in which ylidene)malononitrile is mixed in a mass ratio of 3:7 Compound 23 (2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile) Compound 24 2-(6-methyl-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile and 2-(5-methyl-3-oxo-2,3-dihydro-1H-inden-1- A compound in which ylidene)malononitrile is mixed in a mass ratio of 3:7 Compound 25 2-(5,6-dimethyl-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile Compound 26 2-(6-bromo-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile and 2-(5-bromo-3-oxo-2,3-dihydro-1H-inden-1- a compound of ylidene)malononitrile in a mass ratio of 3:7 Compound 27 2-(6-chloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile2-(5-chloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene) A compound in which malononitrile and 2-(5-chloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile are mixed in a mass ratio of 3:7 Compound 28 2-(3-oxo-2,3-dihydro-1H-cyclopenta[b]naphthalen-1-ylidene)malononitrile Compound 29 2-(6-oxo-5,6-dihydro-4H-cyclopenta[c]thiophen-4-ylidene)malononitrile Compound 30 2-(6-oxo-5,6-dihydro-4H-cyclopenta[b]thiophen-4-ylidene)malononitrile

[Compound 22]

[Compound 23]

[Compound 24]

[Compound 25]

[Compound 26]

[Compound 27]

[Compound 28]

[Compound 29]

[Compound 30]

<Example: Preparation of organic solar cell>

Example 1.

(1) Preparation of complex solution

The following compound poly[(2,6-(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)-benzo[1,2-b:4,5-b']dithiophene) )-Alt-(5,5-(1',3'-di-2-thienyl-5',7'-bis(2-ethylhexyl)benzo[1',2'-c:4',5 '-c']dithiophene-4,8-dione))](poly[(2,6-(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)- benzo[1, 2-b:4,5-b']dithiophene))-alt-(5,5-(1',3'-di-2-thienyl-5',7'- bis(2-ethylhexyl)benzo[1 ',2'-c:4',5'-c']dithiophene-4,8-dione))], PBDB-T) (Mn: 25,000g/mol, Solarmer Co.) as an electron donor material, the preparation Compound 1 synthesized in the example was used as an electron acceptor material and dissolved in chlorobenzene (CB) at a mass ratio of 1:1 to prepare a composite solution having an electron donor + electron acceptor concentration of 2 wt%.

(2) Fabrication of organic solar cells

A glass substrate (11.5Ω/□) coated with ITO 1.5×1.5cm ² bar type was ultrasonically cleaned with distilled water, acetone, and 2-propanol, and the ITO surface was ozone treated for 10 minutes to 1 electrode was formed.

After spin-coating a ZnO nanoparticle solution (N-10, Nanograde Ltd, 2.5wt% in 1-butanol, filtered in 0.45㎛ PTFE) on the first electrode at 4,000rpm for 40 seconds, The electron transport layer was formed by heat treatment at 80° C. for 10 minutes to remove the remaining solvent.

Thereafter, the composite solution prepared in (1) was spin-coated on the electron transport layer at 70° C. at 900 rpm for 25 seconds to form a photoactive layer, and MoO ₃ was applied on the photoactive layer at a rate of 0.2 Å/s and 10 ^A hole transport layer was formed by thermal evaporation to a thickness of 10 nm under vacuum of ^-7 torr.

Thereafter, Ag was deposited in a thickness of 100 nm at a rate of 1 Å/s in the thermal evaporator to form a second electrode, thereby manufacturing an organic solar cell having an inverted structure.

Examples 2 to 30.

When preparing the composite solution in Example 1, the organic solar cells of Examples 2 to 30 were manufactured in the same manner as in Example 1, except that Compounds 2 to 30 were respectively used instead of Compound 1.

Comparative Example 1.

When preparing the composite solution in Example 1, an organic solar cell was manufactured in the same manner as in Example 1, except that the following Comparative Compound 1 was used instead of Compound 1. 6 is a diagram showing a UV-Vis spectrum in a film state for Comparative Compound 1 below.

[Comparative compound 1]

Comparative Example 2.

When preparing the composite solution in Example 1, an organic solar cell was manufactured in the same manner as in Example 1, except that the following Comparative Compound 2 was used instead of Compound 1.

[Comparative compound 2]

The photoelectric conversion characteristics of the organic solar cells prepared in Examples 1 to 30, Comparative Examples 1 and ² were measured under conditions of 100 mW/cm ² (AM 1.5), and the results are shown in Table 4 below.

Spin-speed (rpm) V _oc
(V) J _sc
(mA/cm ² ) FF η
(%) Example 1 900 0.889 16.01 0.69 9.78 Example 2 900 0.896 14.38 0.69 8.87 Example 3 900 0.890 14.43 0.69 8.83 Example 4 900 0.894 13.12 0.64 7.45 Example 5 900 0.843 13.13 0.70 7.78 Example 6 900 0.926 15.83 0.62 9.13 Example 7 900 0.923 15.88 0.63 9.22 Example 8 900 0.825 15.24 0.68 8.49 Example 9 900 0.921 14.99 0.62 8.61 Example 10 900 0.874 16.94 0.64 9.54 Example 11 900 0.865 17.17 0.63 9.41 Example 12 900 0.878 16.99 0.66 9.88 Example 13 900 0.876 17.11 0.66 9.90 Example 14 900 0.869 16.47 0.62 8.87 Example 15 900 0.874 16.34 0.66 9.37 Example 16 900 0.881 15.88 0.64 8.97 Example 17 900 0.878 15.59 0.65 8.91 Example 18 900 0.917 15.54 0.60 8.52 Example 19 900 0.916 15.96 0.60 8.84 Example 20 900 0.923 16.03 0.60 8.90 Example 21 900 0.919 16.18 0.62 9.17 Example 22 900 0.850 17.35 0.67 9.91 Example 23 900 0.849 17.50 0.67 10.01 Example 24 900 0.849 17.52 0.66 9.92 Example 25 900 0.858 17.16 0.66 9.84 Example 26 900 0.858 17.48 0.69 10.41 Example 27 900 0.855 17.38 0.67 10.05 Example 28 900 0.857 14.87 0.70 8.93 Example 29 900 0.855 14.71 0.70 8.87 Example 30 900 0.834 14.62 0.68 8.29 Comparative Example 1 900 0.730 16.10 0.51 6.05 Comparative Example 2 900 0.859 17.583 0.46 6.86

In Table 4, the spin-speed refers to the rotational speed of the equipment when forming the photoactive layer by spin-coating the complex solution on the electron transport layer, V _OC is the open-circuit voltage, J _SC is the short-circuit current, and FF is the charge rate. (Fill factor), η means energy conversion efficiency. The open-circuit voltage and the short-circuit current are the X-axis and Y-axis intercepts in the four quadrants of the voltage-current density curve, respectively, and the higher the two values, the higher the efficiency of the solar cell. Also, the fill factor is a value obtained by dividing the area of a rectangle that can be drawn inside the curve by the product of the short-circuit current and the open-circuit voltage. Energy conversion efficiency (η) can be obtained by dividing the product of the open-circuit voltage (V _oc ), short circuit current (J _sc ), and charging rate (FF) by the intensity of incident light (P _in ), and the higher this value is, the more preferable. .

Looking at the results in Table 4, the organic solar cells of Examples 1 to 30 using compounds 1 to 30 according to an exemplary embodiment of the present specification as an electron acceptor have excellent characteristic values such as open circuit voltage, short circuit current, and charging rate, and , It can be seen that the energy conversion efficiency is 7% or more, preferably 9% or more. This is because the substituents at the X3 to X6 positions were substituted at the meta position of the phenyl group, as well as the alkyl groups at the X1 and X2 positions, thereby raising the LUMO energy level.

On the other hand, in the case of Comparative Example 1 using Comparative Compound 1 in which the position of the alkyl group substituted with the phenyl group is para, and in the case of Comparative Example 2 using Comparative Compound 2 in which hydrogen is present at the X1 and X2 positions, the energy conversion efficiency is as 6% It can be seen that it appears significantly lower than in the examples.

101: first electrode
102: electron transport layer
103: photoactive layer
104: hole transport layer
105: second electrode

Claims (12)

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

In Formula 1,
R1 to R8 are each hydrogen; Or a substituted or unsubstituted alkyl group,
X1 and X2 are each a substituted or unsubstituted alkyl group,
X3 to X6 are each a substituted or unsubstituted alkyl group; A substituted or unsubstituted alkoxy group; Or a substituted or unsubstituted alkylthio group,
Ar1 and Ar2 are each a substituted or unsubstituted aromatic hydrocarbon ring; Or a substituted or unsubstituted heterocycle,
Y1 and Y2 are each a halogen group; Or a substituted or unsubstituted alkyl group,
o to r are each an integer of 0 to 4,
n and m are each an integer of 0-6. The method according to claim 1,
Formula 1 is a heterocyclic compound represented by any one of the following Formulas 2-1 to 2-4:
[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

In Formulas 2-1 to 2-4,
R1 to R8, X1 to X6, Y1, Y2 and m to r are the same as defined in Formula 1,
Each of R9 to R16 is hydrogen; Or a substituted or unsubstituted alkyl group. The method according to claim 1,
The formula 1 is a heterocyclic compound represented by the following formula 3:
[Formula 3]

In Chemical Formula 3,
X1 to X6, Ar1, Ar2, Y1, Y2, n and m are the same as defined in Chemical Formula 1. The method according to claim 1,
Formula 1 is a heterocyclic compound represented by any one of the following Formulas 3-1 to 3-12:
[Formula 3-1]

[Chemical Formula 3-2]

[Chemical Formula 3-3]

[Formula 3-4]

[Formula 3-5]

[Formula 3-6]

[Formula 3-7]

[Formula 3-8]

[Chemical Formula 3-9]

[Chemical Formula 3-10]

[Chemical Formula 3-11]

[Formula 3-12]

In Formulas 3-1 to 3-12,
X1, X2, Y1, Y2, m and n are the same as defined in Formula 1,
Each of R9 to R16 is hydrogen; Or a substituted or unsubstituted alkyl group,
R103 to R106 are each a substituted or unsubstituted alkyl group. The method according to claim 1,
The heterocyclic compound wherein X1 and X2 are a straight or branched alkyl group having 1 to 30 carbon atoms. The method according to claim 1,
Formula 1 is a heterocyclic compound that is any one selected from the following compounds 4-1 to 4-30:
[Formula 4-1]

[Formula 4-2]

[Chemical Formula 4-3]

[Formula 4-4]

[Formula 4-5]

[Formula 4-6]

[Formula 4-7]

[Formula 4-8]

[Formula 4-9]

[Formula 4-10]

[Formula 4-11]

[Formula 4-12]

[Formula 4-13]

[Formula 4-14]

[Formula 4-15]

[Formula 4-16]

[Formula 4-17]

[Formula 4-18]

[Chemical Formula 4-19]

[Formula 4-20]

[Formula 4-21]

[Formula 4-22]

[Formula 4-23]

[Formula 4-24]

[Formula 4-25]

[Formula 4-26]

[Formula 4-27]

[Formula 4-28]

[Formula 4-29]

[Formula 4-30]

A composition for forming an organic active layer of an organic electronic device comprising the heterocyclic compound according to any one of claims 1 to 6. The method of claim 7,
The content of the heterocyclic compound is 0.5wt% to 3wt% based on 100wt% of the composition, the composition for forming an organic active layer of an organic electronic device. A first electrode;
A second electrode provided to face the first electrode; And
It is provided between the first electrode and the second electrode, and includes one or more organic material layers including an organic active layer,
The organic electronic device of the organic active layer comprising the heterocyclic compound according to any one of claims 1 to 6. The method of claim 9,
The organic active layer includes an electron donor and an electron acceptor,
The electron acceptor is an organic electronic device comprising the heterocyclic compound. The method of claim 10,
The mass ratio of the electron donor and the electron acceptor is 1:2 to 2:1 organic electronic device. The method of claim 9,
The organic electronic device is an organic solar cell, an organic photoelectric device, an organic light emitting device, an organic photoreceptor, or an organic transistor.

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