KR101620137B1 - Manufacturing method of fullerene derivatives - Google Patents
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Abstract
The present specification relates to a method for producing fullerene.
Description
The present invention relates to a process for preparing a fullerene derivative.
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.
It is an object of the present invention to provide a method for producing a fullerene derivative.
In one embodiment of the present disclosure, there is provided a process for preparing a fullerene derivative, comprising: introducing a first substituted or unsubstituted alkenyl group into fullerene; Introducing a second substituted or unsubstituted alkenyl group into the fullerene; And subjecting the first alkenyl group and the second alkenyl group to a ring closing metathesis reaction to form a condensed ring.
[Chemical Formula 1]
In formula (1)
F is a C 60 to C 84 fullerene,
n is an integer of 1 to 3,
l and m are each an integer of 0 to 4,
l + m > = 1,
A and B are the same or different and are each independently 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 arylalkyl 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.
Further, in one embodiment of the present invention, the fullerene derivative produced by the above production method is provided.
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 above-mentioned fullerene derivative.
The fullerene derivative produced by the production method according to one embodiment of the present specification can be manufactured by a relatively simple process, and is economical in terms of time and / or cost.
The fullerene derivative produced by the production method according to one embodiment of the present specification can be used as a material of an organic material layer of an organic electronic device including an organic solar cell due to effective charge transfer, / / ≪ / RTI >
1 shows an organic solar cell according to one embodiment.
Hereinafter, the present invention will be described in detail.
As used herein, the term "fullerene derivative " means a material having at least one spherical shell structure in which the molecule is formed of carbon. For example, fullerene as a spherical shell-shaped carbon molecule, fullerene having an inorganic or organic group bonded to carbon constituent fullerene A fullerene derivative in which a spherical shell structure constituting the fullerene derivative is bonded directly or through one or more elements.
According to one embodiment of the present invention, there is provided a process for producing a fullerene derivative represented by the following formula (1).
[Chemical Formula 1]
In formula (1)
F is a C 60 to C 84 fullerene,
n is an integer of 1 to 3,
l and m are each an integer of 0 to 4,
l + m > = 1,
A and B are the same or different and are each independently 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 arylalkyl 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.
In one embodiment of the present invention, the fullerene derivative of Formula 1 may be prepared by introducing a first substituted or unsubstituted alkenyl group into fullerene; Introducing a second substituted or unsubstituted alkenyl group into the fullerene; And a step of forming a condensation ring by a ring closing metathesis reaction between the first alkenyl group and the second alkenyl group.
In the present specification, the ring closure metathesis means a reaction in which two alkenyl groups are disengaged and a new alkenyl group and a ring are formed.
In this specification, the method for producing a fullerene derivative using the ring closure metathesis reaction has an economical advantage in terms of time and / or cost because of a simple manufacturing process.
In one embodiment of the present disclosure, the ring closure metathesis reaction proceeds in the presence of a first- or second-generation Grubbs catalyst 1 st or 2 nd generation.
The first- or second-generation Grubbs catalysts are as follows.
In one embodiment of the present invention, the step of forming the condensation ring by the ring-closing metathesis reaction of the first alkenyl group and the second alkenyl group proceeds at 0 캜 to 200 캜.
In one embodiment of the present specification, the step of introducing the first substituted or unsubstituted alkenyl group into the fullerene proceeds by adding the following chemical formula.
In the above formulas, A and 1 are the same as defined in formula (1).
In one embodiment of the present disclosure, the step of introducing the first substituted or unsubstituted alkenyl group into the fullerene introduces allylmagnesium chloride.
In another embodiment, the step of introducing the first substituted or unsubstituted alkenyl group into the fullerene introduces vinyl magnesium chloride.
In one embodiment of the present specification, the step of introducing the first substituted or unsubstituted alkenyl group into the fullerene proceeds at -20 캜 to 200 캜.
In one embodiment of the present specification, the step of introducing the second substituted or unsubstituted alkenyl group into the fullerene proceeds by adding the following chemical formula.
In the above formulas, R, B and m are the same as defined in formula (1).
In one embodiment of the present disclosure, introducing the second substituted or unsubstituted alkenyl group introduces 3-bromo-1-propene.
In one embodiment of the present specification, the step of introducing the second substituted or unsubstituted alkenyl group introduces 4-bromo-1-butene.
In one embodiment of the present disclosure, the step of introducing the second substituted or unsubstituted alkenyl group introduces 5-bromo-1-pentene.
In one embodiment of the present specification, the step of introducing the second substituted or unsubstituted alkenyl group into the fullerene proceeds at -78 ° C to 200 ° C.
In one embodiment of the present disclosure, the brominated alkene may be substituted with an additional R. Wherein R is the same as defined above.
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.
According to one embodiment of the present disclosure, 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 fullerene derivative increases, which is advantageous in the production of an organic solar cell.
In one embodiment of the present specification, l and m may be adjusted to control the size of the desired condensed ring and / or the position of the double bond in the condensed ring.
In one embodiment of the present disclosure, additional substituents other than R or R may be adjusted to produce a fullerene derivative to match the intended use and properties of the desired fullerene.
In one embodiment of the present specification, l + m is 1? L + m? 4.
As described above, since the formation of the condensed ring in the range of 1? L + m? 4 is stable, the formation of the condensed ring is easy.
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 arylalkyl group is not particularly limited, but in one embodiment of the present specification, the arylalkyl 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, a fluorenyl group is a structure in which two ring organic compounds are connected via one atom,
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,
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.
A method for producing a fullerene derivative according to an embodiment of the present invention may be as follows.
A method for producing a fullerene derivative according to an embodiment of the present invention may be as follows.
A method for producing a fullerene derivative according to an embodiment of the present invention may be as follows.
A method for producing a fullerene derivative according to an embodiment of the present invention may be as follows.
In one embodiment of the present invention, there is provided a fullerene derivative produced by the above production method.
In one embodiment of the present invention, the fullerene derivative produced by the above production method is represented by the following formula (1).
[Chemical Formula 1]
In Formula (1), F, A, B, R, l, m and n are the same as defined above.
In one embodiment of the present invention, the fullerene derivative produced by the above production method is any one of the following fullerenes.
The fullerene derivative produced according to one embodiment of the present invention is contained in one or more organic layers of an organic solar cell.
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 above-prepared fullerene derivative.
Fullerene derivatives prepared according to one embodiment of the present disclosure may have sufficient overlap of the frontier orbitals that an effective charge transfer between neighboring molecules may occur. Therefore, the organic solar cell using the fullerene derivative may have a high efficiency.
The fullerene derivative produced according to one embodiment of the present invention is excellent in solubility and can be easily subjected to a low temperature solution process when an organic solar cell is manufactured so that a thin film can be easily formed on a plastic substrate, .
In addition, the fullerene derivative produced according to one embodiment of the present invention can be in the form of a film having a thin film form such as a single crystal.
The fullerene derivative produced according to one embodiment of the present invention can have effective charge transfer along the direction of intramolecular pi-pi stacking.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram illustrating an organic solar cell including a fullerene derivative produced according to an embodiment of the present invention; FIG. 1, the light emitting device includes a
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 fullerene derivative.
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, Fullerene derivatives.
In one embodiment of the present disclosure, the organic layer includes a photoactive layer, and the photoactive layer includes the fullerene derivative.
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 fullerene derivative.
The fullerene derivative produced 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 may be a material for efficiently transferring electrons and holes to the photoactive layer, thereby increasing the probability that the generated charge moves to the electrode. However, the hole transporting layer and / or the electron transporting layer material are not particularly limited.
The hole transporting layer and / or the electron transporting layer material may be a material for efficiently transferring electrons and holes to the photoactive layer, thereby increasing the probability that the generated charge moves to the electrode. However, the hole transporting layer and / or the electron transporting layer material are not particularly limited. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion together, but the present invention is not limited thereto. The hole transport layer material may be selected from the group consisting of poly (3,4-ethylenediocythiophene) doped with poly (styrenesulfonic acid), N, N'-bis (3-methylphenyl) -N, N'- '-Biphenyl] -4,4'-diamine (TPD).
The electron transporting layer material is an Al complex of 8-hydroxyquinoline; Complexes containing Alq 3 ; Organic radical compounds; Hydroxyflavone-metal complexes, aluminum tri-hydroxy-quinolinyl (Alq 3), a 1,3,4-oxadiazole derivative PBD (2- (4-bipheyl) -5-phenyl-1,3,4-oxadiazole ), Quinoxaline derivatives such as TPQ (1,3,4-tris [(3-phenyl-6-trifluoromethyl) qunoxaline-2-yl] benzene) and triazole derivatives.
As the hole injecting material, it is preferable that the highest occupied molecular orbital (HOMO) of the hole injecting material is between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injecting material include metal porphyrin, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, and perylene- , Anthraquinone, polyaniline and polythiophene-based conductive polymers, 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 can be produced by using a conventional method and material for producing an organic solar cell, except that the above-mentioned fullerene derivative of the formula 1 is used for 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 substrate; 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 fullerene derivative.
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 fullerene derivative.
In one embodiment of the present invention, P3HT is dissolved in an organic solvent to use the fullerene derivative.
The method for producing the fullerene derivative 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
[Formula 1-1]
(1) 720 mg of C 60 is dissolved in 200 ml of o-dichloro benzene, 1.29 ml of DMF is added, and 3 ml of a 1 M allylmagnesium chloride solution is added thereto. After stirring for 10 minutes at room temperature, 0.2 ml of an aqueous ammonium chloride solution was added to the reaction mixture to terminate the reaction, and the organic solvent was blown off. The organic solvent was blown and purified by passing through a silica pad using toluene. A solid black sample was obtained.
(2) A 1M 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 benzonitrile. < / RTI > After stirring for 10 minutes at room temperature, 730 mg of 3-bromo-2-methyl-1-propene 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) The obtained dialkenyl fullerene was dissolved in methylene chloride, and a ring closing metathesis using a 1 mol% Grubbs catalyst was carried out.
[ Manufacturing example 2] Preparation of the compound of the formula 1-2
[Formula 1-2]
Bromo-2-methyl-1-butene (4) instead of 3-bromo-2-methyl-1-propene in Production Example 1 (2) -bromo-2-methyl-1-butene) was added.
[ Manufacturing example 3] Preparation of compound of formula 1-3
[Formula 1-3]
Bromo-2-methyl-1-pentene (5-bromo-2-methyl-1-propene) was used in place of 3-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.
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
A compound solution was prepared by dissolving the compound prepared in Preparation Examples 1 to 3 and P3HT in 1,2-dichlorobenzene (DCB) and chloroform mixed solution or chloroform. 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.
(nm)
(V)
(mA / cm 2 )
(%)
In Formula 1-1, l = 1, m = 1, n = 1 or 2, F is C 60 fullerene, and R is a methyl group.
In Formula 1-2, l = 1, m = 2, n = 1 or 2, F is C 60 fullerene, and R is a methyl group.
Wherein the formula 1-3 is 1 = 1, m = 3, n = 1 or 2, F is a C 60 fullerene, and R is a methyl 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 (10)
Introducing a second substituted or unsubstituted alkenyl group into the fullerene; And
Wherein the first alkenyl group and the second alkenyl group are subjected to a ring closing metathesis reaction to form a condensed ring. The method for producing a fullerene derivative according to claim 1,
[Chemical Formula 1]
In formula (1)
F is a C 60 to C 84 fullerene,
n is an integer of 1 to 3,
l and m are each an integer of 0 to 4,
l + m > = 1,
A and B are the same or different and are each independently 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 arylalkyl 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.
Wherein the ring closure metathesis reaction proceeds in the presence of a first or second generation catalyst (Grubbs catalyst 1 st or 2 nd generation).
Wherein the step of introducing the first substituted or unsubstituted alkenyl group into the fullerene is carried out by adding the following formula:
In the above formula,
A and l are the same as defined in formula (1).
Wherein the step of introducing the second substituted or unsubstituted alkenyl group into the fullerene is carried out by adding the following formula:
In the above formula,
R, B and m are the same as defined in formula (1).
Lt; m + 1 < / RTI >
Wherein the step of introducing the first substituted or unsubstituted alkenyl group into the fullerene proceeds at -20 ° C to 200 ° C.
Wherein the step of introducing the second substituted or unsubstituted alkenyl group into the fullerene proceeds at -78 ° C to 200 ° C.
Wherein the step of forming the condensation ring by the ring-closing metathesis reaction of the first alkenyl group and the second alkenyl group proceeds at 0 캜 to 200 캜.
Wherein at least one of the organic material layers comprises the fullerene derivative according to claim 9.
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