KR102639496B1 - Heterocyclic compound and organic electronic device comprising the same - Google Patents

Abstract

This specification relates to a heterocyclic compound represented by Formula 1, an organic electronic device including the heterocyclic compound in an organic active layer, and a method of manufacturing an organic electronic device using the heterocyclic compound.

Description

Heterocyclic compounds and organic electronic devices containing the same {HETEROCYCLIC COMPOUND AND ORGANIC ELECTRONIC DEVICE COMPRISING THE SAME}

This specification relates to heterocyclic compounds, compositions containing the same for forming an organic active layer of an organic electronic device, and organic electronic devices.

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

Examples of organic electronic devices include organic solar cells, organic photovoltaic devices, organic light-emitting devices, organic photoreceptors (OPCs), and organic transistors, which all use electron/hole injection materials, electron/hole extraction materials, and electrons to drive the devices. /Requires hole transport material or light emitting material. Hereinafter, organic solar cells will be mainly described in detail, but in the organic electronic devices, electron/hole injection materials, electron/hole extraction materials, electron/hole transport materials, or light-emitting materials all operate on similar principles.

Solar cells are batteries that change electrical energy directly from sunlight, and research is actively underway because they are a clean alternative energy source to solve global environmental problems caused by the depletion of fossil energy and its use. Here, a solar cell refers to a battery that absorbs light energy from sunlight and generates current-voltage using the photovoltaic effect, which generates electrons and holes.

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

Much research is being conducted to increase energy conversion efficiency through changes in various layers and electrodes according to the design of solar cells.

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))

The purpose of the present invention is to provide a heterocyclic compound, a composition containing the same for forming an organic active layer of an organic electronic device, and an organic electronic device.

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

[Formula 1]

In Formula 1,

L1 to L4 are the same or different from each other and are each a substituted or unsubstituted arylene group; Or a substituted or unsubstituted divalent heterocyclic group,

L5 and L6 are the same or different from each other and are each a substituted or unsubstituted arylene group,

R1 to R8 are the same or different from each other and are each hydrogen; Substituted or unsubstituted alkyl group; Substituted or unsubstituted alkoxy group; Or a substituted or unsubstituted alkylthio group,

R9 and R10 are the same or different from each other and are each a substituted or unsubstituted alkyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted alkylthio group,

Ar1 and Ar2 are the same or different from each other and are each a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

Y1 and Y2 are the same or different and are each hydrogen; halogen group; Or a substituted or unsubstituted alkyl group,

n and m are the same as or different from each other and are each integers from 0 to 6.

In addition, one embodiment of the present specification is

Provided is a composition for forming an organic active layer of an organic electronic device containing the heterocyclic compound.

In addition, one embodiment of the present specification is

first electrode;

a second electrode provided opposite the first electrode; and

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

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

In one embodiment of the present specification, the heterocyclic compound improves the solubility problem by introducing alkoxy benzene, making it possible to form an organic thin film that is advantageous to the performance of an organic solar cell, and when the heterocyclic compound is used in the organic active layer of an organic electronic device , a high level of photo-electric conversion efficiency can be achieved.

1 is a diagram showing an organic solar cell according to an exemplary embodiment of the present specification.
Figures 2 to 61 show the UV-vis absorption spectra of compounds 1 to 60 in a film state, respectively.

Hereinafter, this specification will be described in more detail.

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

[Formula 1]

In Formula 1,

L1 to L4 are the same or different from each other and are each a substituted or unsubstituted arylene group; Or a substituted or unsubstituted divalent heterocyclic group,

L5 and L6 are the same or different from each other and are each a substituted or unsubstituted arylene group,

R1 to R8 are the same or different from each other and are each hydrogen; Substituted or unsubstituted alkyl group; Substituted or unsubstituted alkoxy group; Or a substituted or unsubstituted alkylthio group,

R9 and R10 are the same or different from each other and are each a substituted or unsubstituted alkyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted alkylthio group,

Ar1 and Ar2 are the same or different from each other and are each a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

Y1 and Y2 are the same or different and are each hydrogen; halogen group; Or a substituted or unsubstituted alkyl group,

n and m are the same or different from each other and are each integers from 0 to 6.

Conventional research on organic electronic devices has focused on finding electron donor materials that produce high efficiency when the electron acceptor of the organic active layer is a fullerene compound such as PCBM. However, organic electronic devices containing fullerene compounds have low absorption area, open-circuit voltage, and Because limitations are being encountered in performance such as device lifespan, research on using non-fullerene compounds such as ITIC as electron acceptors is increasing.

Most non-fullerene compounds are in the form of EWG (electron withdrawing group)-EDG (electron donating group)-EWG (electron withdrawing group). The inventors of the present invention introduced an alkoxy phenyl group into the side chain of EDG, and confirmed that this improved solubility and excellent miscibility with electron donor materials, thereby improving device characteristics of organic solar cells. This is because the phenyl group, which is a side chain introduced into the EDG group, can easily free rotate compared to the thiophene or alkoxy group that has been commonly used, and its electron donating ability is lower than that of thiophene, resulting in low HOMO/high LUMO energy levels. Because it causes it. In addition, by introducing an alkoxy group at the para- or meta- position of the phenyl group, solubility control and energy level control were also possible.

In this specification, when a part 'includes' a certain component, this means that it may further include other components rather than excluding other components unless specifically stated to the contrary.

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

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

In this specification, the term 'substitution' means that a hydrogen atom bonded to a carbon atom of a compound is changed to another substituent, and the position to be substituted is not limited as long as it is the position where the hydrogen atom is substituted, that is, a position where the substituent can be substituted, 2 In the case of more than one substitution, two or more substituents may be the same or different from each other.

In this specification, the term 'substituted or unsubstituted' refers to deuterium; halogen group; hydroxyl group; Alkyl group; Cycloalkyl group; Alkoxy group; Aryloxy group; alkenyl group; Aryl group; and a heterocyclic group, or is substituted with a substituent in which two or more of the above-exemplified substituents are linked, or does not have any substituent.

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

In the present specification, the alkyl group may be straight chain 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, Examples include, but are not limited to, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylhexyl, 4-methylhexyl, and 5-methylhexyl.

In the present specification, the alkylthio group may be straight chain, branched chain, or cyclic chain. The number of carbon atoms of the alkylthio group is not particularly limited, but 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. , but is not limited to this.

In the present specification, the alkoxy group may be straight chain, branched chain, or ring chain. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20 carbon atoms. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, 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. Poetry, etc., but is not limited to this.

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

In this 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, monocyclic aryl groups include phenyl groups, biphenyl groups, and terphenyl groups, but are not limited thereto.

In this specification, when the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. It is preferable to have 10 to 30 carbon atoms. Specifically, polycyclic aryl groups include, but are not limited to, naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, and fluorenyl group. The fluorenyl group may be substituted, and adjacent substituents may combine with each other to form a ring.

In the present specification, the heterocyclic group includes one or more atoms other than carbon and a heteroatom. Specifically, the heteroatom may include one or more atoms 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 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. furanyl groups, etc., but are not limited to these.

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

In the present specification, the description regarding the heterocyclic group described above may be applied, except that the heteroaryl group is aromatic.

In the present specification, an arylene group refers to an aryl group having two bonding positions, that is, a bivalent group. The description of the aryl group described above can be applied, except that each of these is a divalent group.

The aromatic hydrocarbon ring and heterocycle located at Ar1 and Ar2 are excluded from being monovalent groups, and may be, for example, a divalent or higher aryl group or a divalent or higher heterocyclic ring.

In one embodiment of the present specification, L5 and L6 are phenylene groups.

In an exemplary embodiment of the present specification, -OR9 and -OR10 may each be substituted at the meta or para position of the phenylene group. That is, the above Chemical Formula 1 is represented by the following Chemical Formula 1-1 or 1-2.

[Formula 1-1]

[Formula 1-2]

In Formulas 1-1 and 1-2,

R1 to R10, L1 to L4, Ar1, Ar2, Y1, Y2, n and m are the same as defined in Formula 1 above.

In one embodiment of the present specification, Formula 1 is represented by Formula 1-1. When the above formula 1 is expressed as formula 1-2 (when -OR9 and -OR10 are substituted at the para position), the flow of electrons affects the entire molecule, causing HOMO to relatively up-shift and LUMO to down-shift. tends to be On the other hand, if Formula 1 is expressed as Formula 1-1 (-OR9 and -OR10 are substituted at the meta position), this can be improved. In this case, the flow of electrons does not affect the entire molecule, resulting in a relatively high LUMO. It may have an energy level, and accordingly, the open-circuit voltage may appear high.

In an exemplary embodiment of the present specification, L1 to L4 are each a monocyclic or polycyclic arylene group.

In an exemplary embodiment of the present specification, L1 to L4 are each an arylene group having 6 to 10 carbon atoms.

In an exemplary embodiment of the present specification, L1 to L4 are each a phenylene group.

In an exemplary embodiment of the present specification, L1 to L4 are each divalent heterocyclic group containing S or Se.

In an exemplary embodiment of the present specification, L1 to L4 each represent a divalent thiophene group.

In an exemplary embodiment of the present specification, L1 to L4 each represent a divalent selenophene group.

In one embodiment of the present specification, Formula 1 is represented by the following Formula 2-1 or 2-2.

[Formula 2-1]

[Formula 2-2]

In Formulas 2-1 and 2-2,

L5, L6, R1 to R10, Ar1, Ar2, Y1, Y2, n and m are the same as defined in Formula 1 above,

Q1 to Q4 are the same or different from each other and are S or Se, respectively.

In an exemplary embodiment of the present specification, L5 and L6 are each a monocyclic or polycyclic arylene group.

In one embodiment of the present specification, L5 and L6 are arylene groups having 6 to 10 carbon atoms.

In one embodiment of the present specification, L5 and L6 are phenylene groups.

In an exemplary embodiment of the present specification, Formula 1 is represented by the following Formula 3-1 or 3-2.

[Formula 3-1]

[Formula 3-2]

In Formulas 3-1 and 3-2,

R1 to R10, Y1, Y2, Ar1, Ar2, n and m are the same as defined in Formula 1 above, and Q1 to Q4 are the same or different from each other and are S or Se, respectively.

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

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

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

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

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

[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

In Formulas 4-1 to 4-4,

R1 to R10, L1 to L4, Y1, Y2, n and m are the same as defined in Formula 1 above,

R15 to R22 are the same or different from each other and are each hydrogen; Or it is a substituted or unsubstituted alkyl group.

In one embodiment of the present specification, Formula 1 is represented by any one of the following Formulas 5-1 to 5-8.

[Formula 5-1]

[Formula 5-2]

[Formula 5-3]

[Formula 5-4]

[Formula 5-5]

[Formula 5-6]

[Formula 5-7]

[Formula 5-8]

In Formulas 5-1 to 5-8,

R1 to R10, Y1, Y2, n and m are the same as defined in Formula 1 above,

R15 to R22 are the same or different from each other and are each hydrogen; Or a substituted or unsubstituted alkyl group,

Q1 to Q4 are the same or different from each other and are S or Se, respectively.

In an exemplary embodiment of the present specification, Q1 to Q4 are each S.

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

In one embodiment of the present specification, Y1 and Y2 are each a straight-chain alkyl group having 1 to 10 carbon atoms.

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

In an exemplary embodiment of the present specification, Y1 and Y2 are each fluorine, chlorine, or bromine.

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

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

In an exemplary embodiment of the present specification, n and m are each integers from 0 to 4.

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

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

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

In an exemplary embodiment of the present specification, R1 to R4 are each a substituted or unsubstituted alkyl group.

In an exemplary embodiment of the present specification, R1 to R4 are each a straight-chain or branched alkyl group having 1 to 30 carbon atoms.

In one embodiment of the present specification, R1 to R4 are each a straight-chain or branched alkyl group having 1 to 20 carbon atoms.

In an exemplary embodiment of the present specification, R1 to R4 are each a straight-chain or branched alkyl group having 1 to 10 carbon atoms.

In an exemplary embodiment of the present specification, R1 to R4 are each a straight-chain alkyl group having 1 to 10 carbon atoms.

In one embodiment of the present specification, R1 to R4 are each a hexyl group.

In one embodiment of the present specification, R5 to R8 are each hydrogen.

In an exemplary embodiment of the present specification, R9 and R10 are each a straight-chain or branched alkyl group having 1 to 30 carbon atoms.

In an exemplary embodiment of the present specification, R9 and R10 are each a straight-chain or branched alkyl group having 3 to 15 carbon atoms.

In an exemplary embodiment of the present specification, R9 and R10 are each a straight-chain or branched alkyl group having 5 to 10 carbon atoms.

In an exemplary embodiment of the present specification, R9 and R10 are each a branched alkyl group having 5 to 10 carbon atoms.

In an exemplary embodiment of the present specification, R9 and R10 are each ethylhexyl.

In an exemplary embodiment of the present specification, R9 and R10 are each a monocyclic or polycyclic aryl group.

In an exemplary embodiment of the present specification, R9 and R10 are each an aryl group having 6 to 10 carbon atoms.

In an exemplary embodiment of the present specification, R9 and R10 are each a phenyl group.

In an exemplary embodiment of the present specification, R15 to R22 are each hydrogen.

In one embodiment of the present specification, R15 and R17 are each a straight-chain alkyl group having 1 to 10 carbon atoms.

In an exemplary embodiment of the present specification, R15 and R17 are each a methyl group.

In an exemplary embodiment of the present specification, Formula 1 is any one selected from Formulas 6-1 to 6-60 below.

[Formula 6-1]

[Formula 6-2]

[Formula 6-3]

[Formula 6-4]

[Formula 6-5]

[Formula 6-6]

[Formula 6-7]

[Formula 6-8]

[Formula 6-9]

[Formula 6-10]

[Formula 6-11]

[Formula 6-12]

[Formula 6-13]

[Formula 6-14]

[Formula 6-15]

[Formula 6-16]

[Formula 6-17]

[Formula 6-18]

[Formula 6-19]

[Formula 6-20]

[Formula 6-21]

[Formula 6-22]

[Formula 6-23]

[Formula 6-24]

[Formula 6-25]

[Formula 6-26]

[Formula 6-27]

[Formula 6-28]

[Formula 6-29]

[Formula 6-30]

[Formula 6-31]

[Formula 6-32]

[Formula 6-33]

[Formula 6-34]

[Formula 6-35]

[Formula 6-36]

[Formula 6-37]

[Formula 6-38]

[Formula 6-39]

[Formula 6-40]

[Formula 6-41]

[Formula 6-42]

[Formula 6-43]

[Formula 6-44]

[Formula 6-45]

[Formula 6-46]

[Formula 6-47]

[Formula 6-48]

[Formula 6-49]

[Formula 6-50]

[Formula 6-51]

[Formula 6-52]

[Formula 6-53]

[Formula 6-54]

[Formula 6-55]

[Formula 6-56]

[Formula 6-57]

[Formula 6-58]

[Formula 6-59]

[Formula 6-60]

In Formulas 6-1 to 6-60, If it contains a structure shown as, it means that a compound with Y1 substituted at position 5 and a compound with Y1 substituted at position 6 are mixed, and a compound with Y1 substituted at position 5 and a compound with Y1 substituted at position 6 The mass ratio of the substituted compound may be 1:9 to 9:1, specifically 7:3.

In one embodiment of the present specification, the heterocyclic compound exhibits an absorption region of 300 nm to 900 nm, and preferably has a maximum absorption wavelength of 700 nm to 900 nm.

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

In one embodiment of the present specification, the heterocyclic compound is capable of absorbing light in the visible light full-wave range and can also absorb light in the infrared range. Accordingly, the effect of having a wide absorption wavelength range of the device can be achieved.

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

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

When the polymer content exceeds 3 wt%, there is a disadvantage in that it is difficult to form a clean thin film due to solubility problems.

In one 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 1 wt% to 3 wt% based on 100 wt% of the composition.

In an exemplary embodiment of the present specification, the composition may further include, but is not limited to, one or more solvents selected from toluene and xylene, and the heterocyclic compound and Everything remaining except the electron donor material is the solvent.

An exemplary embodiment of the present specification includes a first electrode; a second electrode provided opposite 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.

Additionally, an exemplary embodiment of the present specification includes forming a first electrode on a substrate; forming one or more organic 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 one 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 one embodiment of the present specification, the step of forming the organic material layer is performed by spin-coating, slot die, blade coating, or roll-to-roll coating, and the spin-coating speed is 700 rpm to 1,300 rpm. You can.

When the spin-coating speed is within the above range, the thickness of the organic active layer can be formed to be about 100 nm, thereby improving the performance of the organic electronic device.

The organic electronic device of the present invention can be manufactured by conventional organic electronic device manufacturing methods and materials, except that the heterocyclic compound represented by Formula 1 is included in the organic active layer.

In one 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 this 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 photoreceptor (OPC), or an organic transistor.

Below, organic solar cells will be exemplified. In the organic solar cell, the organic active layer is a photoactive layer, and the above-mentioned organic electronic device can be referred to the description of the organic solar cell described later.

An exemplary embodiment of the present specification includes a first electrode; a second electrode provided opposite 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 one embodiment of the present specification, the organic solar cell may further include an additional organic material layer. The organic solar cell can reduce the number of organic material layers by using organic materials that have multiple functions simultaneously.

In one 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 one embodiment of the present specification, the electron donor may use a material applied in the art, for example, poly 3-hexyl thiophene (P3HT), poly[N-9 (PCDTBT) '-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)).

In one embodiment of the present specification, the electron donor is 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, and more preferably 1:1.

In one embodiment of the present specification, the electron donor and electron acceptor may form a bulk heterojunction (BHJ). Bulk heterojunction means that electron donor materials and electron acceptor materials are mixed together in the photoactive layer.

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

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

In one 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 stacked in that order.

In one 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 stacked in that order.

1 is a diagram showing an organic solar cell according to an exemplary embodiment of the present specification. According to FIG. 1, when light is incident from the first electrode 100 and/or the second electrode 300 and the photoactive layer 200 absorbs light in the entire wavelength range, an exciton is generated inside the organic solar cell. You can. Exciton is separated into holes and electrons in the photoactive layer 200, the separated holes move to the anode side, which is one of the first electrode 100 and the second electrode 300, and the separated electrons move to the first electrode 100 and the anode. It moves to the cathode side, which is the other one of the second electrodes 300, so that current can flow through the organic solar cell.

In one 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 an exemplary embodiment of the present specification may have one or two or more layers of photoactive layers.

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

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

The material of the first electrode may be a transparent and highly conductive material, but is not limited thereto. For example, 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 to these. .

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 can be used.

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

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

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

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

One of the above methods can be selected depending on the state of the first electrode or substrate. However, whichever method is used, it is generally desirable to prevent oxygen escape from the surface of the first electrode or substrate and to suppress the remaining moisture and organic matter as much as possible. At this time, the practical effect of pre-processing can be maximized.

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

However, the method for modifying the surface of the patterned ITO substrate in this specification does not need to be particularly limited, and any method may be used as long as it oxidizes the substrate.

The second electrode may be a metal with a low 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 multi-layered material such as LiF/Al, LiO ₂ /Al, LiF/Fe, Al:Li, Al:BaF ₂ , Al:BaF ₂ :Ba, but is not limited thereto.

The second electrode may be formed by depositing inside a thermal evaporator with a vacuum of 5 × 10 ^-7 torr or less, but the method is not limited to this method.

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

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

The electron transport layer material may be BCP (bathocuproine) or electron-extracting metal oxides, and specifically, BCP (bathocuproine), a metal complex of 8-hydroxyquinoline; Complex containing Alq ₃ ; Metal complexes containing Liq; LIF; Ca; Titanium oxide (TiO _x ); zinc oxide (ZnO); and cesium carbonate (Cs ₂ CO ₃ ), but is not limited to these.

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

A compound according to an exemplary embodiment of the present specification may be produced by a production method described later. Representative examples are described in the production examples described below, but as needed, substituents can be added or excluded, and the positions of the substituents can be changed. Additionally, starting materials, reactants, reaction conditions, etc. can be changed based on techniques known in the art.

In addition, in order to explain the present specification in detail, examples will be given in detail. However, the embodiments according to the present specification may be modified into various other forms, and the scope of the present specification is not to be construed as being limited to the embodiments described in detail below. The embodiments of this specification are provided to more completely explain the present specification to those with average knowledge in the art.

<Preparation example: Synthesis of compounds 1 to 60>

Preparation Example 1. Preparation of compounds 1 to 10

(1) Preparation of Compound A

(4,8-bis(4-((2-ethylhexyl)oxy)phenyl)benzo[1,2-b:4,5-b']dithiophene-2,6-diyl)bis in a round flask equipped with a condenser. (trimethylstannane) 10g was dissolved in 150mL of toluene along with 0.43g of Pd ₂ (dba) ₃ and 0.57g of tri(o-tolyl)phosphine and then refluxed. When the temperature reached 100°C, 5.15 g (2.5 eq) of ethyl 2-bromothiophene-3-carboxylate was dissolved in 5 mL of toluene, slowly injected, and refluxed for 12 hours. After the reaction was completed, the compound A (diethyl 2,2'-(4,8-bis(4-((2-ethylhexyl)oxy)phenyl)benzo[1,2-b:4) was obtained through column chromatography. ,5-b']dithiophene-2,6-diyl)bis(thiophene-3-carboxylate)) was obtained.

(2) Preparation of Compound B

Dissolve 8.16g (5.3eq) of 1-bromo-4-hexylbenzene in 200mL of THF in a round flask, then slowly inject 13.5mL of n-BuLi at -78°C for 1 hour. It was stirred at the same temperature. Compound A prepared in (1) was dissolved in 50 mL of THF, then slowly injected into a stirring round flask and stirred at room temperature for 12 hours. After extracting the organic layer with 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) above was dissolved in 100 mL of THF, and then 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 Compound C was obtained through column chromatography.

(4) Preparation of Compound 1

In a round flask equipped with a condenser, 1 g of compound C 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, 1 mL of pyridine was added, and the mixture was refluxed at 60°C for 12 hours. Compound 1 was obtained through column chromatography after filtration through methanol.

(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 The following compounds 2 to 10 were prepared by following the same process as (4), except that the materials in Table 1 below were used instead of -ylidene) malononitrile).

target compound materials 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- ylidene) A compound mixed with malononitrile 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- ylidene) A compound mixed with malononitrile 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 in which ylidene)malononitrile is mixed at 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 containing malononitrile and 2-(5-chloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile mixed at 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, except that 1-bromo-3-hexylbenzene was used instead of 1-bromo-4-hexylbenzene. Then, the compound B2 was prepared in the same process as (2) of Preparation Example 1.

(2) Preparation of compound C2

Compound C2 was prepared through the same process as 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 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 (3) of Preparation Example 2, 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (2-(3-oxo-2,3-dihydro-1H The following compounds 12 to 20 were prepared by following the same process as (3) of Preparation Example 2, except that the materials in Table 2 below were used instead of -inden-1-ylidene)malononitrile).

target compound materials 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- ylidene) A compound mixed with malononitrile 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- ylidene) A compound mixed with malononitrile 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 in which ylidene)malononitrile is mixed at 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 containing malononitrile and 2-(5-chloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile mixed at 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

(2) of Preparation Example 1, except that 2-hexylthiophene was used instead of 1-bromo-4-hexylbenzene in (2) of Preparation Example 1. ) Compound B3 was prepared in the same manner as above.

(2) Preparation of compound C3

Compound C3 was prepared in the same manner as 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 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

In (3) of Preparation Example 3, 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (2-(3-oxo-2,3-dihydro-1H The following compounds 22 to 30 were prepared by following the same process as (3) in Preparation Example 3, except that the materials in Table 3 below were used instead of -inden-1-ylidene)malononitrile).

target compound materials 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- ylidene) A compound mixed with malononitrile 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- ylidene) A compound mixed with malononitrile 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 in which ylidene)malononitrile is mixed at 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 containing malononitrile and 2-(5-chloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile mixed at 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]

Preparation Example 4. Preparation of compounds 31 to 40

(1) Preparation of Compound D

In (1) of Preparation Example 1, (4,8-bis(4-((2-ethylhexyl)oxy)phenyl)benzo[1,2-b:4,5-b']dithiophene-2,6-diyl ) instead of bis(trimethylstannane) (4,8-bis(3-((2-ethylhexyl)oxy)phenyl)benzo[1,2-b:4,5-b']dithiophene-2,6-diyl)bis( Compound D was prepared in the same manner as in Preparation Example 1 (1), except that trimethylstannane) was used.

(2) Preparation of Compound E

Compound E was prepared in the same manner as Preparation Example 1 (2), except that Compound D synthesized in Preparation Example 4 (1) was used instead of Compound A used in Preparation Example 1 (2). .

(3) Preparation of Compound F

Compound F was prepared in the same manner as Preparation Example 1 (3), except that Compound E synthesized in Preparation Example 4 (2) was used instead of Compound B used in Preparation Example 1 (3). .

(4) Preparation of compound 31

Compound 31 was prepared in the same manner as Preparation Example 1 (4), except that Compound F synthesized in Preparation Example 4 (3) was used instead of Compound C used in Preparation Example 1 (4). .

(5) Preparation of compounds 32 to 40

In (4) of Preparation Example 4, 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (2-(3-oxo-2,3-dihydro-1H Compounds 32 to 40 below were prepared in the same manner as (4) in Preparation Example 4, except that the materials shown in Table 4 below were used instead of -inden-1-ylidene)malononitrile).

target compound materials used Compound 32 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- ylidene) A compound mixed with malononitrile in a mass ratio of 3:7 Compound 33 (2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile) Compound 34 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- ylidene) A compound mixed with malononitrile in a mass ratio of 3:7 Compound 35 2-(5,6-dimethyl-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile Compound 36 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 in which ylidene)malononitrile is mixed at a mass ratio of 3:7 Compound 37 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 containing malononitrile and 2-(5-chloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile mixed at a mass ratio of 3:7 Compound 38 2-(3-oxo-2,3-dihydro-1H-cyclopenta[b]naphthalen-1-ylidene)malononitrile Compound 39 2-(6-oxo-5,6-dihydro-4H-cyclopenta[c]thiophen-4-ylidene)malononitrile Compound 40 2-(6-oxo-5,6-dihydro-4H-cyclopenta[b]thiophen-4-ylidene)malononitrile

[Compound 32]

[Compound 33]

[Compound 34]

[Compound 35]

[Compound 36]

[Compound 37]

[Compound 38]

[Compound 39]

[Compound 40]

Preparation Example 5. Preparation of compounds 41 to 50

(1) Preparation of compound E2

In (2) of Preparation Example 4, except that 1-bromo-3-hexylbenzene was used instead of 1-bromo-4-hexylbenzene. Then, the compound E2 was prepared in the same process as (2) in Preparation Example 4.

(2) Preparation of compound F2

Compound F2 was prepared in the same manner as (3) in Preparation Example 4, except that Compound E2 was used instead of Compound E in (3) of Preparation Example 4.

(3) Preparation of compound 41

Compound 41 was prepared in the same manner as Preparation Example 4 (4), except that Compound F2 was used instead of Compound F in Preparation Example 4 (4).

(4) Preparation of compounds 42 to 50

In (3) of Preparation Example 5, 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (2-(3-oxo-2,3-dihydro-1H Compounds 42 to 50 below were prepared in the same process as (3) of Preparation Example 5, except that the materials shown in Table 5 below were used instead of -inden-1-ylidene)malononitrile).

target compound materials used Compound 42 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- ylidene) A compound mixed with malononitrile in a mass ratio of 3:7 Compound 43 (2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile) Compound 44 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- ylidene) A compound mixed with malononitrile in a mass ratio of 3:7 Compound 45 2-(5,6-dimethyl-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile Compound 46 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 in which ylidene)malononitrile is mixed at a mass ratio of 3:7 Compound 47 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 containing malononitrile and 2-(5-chloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile mixed at a mass ratio of 3:7 Compound 48 2-(3-oxo-2,3-dihydro-1H-cyclopenta[b]naphthalen-1-ylidene)malononitrile Compound 49 2-(6-oxo-5,6-dihydro-4H-cyclopenta[c]thiophen-4-ylidene)malononitrile Compound 50 2-(6-oxo-5,6-dihydro-4H-cyclopenta[b]thiophen-4-ylidene)malononitrile

[Compound 42]

[Compound 43]

[Compound 44]

[Compound 45]

[Compound 46]

[Compound 47]

[Compound 48]

[Compound 49]

[Compound 50]

Preparation Example 6. Preparation of compounds 51 to 60

(1) Preparation of compound E3

(2) of Preparation Example 4, except that 2-hexylthiophene was used instead of 1-bromo-4-hexylbenzene in (2) of Preparation Example 4. ) Compound E3 was prepared in the same manner as above.

(2) Preparation of compound F3

Compound F3 was prepared in the same manner as (3) in Preparation Example 4, except that Compound E3 was used instead of Compound E in (3) of Preparation Example 4.

(3) Preparation of compound 51

Compound 51 was prepared in the same manner as Preparation Example 4 (4), except that Compound F3 was used instead of Compound F in Preparation Example 4 (4).

(4) Preparation of compounds 52 to 60

In (3) of Preparation Example 6, 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (2-(3-oxo-2,3-dihydro-1H The following compounds 52 to 60 were prepared by following the same process as (3) of Preparation Example 6, except that the materials in Table 6 below were used instead of -inden-1-ylidene)malononitrile).

The UV-Vis spectra of the prepared compounds 1 to 60 in the film state are shown in Figures 2 to 61, respectively.

target compound materials used Compound 52 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- ylidene) A compound mixed with malononitrile in a mass ratio of 3:7 Compound 53 (2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile) Compound 54 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- ylidene) A compound mixed with malononitrile in a mass ratio of 3:7 Compound 55 2-(5,6-dimethyl-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile Compound 56 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 in which ylidene)malononitrile is mixed at a mass ratio of 3:7 Compound 57 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 containing malononitrile and 2-(5-chloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile mixed at a mass ratio of 3:7 Compound 58 2-(3-oxo-2,3-dihydro-1H-cyclopenta[b]naphthalen-1-ylidene)malononitrile Compound 59 2-(6-oxo-5,6-dihydro-4H-cyclopenta[c]thiophen-4-ylidene)malononitrile Compound 60 2-(6-oxo-5,6-dihydro-4H-cyclopenta[b]thiophen-4-ylidene)malononitrile

[Compound 52]

[Compound 53]

[Compound 54]

[Compound 55]

[Compound 56]

[Compound 57]

[Compound 58]

[Compound 59]

[Compound 60]

<Example: Manufacturing of organic solar cell>

Example 1.

(1) Preparation of composite 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']dithiophen-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: 25,000 g/mol, Solarmer) as an electron donor material, prepared above Compound 1 synthesized in the example was dissolved in chlorobenzene (CB) at a mass ratio of 1:1 using the electron acceptor material to prepare a composite solution with an electron donor + electron acceptor concentration of 2 wt%.

(2) Manufacturing of organic solar cells

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

After spin-coating a ZnO nanoparticle solution (N-10, Nanograde Ltd, 2.5wt% in 1-butanol, filtered through 0.45㎛ PTFE) on the first electrode at 4,000rpm for 40 seconds, An 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 speed of 0.2 Å/s and 10 A hole transport layer was formed by thermal deposition to a thickness of 10 nm under ^-7 torr vacuum.

Afterwards, Ag was deposited to a thickness of 100 nm at a speed of 1 Å/s inside a thermal evaporator to form a second electrode, thereby manufacturing an organic solar cell with an inverted structure.

Examples 2 to 60.

Organic solar cells of Examples 2 to 60 were prepared in the same process as Example 1, except that Compounds 2 to 60 were used instead of Compound 1 when preparing the composite solution in Example 1.

Comparative Example 1.

An organic solar cell was prepared in the same manner as in Example 1, except that Comparative Compound 1 below was used instead of Compound 1 when preparing the composite solution in Example 1.

[Comparative Compound 1]

The photoelectric conversion characteristics of the organic solar cells prepared in Examples 1 to 60 and Comparative Example 1 were measured under 100 mW/cm ² (AM 1.5) conditions, and the results are shown in Table 7 below.

Spin-speed (rpm) V _oc
(V) J _sc
(mA/ ^cm2 ) FF η
(%) Example 1 900 0.888 16.67 0.69 10.17 Example 2 900 0.885 16.82 0.69 10.28 Example 3 900 0.901 14.66 0.63 8.35 Example 4 900 0.900 14.42 0.63 8.24 Example 5 900 0.890 14.38 0.67 8.61 Example 6 900 0.889 14.42 0.67 8.56 Example 7 900 0.892 15.93 0.65 9.24 Example 8 900 0.893 15.53 0.67 9.31 Example 9 900 0.894 15.72 0.66 9.31 Example 10 900 0.891 15.72 0.68 9.53 Example 11 900 0.889 15.15 0.69 9.32 Example 12 900 0.888 14.93 0.70 9.24 Example 13 900 0.893 14.43 0.66 8.55 Example 14 900 0.888 13.96 0.69 8.57 Example 15 900 0.866 18.80 0.59 9.57 Example 16 900 0.865 18.83 0.62 10.15 Example 17 900 0.859 16.69 0.59 8.41 Example 18 900 0.861 17.16 0.63 9.30 Example 19 900 0.861 14.52 0.64 8.02 Example 20 900 0.859 14.45 0.65 8.01 Example 21 900 0.861 17.16 0.63 9.30 Example 22 900 0.841 18.98 0.49 7.90 Example 23 900 0.846 19.43 0.57 9.42 Example 24 900 0.843 19.70 0.58 9.61 Example 25 900 0.849 18.88 0.58 9.33 Example 26 900 0.850 19.43 0.58 9.58 Example 27 900 0.851 18.14 0.59 9.09 Example 28 900 0.850 18.15 0.59 9.16 Example 29 900 0.861 14.52 0.64 8.02 Example 30 900 0.859 14.45 0.65 8.01 Example 31 900 0.928 17.91 0.55 9.16 Example 32 900 0.919 18.04 0.59 9.87 Example 33 900 0.916 17.85 0.57 9.39 Example 34 900 0.916 17.86 0.57 9.41 Example 35 900 0.904 15.50 0.63 8.88 Example 36 900 0.918 17.93 0.607 9.99 Example 37 900 0.914 18.43 0.616 10.38 Example 38 900 0.916 16.62 0.566 8.63 Example 39 900 0.926 16.50 0.650 9.94 Example 40 900 0.924 16.37 0.652 9.86 Example 41 900 0.925 17.16 0.629 9.98 Example 42 900 0.904 17.62 0.558 8.90 Example 43 900 0.921 18.31 0.543 9.16 Example 44 900 0.925 15.54 0.656 9.44 Example 45 900 0.923 14.96 0.663 9.16 Example 46 900 0.924 17.20 0.639 10.16 Example 47 900 0.925 17.16 0.629 9.98 Example 48 900 0.924 17.20 0.639 10.16 Example 49 900 0.926 16.50 0.650 9.94 Example 50 900 0.924 16.37 0.652 9.86 Example 51 900 0.910 16.05 0.644 9.40 Example 52 900 0.919 17.03 0.580 9.07 Example 53 900 0.920 16.06 0.65 9.56 Example 54 900 0.917 16.07 0.66 9.69 Example 55 900 0.903 18.41 0.65 10.81 Example 56 900 0.912 17.53 0.65 10.35 Example 57 900 0.907 18.17 0.65 10.73 Example 58 900 0.896 18.10 0.66 10.63 Example 59 900 0.906 17.61 0.65 10.33 Example 60 900 0.901 17.23 0.66 10.25 Comparative Example 1 900 0.731 19.70 0.54 7.77

In Table 7, Spin-speed is the rotation speed of the equipment when forming a photoactive layer by spin-coating the composite solution on the electron transport layer, V _OC is the open-circuit voltage, J _SC is the short-circuit current, and FF is the charging rate. (Fill factor) and η means energy conversion efficiency. The open-circuit voltage and short-circuit current are the X-axis and Y-axis intercepts in the fourth quadrant of the voltage-current density curve, respectively, and the higher these two values, the higher the efficiency of the solar cell. Additionally, the fill factor is the area of the rectangle that can be drawn inside the curve divided 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, the more preferable. .

Looking at the results in Table 7, the organic solar cells of Examples 1 to 60 using Compounds 1 to 60 according to an exemplary embodiment of the present specification as electron acceptors are the organic solar cells of Comparative Example 1 using a comparative compound not containing alkoxyphenyl. It can be seen that compared to solar cells, the open-circuit voltage is high, the device efficiency such as charging rate is excellent, and the energy conversion efficiency is excellent. This is because alkoxyphenyl causes lower HOMO/higher LUMO energy levels compared to thiophene, resulting in higher open-circuit voltage.

In addition, the open-circuit voltages of Examples 31 to 60 using Compounds 31 to 60 in which the alkoxy group was substituted in the meta position of the benzene ring were generally lower than those in Examples 1 to 30 using Compounds 1 to 30 in which the alkoxy group was substituted in the para position. It can be seen that it is higher, and thus the energy conversion efficiency is also mostly superior. This is because the alkoxy group substituted at the meta position forms a relatively higher LUMO energy level than the alkoxy group substituted at the para position.

100: first electrode
200: Photoactive layer
300: second electrode

Claims (12)

Heterocyclic compounds represented by any of the following formulas 5-1 to 5-8:
[Formula 5-1]

[Formula 5-2]

[Formula 5-3]

[Formula 5-4]

[Formula 5-5]

[Formula 5-6]

[Formula 5-7]

[Formula 5-8]

In Formulas 5-1 to 5-8,
R1 to R4 are the same or different from each other and are each a straight-chain or branched alkyl group having 1 to 30 carbon atoms,
R5 to R8 are hydrogen,
R9 and R10 are the same or different from each other and are each a straight-chain or branched alkyl group having 1 to 30 carbon atoms; or an aryl group having 6 to 10 carbon atoms,
Y1 and Y2 are the same or different from each other and are each a halogen group; or a straight-chain alkyl group having 1 to 10 carbon atoms,
n and m are the same or different from each other and are each integers from 0 to 6,
R15 to R22 are the same or different and are each hydrogen; or a straight-chain alkyl group having 1 to 10 carbon atoms,
Q1 to Q4 are the same or different from each other and are S or Se, respectively. delete delete delete delete delete In claim 1,
The heterocyclic compound is any one selected from the following formulas 6-1 to 6-60:
[Formula 6-1]

[Formula 6-2]

[Formula 6-3]

[Formula 6-4]

[Formula 6-5]

[Formula 6-6]

[Formula 6-7]

[Formula 6-8]

[Formula 6-9]

[Formula 6-10]

[Formula 6-11]

[Formula 6-12]

[Formula 6-13]

[Formula 6-14]

[Formula 6-15]

[Formula 6-16]

[Formula 6-17]

[Formula 6-18]

[Formula 6-19]

[Formula 6-20]

[Formula 6-21]

[Formula 6-22]

[Formula 6-23]

[Formula 6-24]

[Formula 6-25]

[Formula 6-26]

[Formula 6-27]

[Formula 6-28]

[Formula 6-29]

[Formula 6-30]

[Formula 6-31]

[Formula 6-32]

[Formula 6-33]

[Formula 6-34]

[Formula 6-35]

[Formula 6-36]

[Formula 6-37]

[Formula 6-38]

[Formula 6-39]

[Formula 6-40]

[Formula 6-41]

[Formula 6-42]

[Formula 6-43]

[Formula 6-44]

[Formula 6-45]

[Formula 6-46]

[Formula 6-47]

[Formula 6-48]

[Formula 6-49]

[Formula 6-50]

[Formula 6-51]

[Formula 6-52]

[Formula 6-53]

[Formula 6-54]

[Formula 6-55]

[Formula 6-56]

[Formula 6-57]

[Formula 6-58]

[Formula 6-59]

[Formula 6-60]
A composition for forming an organic active layer of an organic electronic device comprising the heterocyclic compound according to claim 1 or 7. In claim 8,
A composition for forming an organic active layer of an organic electronic device, wherein the content of the heterocyclic compound is 0.5 wt% to 3 wt% based on 100 wt% of the composition. first electrode;
a second electrode provided opposite the first electrode; and
It is provided between the first electrode and the second electrode, and includes one or more organic layers including an organic active layer,
An organic electronic device wherein the organic active layer includes the heterocyclic compound according to claim 1 or 7. In claim 10,
The organic active layer includes an electron donor and an electron acceptor,
An organic electronic device wherein the electron acceptor includes the heterocyclic compound. In claim 10,
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.