KR101605937B1 - Fused cyclic compound, organic solar cell comprising the same and fabricating method thereof - Google Patents

Abstract

The present invention relates to a condensed ring compound, an organic solar cell comprising the same, and a method for producing the same.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a condensed ring compound, an organic solar cell including the condensed ring compound, and a method for producing the condensed ring compound.

The present invention relates to a condensed ring compound, an organic solar cell using the same, and a manufacturing method thereof.

Organic solar cells have attracted attention because of their easy processability, variety, cheap manufacturing cost and high flexibility. They are growing fast with the development of new materials.

Organic semiconductors are essential for the production of low-cost solar cells, such as thin-film devices, large-area devices, and flexible devices capable of roll-to-roll methods, It is expected to appear as a material.

The possibility of organic solar cells was first suggested in the 1970s, but efficiency was too low to be practical.

However, in 1986, Eastman Kodak's CWTang showed a possibility of practical use as various solar cells with a double layer structure using copper phthalocyanine (CuPc) and perylene tetracarboxylic acid derivatives , Interest and interest in organic solar cells and research have been rapidly increasing and have brought many improvements.

In 1995, Yu et al. Introduced the concept of bulk heterojunction (BHJ), and developed fullerene derivatives such as PCBM, which have improved solubility, as n-type semiconductors. there was.

However, the problem that the starting material, fullerene, is expensive, difficult to synthesize, and poor in solubility is still a major obstacle to the development of electron acceptor materials.

The development of e-donor materials with low bandgap and e-acceptor materials with good charge mobility has been continuously studied to replace existing materials.

1. Two-layer organic photovoltaic cell (C. W. Tang, Appl. Phys. Lett., 48, 183. (1996) 2. 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 condensed ring compound having thermal stability, high solubility and electron mobility, an organic solar cell containing the same, and a method for producing the same.

In one embodiment of the present disclosure,

There is provided a condensed ring compound represented by the following formula (1).

[Chemical Formula 1]

In formula (1)

Cy is a substituted or unsubstituted aliphatic condensed ring; A condensed ring of substituted or unsubstituted aromatic groups; A condensed ring of substituted or unsubstituted aliphatic hetero atoms containing at least one of N, O and S atoms; A condensed ring of substituted or unsubstituted aromatic hetero comprising one or more of N, O and S atoms; A condensed ring of a substituted or unsubstituted aliphatic ring and an aromatic ring; A condensed ring of an aromatic heterocycle containing at least one of an aliphatic heterocycle containing at least one of substituted or unsubstituted N, O and S atoms and at least one of N, O and S atoms; A condensed ring of a substituted or unsubstituted hydrocarbon ring and a ring of heterocycle containing at least one of N, O and S atoms; Or C ₆₀ to C ₈₄ substituted or unsubstituted fullerene,

n is an integer of 2 or 3,

m is an integer of 1 to 3,

A is a substituted or unsubstituted alkylene group,

R is hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; An amino group; Thiol group; Thioester group; Ester group; A carbonyl group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aralkyl group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted carbazole group; And a substituted or unsubstituted heterocyclic group containing at least one of N, O and S atoms.

According to an embodiment of the present invention, there is provided a light emitting device comprising a first electrode, a second electrode facing the first electrode, and at least one organic layer provided between the first electrode and the second electrode, And at least one of the layers contains the condensed ring compound.

Further, in one embodiment of the present disclosure, there is provided a method of manufacturing a semiconductor device, comprising: preparing a substrate; Forming a first electrode on the substrate; Forming at least one organic layer including a photoactive layer on the first electrode; And forming a second electrode on the organic material layer, wherein the one or more organic material layers include the condensed ring compound.

Can be used as a material for an organic material layer of an organic electronic device including an organic solar cell including a condensed ring compound according to an embodiment of the present invention, and an organic electronic device including the organic solar cell using the same can exhibit excellent characteristics .

The condensed ring compound according to one embodiment of the present invention can be used purely in an organic electronic device including an organic solar cell, mixed with impurities, and can be applied by vacuum deposition, solution coating, or the like.

In addition, the condensed ring compound according to one embodiment of the present invention improves light efficiency, is excellent in thermal stability, and can improve lifetime characteristics of the device.

1 shows an organic solar cell according to one embodiment.

Hereinafter, the present invention will be described in detail.

This specification provides condensed ring compounds of formula (1).

In one embodiment of the present disclosure, the condensed ring compound comprises a monocyclic ring comprising a double bond.

In the present specification, the condensed ring is an aliphatic condensed ring; Aromatic fused rings; A condensed ring of an aliphatic hetero comprising at least one of N, O and S atoms; A fused ring of aromatic hetero comprising at least one of N, O and S atoms; A condensed ring of an aliphatic ring and an aromatic ring; A condensed ring of an aromatic heterocyclic ring containing at least one of an aliphatic heterocycle containing at least one of N, O and S atoms and N, O and S atoms; A condensed ring of a hydrocarbon ring and a ring of heterocycle containing at least one of N, O and S atoms; Or C ₆₀ to C ₈₄ fullerene.

In one embodiment of the present disclosure, Cy is a condensed ring of substituted or unsubstituted aromatic groups; Or C ₆₀ to C ₈₄ substituted or unsubstituted fullerene.

In this specification, the condensed ring means an annular structure in which two or more rings share two or more atoms.

In one embodiment of the present disclosure, the aliphatic condensation ring is cyclohexane, cyclopentane, cycloheptane, cyclooctane or cyclohexanedione.

In one embodiment of the present disclosure, the condensed ring of the aromatic group is selected from the group consisting of naphthalene; anthracene; Phenanthryl; Triphenylene; Fluoranthene; Pyrene; Perylene; Krysein; Acenaphthalene; Fluorene; Or tetracene.

In one embodiment of the present disclosure, the condensed ring of aliphatic heteroatoms containing at least one of the N, O and S atoms is selected from piperidine, tetrahydrothiopyran, tetrahydropyran, dioxane, pyrrolidine, tetra Lt; / RTI > is tetrahydrofuran or tetrahydrothiophene.

In one embodiment of the present disclosure, the condensed ring of aromatic hetero comprising at least one of the N, O and S atoms is selected from the group consisting of quinoline; Sinnolin; Quinazoline; Quinoxaline; Phthalazine; Naphthyridine; Phenanthroline; Acridine; Carbazole; Dibenzofuran; Benzoimidazole; Dibenzothiophene; Benzothiophene; Benzofuran; Benzothiadiazole; Pyridopyrimidine; Pyridopyrazine; Pyrazinopyrazine; Isoquinoline; Indole; Benzoxazole; Benzothiazole; Benzocarbazole; Benzothiazole; Or phenothiazine.

The condensed ring may further include deuterium; A halogen group; An alkyl group; An alkenyl group; An alkoxy group; A cycloalkyl group; Silyl group; An arylalkenyl group; An aryl group; An aryloxy group; An alkyloxy group; An alkylsulfoxy group; Arylsulfoxy group; Boron group; An alkylamine group; An aralkylamine group; An arylamine group; A heteroaryl group; Carbazole group; An arylamine group; An aryl group; A fluorenyl group; A nitrile group; A nitro group; A hydroxy group and a heterocyclic group containing at least one of N, O, and S atoms, or a substituent adjacent thereto is a cycloalkyl group; Cycloalkenyl; Aromatic rings; An aliphatic heterocycle containing at least one of N, O and S atoms; Or an aromatic heterocyclic ring containing at least one of N, O and S atoms, or a substituent in the same carbon is a spiro bond; A carbonyl group; A substituted or unsubstituted imine group; Or a substituted or unsubstituted alkenyl group.

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

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

In another embodiment, m is 3.

In one embodiment of the present invention, the condensed cyclic compound represented by the formula (1) is represented by any one of the following formulas (2) to (4).

(2)

(3)

[Chemical Formula 4]

In formulas (2) to (4)

Cy, R, A and n are the same as defined in formula (1)

R 'and R "are the same as or different from each other, and each independently is the same as defined for R,

A " and A "are the same as or different from each other, and each independently is the same as defined in A,

n 'and n "are the same as or different from each other, and each independently is the same as n.

The position of the monocyclic ring substituent of the condensed ring compound according to the present specification is not limited. Thus, it includes those in which any position of the double bond of the fullerene can be substituted.

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

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

In one embodiment of the present invention, the condensed cyclic compound represented by Formula 1 provides the condensed cyclic compound represented by Formula 5 or 6 below.

[Chemical Formula 5]

[Chemical Formula 6]

In formulas (5) and (6)

Cy, R and m are the same as defined in formula (1).

In one embodiment of the present disclosure, R is selected from the group consisting of hydrogen; Amide group; A hydroxy group; An amino group; Thiol group; Thioester group; Ester group; A substituted or unsubstituted alkyl group; And a substituted or unsubstituted alkoxy group.

R is hydrogen; Amide group; A hydroxy group; An amino group; Thiol group; Thioester group; Ester group; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted alkoxy group, the solubility of the condensed ring compound increases, which is advantageous in the production of an organic solar cell.

In one embodiment of the present disclosure, Cy is substituted or unsubstituted perylene; Or a C ₆₀ to C ₈₄ fullerene.

In one embodiment of the present invention, Cy is a perylene group substituted with an alkyl group.

In one embodiment of the present specification, Cy is a perylene group substituted with a pentyl group.

In one embodiment of the present disclosure, Cy is substituted or unsubstituted fullerene of C ₆₀ to C ₈₄ .

In one embodiment of the present disclosure, Cy is C ₆₀ to C ₈₄ fullerene.

In one embodiment of the present invention, the condensed ring compound represented by Formula 5 is represented by a condensed ring compound represented by Formula 51 or Formula 52 below.

 In one embodiment of the present invention, the condensed cyclic compound represented by the formula (6) is represented by a condensed cyclic compound represented by the following formula (61).

(51)

(61)

(52)

In formulas (51), (61) and (52), the definitions of R and R 'are the same as those defined above.

Illustrative examples of such substituents are set forth below, but are not limited thereto.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 20. Specific examples include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl and heptyl.

In the present specification, the alkenyl group may be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, Butenyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, (Diphenyl-1-yl) vinyl-1-yl, stilbenyl, stilenyl, and the like.

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

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

In the present specification, the number of carbon atoms of the aralkyl group is not particularly limited, but in one embodiment of the present specification, the aralkyl group has 7 to 50 carbon atoms. Specifically, the aryl moiety has 6 to 49 carbon atoms and the alkyl moiety has 1 to 44 carbon atoms. Specific examples thereof include benzyl group, p-methylbenzyl group, m-methylbenzyl group, p-ethylbenzyl group, m-ethylbenzyl group, 3,5-dimethylbenzyl group, Group, an?,? -Methylphenylbenzyl group, a 1-naphthylbenzyl group, a 2-naphthylbenzyl group, a p-fluorobenzyl group, a 3,5-difluorobenzyl group, , p-methoxybenzyl group, m-methoxybenzyl group,? -phenoxybenzyl group,? -benzyloxybenzyl group, naphthylmethyl group, naphthylethyl group, naphthylisopropyl group, pyrrolylmethyl group, But are not limited to, an ethyl group, an aminobenzyl group, a nitrobenzyl group, a cyanobenzyl group, a 1-hydroxy-2-phenylisopropyl group, a 1-chloro-2-phenylisopropyl group and the like.

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

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

In the present specification, the aryl group may be monocyclic, and the number of carbon atoms is not particularly limited, but is preferably 6 to 60 carbon atoms. Specific examples of the aryl group include monocyclic aromatic and naphthyl groups such as phenyl group, biphenyl group, triphenyl group, terphenyl group and stilbene group, anthracenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, tetracenyl group, A cyclic aromatic group such as a fluorenyl group, an acenaphthacenyl group, a triphenylene group, and a fluoranthene group, but is not limited thereto.

In the present specification, the heterocyclic group is a hetero ring group containing O, N or S as a heteroatom, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrolyl group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a triazine group, , A quinolinyl group, an isoquinoline group, an indole group, a carbazole group, a benzoxazole group, a benzoimidazole group, a benzothiazole group, a benzocarbazole group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, (phenanthroline), dibenzofuranyl group, and the like, but are not limited thereto.

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

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

In the present specification, the general formula of the ester group can be expressed by a general formula of -COORa. Ra is hydrogen; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; A substituted or unsubstituted arylalkyl group having 7 to 50 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms containing at least one of N, O and S atoms.

Specifically, it may be a compound of the following structural formula, but is not limited thereto.

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

,

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

,

.

및

등이 있다. In the present specification, a fluorenyl group includes a structure of an open fluorenyl group, wherein an open fluorenyl group is a structure in which one ring compound is disconnected in a structure in which two ring compounds are connected through one atom, For example,

And

.

In the present specification, the number of carbon atoms of the amine group is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group include a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, a phenylamine group, a naphthylamine group, a biphenylamine group, an anthracenylamine group, a 9- , A diphenylamine group, a phenylnaphthylamine group, a ditolylamine group, a phenyltolylamine group, a triphenylamine group, and the like, but are not limited thereto.

In the present specification, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group or a polycyclic aryl group. The arylamine group having at least two aryl groups may contain a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group at the same time.

Specific examples of the arylamine group include phenylamine, naphthylamine, biphenylamine, anthracenylamine, 3-methylphenylamine, 4-methyl-naphthylamine, 2-methyl- But are not limited to, cenylamine, diphenylamine, phenylnaphthylamine, ditolylamine, phenyltolylamine, carbazole and triphenylamine groups.

In the present specification, the aryl group in the aryloxy group, the arylthioxy group, the arylsulfoxy group and the aralkylamine group is the same as the aforementioned aryl group.

 In the present specification, the alkyl group in the alkylthio group, alkylsulfoxy group, alkylamine group, and aralkylamine group is the same as the alkyl group described above.

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

In the present specification, adjacent groups mean substituents substituted on adjacent carbon atoms.

In the present specification, a substituent in the same carbon means a substituent sharing one carbon.

The term "substituted or unsubstituted" A halogen group; An alkyl group; An alkenyl group; An alkoxy group; A cycloalkyl group; Silyl group; An arylalkenyl group; An aryl group; An aryloxy group; An alkyloxy group; An alkylsulfoxy group; Arylsulfoxy group; Boron group; An alkylamine group; An aralkylamine group; An arylamine group; A heteroaryl group; Carbazole group; An arylamine group; An aryl group; A fluorenyl group; A nitrile group; A nitro group; A heterocyclic group containing at least one of a hydroxyl group and at least one of N, O and S atoms, or has no substituent group.

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

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

In one embodiment of the present specification, R is a methyl group.

In one embodiment of the present specification, R is an ethyl group.

In one embodiment of the present specification, R is a substituted or unsubstituted ester group.

In one embodiment of the present invention, R is an ester group substituted with an alkyl group.

In one embodiment of the present specification, R is an ester group substituted with a methyl group.

In one embodiment of the present specification, R is an ester group substituted with an ethyl group.

In one embodiment of the present invention, the compound represented by Formula 1 is represented by any one of Chemical Formulas 1-1 to 1-8, but the present invention is not limited thereto.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

[Chemical Formula 1-7]

[Chemical Formula 1-8]

In one embodiment of the present invention, the condensed ring compound has a LUMO energy level of -3.6 eV to -3.7 eV.

The condensed ring compound according to one embodiment of the present invention can have molecular orbitals, that is, HOMO and LUMO energy, in which injection of holes and electrons can easily occur when an electric field is applied, thereby improving charge injection and current mobility.

In addition, condensed ring compounds according to one embodiment of the present disclosure can have sufficient overlap of the frontier orbitals that an effective charge transfer between neighboring molecules can occur. Therefore, the organic solar cell using the condensed ring compound can have high efficiency.

The condensed ring compound according to one embodiment of the present invention is excellent in solubility, and therefore, when an organic solar cell is manufactured, a low-temperature solution process can be performed, so that a thin film can be easily formed on a plastic substrate.

The condensed ring compound according to one embodiment of the present invention may be in the form of a film having a thin film form such as a single crystal.

Condensed ring compounds according to one embodiment of the present disclosure can have effective charge transfer along the direction of intramolecular pi-pi stacking.

The condensed ring compound of formula (1) is prepared by introducing a substituted or unsubstituted alkenyl group into the carbon cluster compound of Cy as described below and ring cloing metathesis using a Grubbs catalyst.

First or second generation catalysts (grubbs catalyst 1 ^st or 2 ^nd generation)

에서, R 및 n을 조절하여, 원하고자 하는 플러렌 유도체를 제조할 수 있다. In the present specification,

, The desired fullerene derivative can be prepared by controlling R and n.

In one embodiment of the present disclosure, the organic light emitting device includes a first electrode, a second electrode facing the first electrode, and at least one organic material layer provided between the first electrode and the second electrode, Layer or more contains the condensed ring compound.

1 is a view illustrating an organic solar cell according to an embodiment of the present invention. 1, the light emitting device includes a substrate 101, a first electrode 102, a hole transport layer 103, a photoactive layer 104, and a second electrode 105.

The principle of an organic solar cell is that a p-type semiconductor forms an exciton paired with electrons and holes, and the exciton is separated into an electron and a hole at a p-n junction. The separated electrons and holes migrate to the n-type semiconductor thin film and the p-type semiconductor thin film, respectively, and they are collected in the first electrode and the second electrode, respectively, so that they can be used as electric energy from the outside.

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

In another embodiment, the organic material layer includes an electron injecting layer, an electron transporting layer, or a layer that simultaneously performs electron injection and electron transport, and the electron injecting layer, the electron transporting layer, Condensed ring compound.

In one embodiment of the present disclosure, the organic layer includes a photoactive layer, and the photoactive layer includes the condensed ring compound.

In another embodiment, the organic layer comprises a photoactive layer, wherein the photoactive layer comprises an electron donor material and an electron acceptor material, wherein the electron acceptor material comprises the condensed ring compound.

The condensed ring compound according to one embodiment of the present invention can efficiently produce an electron acceptor material having excellent solubility in an organic solvent through a simple production method. In addition, a material having photoreactivity, light stability and conductivity can be used as a starting material, and an electron acceptor material having high solubility in the reaction can be prepared.

In one embodiment of the present invention, the organic solar cell provides an organic solar cell in which the electron donor material and the electron acceptor material are bulk heterojunction (BHJ) junction type.

Bulk heterojunction means that the electron donor material and the electron acceptor material are mixed in the photoactive layer.

The electron donor material may be a polymer compound that is well compatible with the optical absorption wavelength range or the solar spectrum, and has strong optical absorption and excellent electrical properties such as charge mobility.

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

n is an integer of 1 to 1000,

Rm is hydrogen, a substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted aromatic or aliphatic heterocyclic group containing at least one of N, O and S atoms, or a substituted or unsubstituted aryl group.

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

The electron donor material and the electron acceptor material are mixed in a ratio (w / w) of 1:10 to 10: 1. After the electron donor and electron donor materials are mixed, annealing may be performed at 30 to 300 ° C for 1 second to 24 hours to maximize the properties.

In one embodiment of the present disclosure, the thickness of the photoactive layer is from 10 A to 10,000 A.

The substrate may be a glass substrate or a transparent plastic substrate having excellent transparency, surface smoothness, ease of handling, and waterproofness, but is not limited thereto and is not limited as long as it is a substrate commonly used in organic solar cells. Specifically, glass or polyethylene terphthalate (PEN), polyethylene naphthalate (PEN), polypropylene (PP), polyimide (PI), and triacetyl cellulose (TAC) But is not limited thereto.

In one embodiment of the present disclosure, 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.

The anode is preferably a material having a large work function so that injection of holes into the organic material layer can be smoothly performed. In addition, the material may be transparent and excellent in conductivity, but is not limited thereto. Specific examples of the anode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), tin oxide (SnO ₂ ), zinc oxide (ZnO) and indium zinc oxide (IZO); ZnO: Al or SNO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline.

The cathode is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; Layer structure materials such as Al / Li, Al / BaF ₂ , Al / BaF ₂ / Ba, LiF / Al or LiO ₂ / Al.

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

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

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

In one embodiment of the present invention, the organic solar battery is arranged in the order of an anode, a photoactive layer, and a cathode. In another embodiment, the cathode, the photoactive layer and the anode are arranged in this order.

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

The organic solar cell according to one embodiment of the present invention uses a conventional method and material for producing an organic solar cell, except that the condensed ring compound of the above-mentioned formula (1) is used in at least one layer of the organic material layer of the organic solar battery .

In one embodiment of the present disclosure, there is provided a method comprising: preparing a market; Forming a first electrode on the substrate; Forming one or more organic layers including a photoactive layer on the first electrode; And forming a second electrode on the organic material layer, wherein the one or more organic material layers include the condensed ring compound.

Specifically, in one embodiment of the present disclosure, there is provided a method of manufacturing a light emitting device, comprising: preparing a substrate; forming an anode on the substrate; forming a hole transport layer on the anode; forming a photoactive layer on the hole transport layer; Forming an electron transport layer on the photoactive layer, and forming a cathode on the electron transport layer.

In another embodiment, there is provided a method of manufacturing a light emitting device, comprising: preparing a substrate; forming a cathode on the substrate; forming an electron transport layer on the cathode; forming a photoactive layer on the electron transport layer; A step of forming a hole transporting layer and a step of forming an anode on the hole transporting layer. The organic solar cell of the present specification can be produced, for example, by sequentially laminating an anode, a photoactive layer and a cathode on a substrate.

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

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

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

In one embodiment of the present disclosure, an anode deposition step, a photoactive layer stacking step, a photoactive layer aligning step, a photoactive layer heat treatment step, and a cathode deposition step may be included.

In the step of laminating the photoactive layer, a composite thin film structure in which a solution prepared by mixing an electron donor material and an electron acceptor material is sprayed on the upper side of the anode, that is, a bulk heterojunction can be disposed.

The electron acceptor material may be a mixed solution of a complex polymer material dissolved in an organic solvent, and may include the condensed ring compound.

In one embodiment of the present specification, P3HT is dissolved in an organic solvent and used in the condensed ring compound.

The method for producing the condensed ring compound and the production of the organic solar cell using the same will be described in detail in the following Production Examples and Examples. However, the following examples are intended to illustrate the present specification, and the scope of the present specification is not limited thereto.

[ Manufacturing example  1] 1- 1 of  Produce

(One)

720 mg of C ₆₀ was dissolved in 200 ml of o-dichloro benzene, 1.29 ml of dimethylformamide was added, and 3 ml of a 1 M allylmagnesium chloride solution was added. After stirring for 10 minutes at room temperature, 0.2 ml of aqueous ammonium chloride solution was added to complete the reaction, and the organic solvent was blown off. The organic solvent was blown off and purified by passing through a silica pad using toluene. A sample was obtained.

(2)

A 1 M solution of potassium t-butoxide in tetrahydrofuran (THF) was prepared, and 0.3 ml of this solution was added to 190 mg of allyl dihydrofullerene compound in 50 ml of benzonitrile Was added to the dissolved solution. After stirring for about 10 minutes at room temperature, 730 mg of 4-bromo-2-methyl-1-butene was added. Depending on the degree of reactivity, some heating was applied at room temperature. When the reaction was completed, 1 ml of ammonium chloride aqueous solution was added and the solvent was blown away. It was dissolved in toluene, passed through a silica pad, concentrated again, and precipitated in methanol to obtain a solid sample.

(3)

83 mg of the obtained dialkenyl fullerene was dissolved in chloroform, 1 mg of Grubbs catalyst was added thereto, and the mixture was stirred. When the reaction was completed, the solvent was distilled off and purified by column chromatography.

[ Manufacturing example  2] Preparation of the compounds of formulas 1-4

Bromo-2-methyl-1-pentene (5-bromo-2-methyl-1-butene) instead of 4-bromo- bromo-2-methyl-1-pentene) was added.

In order to observe the electrochemical characteristics of the compound prepared in the above Preparation Example, oxidation / reduction characteristics were observed using cyclic voltammetry (CV).

The CV equipment used was AUTOLAB, and a 0.1 M solution of tetrabutylammonium tetrafluoroborate (Bu ₄ NBF ₄ ) was used as an electrolyte in acetonitrile. The sample was dissolved in a concentration of 10 ^-3 M And then melted.

A glass carbon electrode was used as a working electrode and Pt and Ag / AgCl electrodes were used as a counter electrode and a reference electrode, and the results are shown in Table 1 below.

compound HOMO energy level (eV) LUMO energy level (eV) (1-1) 6.42 3.68 Formula 1-4 6.43 3.66 P3HT 5.0 3.0

In general, the open circuit voltage of an organic solar cell is known to be caused by a difference between a HOMO energy level of an electron donor material and a LUMO energy level of an electron acceptor material. The aromatic ring compounds of the present invention are 0.3 ~ It has HOMO energy level as low as 0.4 eV, so that higher open-circuit voltage can be obtained in organic solar cell.

[ Example  1] Organic solar cell

The compound prepared in Preparation Examples 1 to 3 and P3HT were dissolved in 1,2-dichlorobenzene (DCB) and chloroform mixed solution or chloroform to prepare a composite solution. At this time, the concentration was adjusted to 1.0 wt%, and the organic solar cell had the structure of ITO / PEDOT: PSS / photoactive layer / Al. The ITO-coated glass substrate was ultrasonically cleaned using distilled water, acetone, and isopropanol. The ITO surface was subjected to ozone treatment for 10 minutes, then spin coated with PEDOT: PSS (Baytron P) to a thickness of 45 nm, Respectively. For coating the photoactive layer, the P3HT: compound complex solution was filtered with a 0.45 μm PP syringe filter, followed by spin coating and heat treatment at 120 ° C. for 5 minutes. The photoelectric conversion characteristics of the organic solar cell thus prepared were measured under the condition of 100 mW / cm ² (AM 1.5), and the results are shown in Table 2 below.

Active layer Total thickness
(nm) V _OC
(V) J _SC
(mA / cm ² ) FF PCE
(%) P3HT / formula 1-1 = 1: 0.7 98 0.67 2 0.7 0.94 P3HT / Formula 1-4 = 1: 0.7 94 0.66 2.1 0.62 0.86

In Formula 1-1, n is 2, Cy is C ₆₀ fullerene, and R is an alkyl group.

In Formula 1-4, n is 3, Cy is C ₆₀ fullerene, and R is an alkyl group.

Although the embodiments of the present invention have been described above, it will be apparent to those skilled in the art that various changes and modifications may be made without departing from the scope of the present invention. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

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

Claims (15)

A condensed ring compound represented by the following formula (1):
[Chemical Formula 1]

In formula (1)
Cy is a C ₆₀ to C ₈₄ fullerene,
n is an integer of 2 or 3,
m is an integer of 1 to 3,
A is a methylene group,
R is an alkyl group having 1 to 20 carbon atoms or -COORa, and Ra is an alkyl group having 1 to 20 carbon atoms. The method according to claim 1,
The condensed ring compound represented by the formula (1) is represented by any one of the following formulas (2) to (4)
(2)

(3)

[Chemical Formula 4]

In formulas (2) to (4)
Cy, R, A and n are the same as defined in formula (1)
R 'and R "are the same as or different from each other, and each independently is the same as defined for R,
A " and A "are the same as or different from each other, and each independently is the same as defined in A,
n 'and n "are the same as or different from each other, and each independently is the same as n. The method according to claim 1,
And m is 2. The method according to claim 1,
The condensed ring compound represented by the formula (1) is a condensed ring compound represented by the following formula (5) or (6)
[Chemical Formula 5]

[Chemical Formula 6]

In formulas (5) and (6)
Cy, R and m are the same as defined in formula (1). delete delete delete The method according to claim 1,
Wherein the condensed ring compound represented by the formula (1) is represented by any one of the following formulas (1-1) to (1-7).
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

[Chemical Formula 1-7]

A first electrode, a second electrode facing the first electrode, and at least one organic layer disposed between the first electrode and the second electrode,
Wherein at least one of the organic material layers comprises the condensed ring compound according to any one of claims 1 to 4 and 8. The method of claim 9,
Wherein the organic material layer includes a hole transporting layer, a hole injecting layer, or a layer simultaneously transporting holes and injecting holes,
Wherein the hole transporting layer, the hole injecting layer, or the layer simultaneously transporting the holes and the hole injecting comprises the condensed ring compound. The method of claim 9,
Wherein the organic material layer includes an electron injection layer, an electron transport layer, or a layer that simultaneously performs electron injection and electron transport,
Wherein the electron injecting layer, the electron transporting layer, or the layer simultaneously injecting electrons and transporting electrons comprises the condensed ring compound. The method of claim 9,
Wherein the organic layer comprises a photoactive layer,
Wherein the photoactive layer comprises the condensed ring compound. The method of claim 9,
Wherein the organic layer comprises a photoactive layer,
Wherein the photoactive layer comprises an electron donor material and an electron acceptor material,
Wherein the electron acceptor material comprises the condensed ring compound. 14. The method of claim 13,
Wherein the electron donor material and the electron acceptor material are in a bulk heterojunction junction type. Preparing a substrate;
Forming a first electrode on the substrate;
Forming at least one organic layer including a photoactive layer on the first electrode; And
And forming a second electrode on the organic material layer,
Wherein the one or more organic layers include the condensed ring compound of any one of claims 1 to 4 and 8.

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