KR101676526B1 - Novel compound and photoelectric conversion device having the same - Google Patents
Novel compound and photoelectric conversion device having the same Download PDFInfo
- Publication number
- KR101676526B1 KR101676526B1 KR1020140065280A KR20140065280A KR101676526B1 KR 101676526 B1 KR101676526 B1 KR 101676526B1 KR 1020140065280 A KR1020140065280 A KR 1020140065280A KR 20140065280 A KR20140065280 A KR 20140065280A KR 101676526 B1 KR101676526 B1 KR 101676526B1
- Authority
- KR
- South Korea
- Prior art keywords
- compound
- formula
- independently
- group
- present
- Prior art date
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Photovoltaic Devices (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The present invention provides a compound capable of greatly improving the lifetime, efficiency, electrochemical stability, and thermal stability of a photoelectric conversion element, and a photoelectric conversion element containing the compound. Specifically, an organic solar cell is provided in the photoelectric conversion element.
Description
The present invention relates to a photoelectric conversion device comprising a nitrogen-containing compound and a solar cell including the same.
A photoelectric conversion element is an element that converts a light signal into an electric signal by using a photoelectric effect.
Photoelectric effect refers to the phenomenon that, when a material is irradiated, the electrons inside the material absorb the light energy and emit photoelectrons. The photoelectric effect includes the external photoelectric effect that photoelectrons are emitted from the solid surface, the photoionization that photoelectrons are emitted from electrons or molecules, the internal photoelectric effect that the conduction electrons are generated inside the solid such as the insulator or semiconductor, And a photovoltaic effect in which an electromotive force is generated. With this photoelectric effect, you can turn a light signal into an electrical signal or turn light energy into electrical energy.
Using these properties, a phototube, a photodiode, a phototransistor, a photoconductive element, a photovoltaic cell, and a solar cell can be manufactured.
Solar cells are devices that can convert solar energy directly into electrical energy by applying a photovoltaic effect. Solar cells can be divided into inorganic solar cells and organic solar cells depending on the material constituting the thin film. A typical solar cell is made of p-n junction by doping crystalline silicon (Si), which is an inorganic semiconductor. Electrons and holes generated by absorption of light are diffused to the p-n junction, accelerated by the electric field, and moved to the electrode. The power conversion efficiency of this process is defined as the ratio of the power given to the external circuit to the solar power entering the solar cell, and is achieved up to 24% when measured under the current standardized virtual solar irradiation conditions. However, since conventional inorganic solar cells have already been limited in economical efficiency and supply / demand of materials, organic solar cells using organic materials which are easy to process, inexpensive, and have various functions are attracting attention as long-term alternative energy sources.
The possibility of organic solar cells was first suggested in the 1970s, but efficiency was too low to be practical. However, in 1986, CW Tang of Eastman Kodak showed the possibility of practical use as various solar cells with a double layer structure using copper phthalocyanine (CuPc) and perylene tetracarboxylic acid derivatives Two-layer organic photovoltaic cell CW Tang, Appl. Phys. Lett., 48, 183 (1986)). In 1995, the concept of BHJ (Bulk heteojunction) was introduced by Yu et al. (Network of Internal Donor-Acceptor Heterojunctions, G. Yu, J. Gao, JC Hummelen, F. Wudl, AJ Heeger, 1789 (1995)), and fullerene derivatives having improved solubility such as PCBM have been developed as n-type semiconductor materials, thereby remarkably improving the efficiency of organic solar cells. In addition, current organic solar cells are attracted more attention than conventional inorganic solar cells because they can be manufactured at low cost and simple manufacturing process, can form a large-area thin film through coating, Can be used. There are also a variety of areas that can be applied in the design of many types of portable electronic products and buildings. However, in order to commercialize organic solar cells, development of materials for organic solar cells is continuously required.
The present invention provides novel compounds.
The present invention also provides a photoelectric conversion element comprising the above compound.
The present invention also provides a solar cell including the photoelectric conversion element.
The technical problems to be solved in the present invention are not limited to the above-mentioned technical problems, and other technical problems which are not mentioned can be clearly understood by the average technician from the following description.
The present invention provides a compound represented by the following formula (1).
[Chemical Formula 1]
In formula (1)
R3 and R6 are each independently H; Or a linear or branched C 1 to C 20 alkyl group,
R4 and R5 are each independently a linear or branched C 6 to C 22 alkyl group; Or - a (C = O) OC (CH 3) 3,
R is H; Or a linear or branched alkyl group of the type C 1 ~ C 22, X, Y , Z and Q is a bond, each independently; A substituted or unsubstituted C 6 -C 20 arylene group; Aryl vinyl group-substituted or unsubstituted C 8 ~ C 20 ring; Or a substituted or unsubstituted C 2 -C 20 heteroarylene group containing at least one of N, O and S atoms,
l and m are each independently an integer of 0 to 2; o and p are each independently an integer of 0 to 7; r and s are each independently an integer of 0 to 4;
The present invention also provides a positive electrode comprising: a positive electrode; A cathode opposing the anode; And at least one photoactive layer disposed between the anode and the cathode, wherein at least one of the photoactive layers provides the photoelectric conversion element.
The present invention also provides a solar cell including the photoelectric conversion element.
The compound represented by formula (1) of the present invention can be used as an organic semiconductor device, particularly as a material for a solar cell.
The compounds according to one embodiment described herein are excellent in thermal stability.
A solar cell containing a compound according to one embodiment described herein exhibits excellent properties in terms of efficiency and stability.
The compounds according to one embodiment described herein exhibit various HOMO, LUMO level states, various band gaps and device stability depending on substituents.
The compound represented by the formula (1) in the present specification may be used purely in a solar cell or may be mixed with impurities.
The compounds according to one embodiment described herein can be applied by solution coating.
A solar cell comprising a compound according to one embodiment described herein can improve the light efficiency.
The lifetime characteristics of the solar cell can be improved by the thermal stability of the compound according to one embodiment described herein.
1 is a graph showing the UV spectrum of a compound of Synthesis Example 1 dissolved in an organic solvent using an ultraviolet absorption spectrometer.
FIG. 2 is a graph showing the UV spectrum of a compound of Synthesis Example 1 dissolved in an organic solvent by spin coating the substrate and measuring the UV spectrum using an ultraviolet absorption spectroscope. FIG.
3 is a graph showing the oxidation / reduction characteristics of the compound of Synthesis Example 1 using Cyclovoltametry (CV).
4 is a graph showing the results of the measurement of the molecular weight of 2,5-diethylhexyl-3,6-bis (5-bromothiophen-2-yl) pyrrolo [3,4- Ion spectroscopy.
5 is a graph showing the results of the measurement of the molecular weight of 2,5-diethylhexyl-3,6-bis (5-bromothiophen-2-yl) pyrrolo [3,4- 1 < / RTI >
6 is a graph showing the results obtained by the same procedure as in Synthesis Example 1 except that 2,5-diethylhexyl-3,6-bis (9,10-di (2-naphthyl) anthracene- -1,4-dione. ≪ tb >< TABLE >
7 shows the NMR measurement results of the compound synthesized in (1) of Synthesis Example 2. FIG.
8 shows the NMR measurement results of the compound synthesized in (1) of Synthesis Example 3. Fig.
9 shows NMR measurement results of the
10 shows NMR measurement results of the
11 is a current density / voltage curve of Examples 1 to 6;
Hereinafter, the present invention will be described in detail.
An embodiment of the present invention provides a compound of the formula (1).
[Chemical Formula 1]
In
In formula (1),
In Formula (1), X, Y, Z, and Q are each independently a direct bond; A substituted or unsubstituted C 6 -C 20 arylene group; Aryl vinyl group-substituted or unsubstituted C 8 ~ C 20 ring; Or a substituted or unsubstituted C 2 -C 20 heteroarylene group containing at least one of N, O and S atoms.
In formula (1), r and s may each independently be an integer of 0 to 4.
R3 and R6 are each independently H; Or a linear or branched C 1 to C 20 alkyl group,
R4 and R5 are each independently a linear or branched C 6 to C 22 alkyl group; Or - a (C = O) OC (CH 3) 3,
R is H; Or a linear or branched C 1 to C 22 alkyl group,
X, Y, Z and Q are each independently a direct bond; A substituted or unsubstituted C 6 -C 20 arylene group; Aryl vinyl group-substituted or unsubstituted C 8 ~ C 20 ring; Or a substituted or unsubstituted C 2 -C 20 heteroarylene group containing at least one of N, O and S atoms,
l and m are each independently an integer of 0 to 2; o and p are each independently an integer of 0 to 7; r and s are each independently an integer of 0 to 4;
In one embodiment,
In some embodiments of the invention it is in the above-mentioned formula (I), wherein R1, R2, R7 and R8 may be aryl date of each independently represent a substituted or unsubstituted C 6 ~ C 20 ring.
In one embodiment of the present invention,
In one embodiment,
In one embodiment of the present invention,
In one embodiment of the present invention, in
In one embodiment of the present invention, in
In one embodiment of the present invention, in the above formula (1),
In one embodiment of the present invention, in
In one embodiment of the present invention, in
In one embodiment of the present invention in the
In one embodiment of the present invention, the compound of
In one embodiment of the present invention, the compound of
In one embodiment of the present invention, the compound of
In one embodiment of the present invention, the compound of
The compound represented by the formula (1) may be represented by the following formula (2), but is not limited thereto.
(2)
In
R3 and R6 are each independently H; Or a linear or branched C 1 to C 20 alkyl group,
R4 and R5 are each independently a linear or branched C 6 to C 22 alkyl group; Or - a (C = O) OC (CH 3) 3,
R is H; Or a linear or branched C 1 to C 22 alkyl group,
X, Y, Z and Q are each independently a direct bond; A substituted or unsubstituted C 6 -C 20 arylene group; Aryl vinyl group-substituted or unsubstituted C 8 ~ C 20 ring; Or a substituted or unsubstituted C 2 -C 20 heteroarylene group containing at least one of N, O and S atoms,
l and m are each independently an integer of 0 to 2; o and p are each independently an integer of 0 to 7; r and s are each independently an integer of 0 to 4;
In one embodiment,
In one embodiment of the present invention,
In one embodiment of the present invention,
In one embodiment of the invention,
In one embodiment of the present invention,
In one embodiment of the present invention, in
In one embodiment of the present invention, in the above formula (2), R4 and R5 may be the same, but may be the same, linear or branched C 6 -C 22 alkyl group. In this case, there is an advantage that the solution process has a solubility as much as possible. If it has an alkyl group of C 1 to C 5 , it will have a solubility such that the solution process can not be performed.
In one embodiment of the present invention, r and s are each independently an integer of 1 to 4 in the formula (2), whereby the compound of the formula (2) contains a thiophene substituent. In this case, it is possible to strongly absorb light in a wide area. In addition, the intermolecular crystallinity is improved and the light absorption amount is improved, and high charge separation and migration can occur.
In one embodiment of the present invention, in
In one embodiment of the present invention,
In one embodiment of the present invention, in the
In one embodiment of the present invention, the compound of
In one embodiment of the present invention, in the
The compound represented by
(3)
In
R3 and R6 are each independently H; Or a linear or branched C 1 to C 20 alkyl group,
R4 and R5 are each independently a linear or branched C 6 to C 22 alkyl group; Or - a (C = O) OC (CH 3) 3,
R is H; Or a linear or branched C 1 to C 22 alkyl group,
l and m are each independently an integer of 0 to 2; o and p are each independently an integer of 0 to 7; r and s are each independently an integer of 0 to 4;
In one embodiment,
In one embodiment of the present invention,
In one embodiment of the present invention,
In one embodiment of the invention,
In one embodiment of the present invention, in
In one embodiment of the present invention, in
In one embodiment of the present invention, in the above formula (3), R4 and R5 may be the same, but may be the same, linear or branched C 6 -C 22 alkyl group. In this case, there is an advantage that the solution process has a solubility as much as possible. If it has an alkyl group of C 1 to C 5 , it will have a solubility such that the solution process can not be performed.
In one embodiment of the present invention, r and s are each independently an integer of 1 to 4 in the formula (3), whereby the compound of the formula (3) contains a thiophene substituent. In this case, it is possible to strongly absorb light in a wide area. Further, the intermolecular light absorption amount is improved and high charge separation and migration can occur.
In one embodiment of the present invention, in
In one embodiment of the present invention,
In one embodiment of the present invention, in the
In one embodiment of the present invention, the compound of
In one embodiment of the present invention, in the
The compound represented by the formula (1) may be represented by the following formula (4), but is not limited thereto.
[Chemical Formula 4]
In
R3 and R6 are each independently H; Or a linear or branched C 1 to C 20 alkyl group,
R4 and R5 are each independently a linear or branched C 6 to C 22 alkyl group; Or - a (C = O) OC (CH 3) 3,
R is H; Or a linear or branched C 1 to C 22 alkyl group,
l and m are each independently an integer of 0 to 2, and o and p are each independently an integer of 0 to 7.
In one embodiment,
In one embodiment of the present invention,
In one embodiment,
In one embodiment of the present invention,
In one embodiment,
In one embodiment of the present invention, in
In one embodiment of the present invention, in the above formula (4), R4 and R5 may be the same, but may be the same, linear or branched C 6 -C 22 alkyl group. In this case, there is an advantage that the solution process has a solubility as much as possible.
In one embodiment of the present invention, in the above formula (4), R4 and R5 may be the same, but may be the same, linear or branched C 6 -C 22 alkyl group. If it has an alkyl group of C 1 to C 5 , it will have a solubility such that the solution process can not be performed.
In one embodiment of the present invention, in
In one embodiment of the present invention in the
In one embodiment of the present invention, in the
In one embodiment of the present invention, the compound of
In one embodiment of the present invention, the compound of
The compound represented by
[Chemical Formula 5]
The C 6 -C 20 aryl group may be monocyclic or polycyclic and includes, for example, a phenyl group, a tolyl group, a biphenyl group, a pentalenyl group, an indenyl group a naphthyl group, a biphenylenyl group, an anthracenyl group, an azulenyl group, a heptalenyl group, an acenaphthylenyl group acenaphthylenyl group, phenalenyl group, fluorenyl group, methylanthryl group, phenanthrenyl group, triphenylenyl group, pyrenyl group, pyrenyl group, group, a chrysenyl group, an ethyl-chrysenyl group, and a perylenyl group, but the present invention is not limited thereto.
The C 2 -C 20 heteroaryl group containing at least one of the N, O, and S atoms may be monocyclic or polycyclic, and at least one of the aryl groups may be substituted with any one or more of N, O, and S atoms will be.
The C 1 -C 20 alkyl group may be linear or branched and includes, for example, methyl, ethyl, propyl, isopropyl, butyl, and t-butyl groups.
The C 6 -C 22 alkyl group may be linear or branched and includes, for example, linear or branched hexyl, linear or branched heptyl, linear or branched octyl, linear or branched And the like, but the present invention is not limited thereto.
The C 2 -C 20 alkenyl group may be linear or branched and may be an ethenyl group, a propenyl group, an isopropenyl group, a butenyl group, a t-butenyl group, (t-butenyl group), but are not limited thereto.
Wherein the alkylene group is an alkyl group having one hydrogen atom, the alkenylene group is an alkenyl group having one hydrogen atom, and the heteroarylene group is a heteroaryl group having one hydrogen atom.
The arylvinylene group is an aryl group substituted with a vinyl group having one hydrogen atom.
The term "substituted or unsubstituted" in the present specification refers to a group selected from the group consisting of halogen, nitrile, nitro, hydroxy, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, thiol, An alkyl group, an aryl group, an aryl group, a fluorenyl group, a carbazole group, an arylalkyl group, an arylalkenyl group, a heterocyclic group, and an acetylene group Quot; means a hydrogen atom which is substituted with at least one substituent selected from the group consisting of the substituents, or has no substituent group.
The compound of the present invention can be obtained by an alkylation reaction, a Grignard reaction, a Suzuki coupling reaction, a stille reaction, an amination reaction or the like, but the production method is not limited thereto.
The compounds of the present invention absorb light of 300 to 800 nm.
The number average molecular weight of the present invention may be from 500 to 10,000 and, if necessary, from 1,000 to 3,000.
Specifically, when the number average molecular weight is 1,000 to 3,000, the electrical characteristics and the mechanical properties are further improved, and the solubility is improved, which is more advantageous in application of the solution coating method.
In the present specification, the number average molecular weight (Mn) means a value defined by Mn = 1 / (sum (Wi / Mi)).
A photoelectric conversion device comprising a compound represented by
A photoelectric conversion element comprising a hole transporting layer and / or an electron transporting layer according to an embodiment of the present invention is provided.
The present invention relates to a positive electrode; A cathode opposing the anode; And at least one photoactive layer disposed between the anode and the cathode, wherein at least one layer of the photoactive layer comprises a compound represented by
The material of the anode is not particularly limited as long as it is a transparent and conductive material. Specifically, indium tin oxide (ITO), tin oxide (SnO 2 ), zinc oxide (ZnO)
The material of the negative electrode may be a metal having a small work function, but is not limited thereto. For example, metals such as lithium (Li), magnesium (Mg), aluminum (Al), or alloys thereof; Or a multilayer structure such as aluminum: lithium (Al: Li), aluminum: barium fluoride (Al: BaF 2 ), aluminum: barium fluoride: barium (Al: BaF 2 : Ba).
The anode or the cathode may be formed by coating on a substrate. The cathode, the photoactive layer, and the cathode may be sequentially laminated on the substrate, or the cathode, the photoactive layer, and the cathode may be sequentially laminated on the substrate.
At this time, the substrate is not particularly limited as long as it is a substrate commonly used in a photoelectric conversion element, and may be specifically a glass substrate, a transparent plastic substrate, or the like.
The substrate preferably has better physical properties such as transparency, surface smoothness, ease of handling, and waterproofness.
The photoactive layer comprises an electron donor material and an electron acceptor material.
In the present specification, an electron donor is also referred to as an electron donor and generally has a pair of negative or non-covalent electrons, which means donating electrons to a portion lacking a positive charge or electron pair.
The electron donor material in the present specification is an excited electron excited by an electron acceptor having a high electronegativity due to the abundant electron retention property of the molecule itself when light is received in a state where it is mixed with an electron acceptor even though it has no negative or non- And the like.
In this specification, an electron acceptor means accepting electrons from an electron donor material.
The photoactive layer of the present invention may be two or more layers comprising a layer comprising an electron acceptor material and a layer comprising an electron donor material.
The photoactive layer of the present invention may be a single layer of a mixture of an electron acceptor material and an electron donor material.
The photoactive layer may comprise an electron donor material and an electron acceptor material. As the electron donor, the aromatic compound of
The electron acceptor material may be a fullerene, a fullerene derivative, a heterocyclic compound, a semiconductor element, a semiconducting compound, an inorganic compound, or a combination thereof. Specifically, PC 61 BM (phenyl C 61 -butyric acid methyl ester) BM 71 may be (phenyl C 71 -butyric acid methyl ester ).
The photoactive layer may form a bulk heterojunction with the electron donor material and the electron acceptor material. The electron donor material and the electron acceptor material may be mixed at a ratio (w / w: mass ratio) 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.
The thickness of the photoactive layer may be 10 to 10,000 angstroms, but is not limited thereto.
In one embodiment of the present invention, a hole transporting layer disposed between an anode and a photoactive layer; And an electron transporting layer disposed between the cathode and the photoactive layer.
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.
For example, the hole transport layer material may be selected from the group consisting of PEDOT: PSS (poly (3,4-ethylenediocy- thiophene) doped with poly (styrenesulfonic acid) Phenyl- [1,1'-biphenyl] -4,4'-diamine (TPD). The electron transport layer material may include aluminum trihydroxyquinoline (Alq 3 ), a 1,3,4-oxadiazole derivative such as 2- (4-biphenyl) -5-phenyl-1,3,4-oxadiazole (4-bipheyl) -5-phenyl-1,3,4-oxadiazole, PBD), a quinoxaline derivative such as 1,3,4-tris [(3-phenyl-6-trifluoromethyl) 3-phenyl-6-trifluoromethyl) quinoxaline-2-yl] benzene, TPQ), triazole derivatives, and the like.
The hole transport layer material and / or the electron transport layer material may include a compound represented by the formula (1).
The electron transporting layer and the hole transporting layer efficiently transport electrons and holes to the photoelectric conversion polymer, respectively, thereby enhancing the probability of transfer of charges generated to the electrodes.
The photoelectric conversion element of the present invention is an element that converts a light signal into an electric signal by using a photoelectric effect.
The photon effect is a phenomenon in which, when a material is irradiated with light, electrons in the material absorb light energy and emit photoelectrons. The photoelectric effect includes the external photoelectric effect that photoelectrons are emitted from the solid surface, the photoionization that photoelectrons are emitted from electrons or molecules, the internal photoelectric effect that the conduction electrons are generated inside the solid such as the insulator or semiconductor, And a photovoltaic effect in which an electromotive force is generated. With this photoelectric effect, you can turn a light signal into an electrical signal or turn light energy into electrical energy.
Using these properties, a photovoltaic tube, a photodiode, a phototransistor, a photoconductive element, a photovoltaic cell, an organic solar cell, an inorganic solar cell, and the like including the photoelectric conversion element of the present invention can be manufactured.
As an embodiment of the present invention, there is provided a solar cell including the photoelectric conversion element.
The solar cell is a device capable of directly converting solar energy into electrical energy by applying a photovoltaic effect. Solar cells can be divided into inorganic solar cells and organic solar cells depending on the material constituting the thin film.
The solar cell of the present invention may be an organic solar cell.
In the organic solar cell, a p-type semiconductor forms an exciton paired with electrons and holes by photoexcitation, and the exciton can be 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.
The organic solar cell may be a bi-layer p-n junction organic solar cell and a bulk heterojunction (BHJ) junction depending on the structure of the photoactive layer. A bi-layer p-n junction type organic solar cell includes a photoactive layer consisting of two layers of a p-type semiconductor thin film and an n-type semiconductor thin film. A bulk heterojunction junction type organic solar cell includes a photoactive layer in which an n-type semiconductor and a p-type semiconductor are blended.
The organic solar cell is characterized in that efficiency is improved remarkably due to a new device configuration and a change in process conditions. Therefore, in order to replace conventional materials, an electron donor material having a low band gap and a new electron donor material having a good charge mobility are included.
Many researches have been conducted on p-type conductive polymers, and as a result, a number of polymers having a high solubility and absorbing a large part of the solar spectrum with a low band gap have been developed. In addition, the efficiency of the bulk heterojunction device through combination with an electron acceptor material such as a fullerene derivative is at the late 8% level. However, since the reproducibility is not exhibited in terms of polymer production, it has limitations in the process. Therefore, for commercialization, development of reproducible materials should be prioritized, and new photoactive materials having improved electronic properties have been demanded.
However, the organic solar cell according to one embodiment of the present invention exhibits excellent characteristics in terms of increase in efficiency and increase in stability. The compound represented by formula (1) of the present invention has excellent thermal stability, deep HOMO level, various bandgaps, various LUMO level states and electronic stability, and exhibits excellent characteristics. The compound represented by the formula (1) of the present invention is excellent in solubility and can be applied by a solution coating method in an organic solar cell. In addition, the organic solar cell using the compound represented by
The role of the photoactive material that absorbs light to generate energy in the organic solar cell is mainly performed by the electron donor material. Therefore, it is desirable that the electron donor material is capable of absorbing light in a wide spectral range so as to absorb as much sunlight as possible.
The compound according to an embodiment of the present invention can absorb a wavelength of a solar light corresponding to a wide range from 300 to 800 nm, and thus can be used as an electron donor material of an organic solar cell.
The organic solar cell of the present specification can be produced by materials and methods known in the art, except that the photoactive layer includes the compound of the present invention, i.e., the compound represented by the above formula (1).
The organic solar cell of the present specification can be produced by materials and methods known in the art except that the hole transporting layer and / or the electron transporting layer contains the compound of the present invention, i.e., the aromatic compound represented by the above formula (1) .
A method of fabricating an organic solar cell according to an embodiment of the present invention includes the steps of preparing a substrate, forming an anode on one region of the back surface of the substrate, forming a photoactive layer on the anode, And forming a cathode.
A method of fabricating an organic solar cell according to an embodiment of the present invention includes the steps of preparing a substrate, forming a cathode on one region of a back surface of the substrate, forming a photoactive layer on the cathode, And forming an anode.
The method of manufacturing an organic solar cell according to one embodiment of the present invention includes the steps of preparing a substrate, forming an anode on one region of the back surface of the substrate, forming a hole transport layer on the anode, Forming a photoactive layer on the transport layer, forming an electron transport layer on the photoactive layer, and forming a cathode on the electron transport layer.
A method of manufacturing an organic solar cell according to an embodiment of the present invention includes the steps of preparing a substrate, forming a cathode on one region of the back surface of the substrate, forming an electron transport layer on the cathode, Forming a photoactive layer on the transport layer, forming a hole transport layer on the photoactive layer, and forming an anode on the hole transport layer.
The organic solar cell of the present invention can be produced, for example, by sequentially laminating an anode, a photoactive layer and a cathode on a substrate.
In addition, the organic solar cell of the present specification can be produced by sequentially laminating an anode, a hole transporting layer, a photoactive layer, an electron transporting layer and a cathode on a substrate.
At this time, each layer may be coated by a wet process such as gravure printing, offset printing, screen printing, ink jet, spin coating and spray coating, but not limited thereto.
The following Synthesis Examples and Examples are described in detail. However, the following Synthesis Examples and Examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.
≪ Synthesis Example 1 &
(1) 2,5- Diethylhexyl -3,6- Dithiophene -2 days Pyrrolo [3,4-c] pyrrole -1,4- Dion's synthesis
Under a nitrogen atmosphere, a 500 ml two-neck round bottom flask was charged with 3,6-dithiophen-2-yl-2,5-dihydropyrrolo [3,4-c] pyrrole- 2-yl-2,5-dihydropyrrolo [3,4-c] pyrrole-1,4-dione) (13 g, 43.3 mmol) was added to 300 mL of dimethylformamide (DMF) Potassium carbonate (K 2 CO 3 ) (4 eq.) Was added and stirred at 140 ° C. Then, 2-ethylhexylbromomide (4.6 eq.) Was added thereto and stirred for 12 hours. The reaction was stopped by thin layer chromatography (TLC) confirmation, washed with ice water, filtered through a filter, and then subjected to silica column chromatography with chloroform to obtain 2,5-diethylhexyl-3,6- Yl] pyrrolo [3,4-c] pyrrol-1, 4-dione (18.01 g, Y = 79%).
(2) 2,5- Diethylhexyl -3,6-bis (5- Bromothiophene -2 days) Pirolo [3,4-c] Pirolo -1,4-dione Synthesis
Under a nitrogen atmosphere, 3.56 g of 2,5-diethylhexyl-3,6-dithiophen-2-ylpyrrolo [3,4-c] pyrrolo-1,4-dione was added to a 500 ml two- After dissolving in 150 ml of chloroform (CF), 2.50 g of N-bromosuccinimide (NBS) was added, a small amount of acetic acid was added, and the mixture was stirred at room temperature for 12 hours. After the reaction is completed by confirming thin-layer chromatography (TLC), the solvent is concentrated to about 20 ml under reduced pressure, and ethanol is added to precipitate a solid to obtain a compound through a filter. The solids thus separated are again dissolved in chloroform, and silica is used to obtain a short column to obtain a silica gel powder. (70% yield). The results of the Ms spectrum measurement are shown in FIG. 4, and the results of 1 HNMR measurement are shown in FIG.
1 H NMR (CDCl 3 , 400 MHz): 8.64 (d, 2H), 7.18 (d, 2H), 3.91 (m, 4H), 1.82 ), MS: [M = H] < + > = 683.1
(3) 2,5- Diethylhexyl -3,6-bis (9,10- Di (2-naphthyl) anthracene -2 days) Pyrrole in[ 3,4-c] pyrrolo -1,4- Dion's synthesis
To a 250 ml two-necked round bottom flask under a nitrogen atmosphere was added 2,5-diethylhexyl-3,6-bis (5-bromothiophen-2-yl) pyrrolo [3,4- 830 mg of 2- (4,4,5,6-tetramethyl-1,3,2-dioxaborolane) -9,10-di (2-naphthyl) anthracene was added to 200 ml of tetrahydrofuran (THF) After that, dissolve completely while applying heat. Then, tetrakis triphenylphosphine palladium (Pd (0)) was rapidly added and stirred sufficiently. Then, 2M potassium carbonate (K 2 CO 3 ) was injected slowly using a syringe, Lt; RTI ID = 0.0 > 115 C < / RTI > and stirred for 24 hours. The MS spectrum measurement result is shown in Fig.
MS: [M + H] < + > = 1381.6
<Experimental Example 1>
UV spectroscopy was carried out using UV 2550 shimadzu as a UV / vis spectrophotometer in order to observe the optical characteristics of the compound prepared in Synthesis Example 1, after the UV spectrum was measured in FIGS. 1 and 2.
1 was determined by dissolving the compound of Synthesis Example 1 in toluene, and the band gap of the solution was measured to 1.8 Ev at 500 ~ 700nm of the π-π * transition in the short-wavelength absorption at 300 ~ 500nm and a conjugated molecule Is observed.
FIG. 2 shows the results of measurement after spin-coating the compound of Synthesis Example 1 on a quartz substrate by dissolving in the solution and showing a broad absorption band ranging from 500 to 800 nm with red shift compared with the solution state. Thus, it is considered that the intermolecular interaction increases and the light absorption boundary point shifts to the long wavelength, and the band gap becomes smaller.
<Experimental Example 2>
In order to observe the electrochemical properties of the compound prepared in Synthesis Example 1, the oxidation / reduction characteristics using Cyclovoltametry (CV) were observed.
As shown in FIG. 3, the compound of Synthesis Example 1 showed an oxidation level in a range of 0.82 V in CV, and it was confirmed that the molecule exists in a more stable state in the measurement. This shows that the stability of anthracene is very good.
≪ Synthesis Example 2 &
(1) 3,6- Bis (5- Bromothiophene -2-yl) -2,5-bis (2- Hexyldecyl ) Pirolo ([3,4-c] pyrrole-1,4- (2H, 5H) -dione (3,6- Bis (5- bromothiphen -2- yl Synthesis of 2,5-bis (2-hexyldecyl) pyrrolo ([3,4-c] pyrrole-1,4- (2H, 5H)
Was synthesized in the same manner as in Synthesis Example 1 (1) and (2) except that 7-bromopentadecane was used instead of 2-ethylhexyl bromide.
(2) 3,6- Bis (5- bromothiphen -2- yl ) 2,5-bis (2- hexyldecyl ) pyrrolo ([3,4-c] pyrrole-1,4- (2H, 5H) -dione (3,6- Bis (5- Bromothiophene -2-yl) -2,5-bis (2- Hexyldecyl ) Pirolo ([3,4-c] pyrrole-l, 4- (2H, 5H) Dion's synthesis
The compound (3) of Synthesis Example 1 was synthesized in the same manner except that the compound synthesized in Synthesis Example 2 (1) was used instead of the compound prepared in Synthesis Example 1 (2).
≪ Synthesis Example 3 &
(1) 3,6- Bis (5- Bromothiophene -2-yl) -2,5-bis (2- Octyldodecyl ) Pirolo ([3,4-c] pyrrole-l, 4- (2H, 5H) Dion (3,6- Bis (5- bromothiphen -2- yl Synthesis of 2,5-bis (2-octyldodecyl) pyrrolo ([3,4-c] pyrrole-1,4- (2H, 5H)
Synthesis was conducted in the same manner as in Synthesis Example 1 except that 9- (bromomethyl) nonadecane was used in place of 2-ethylhexyl bromide in (1) and (2).
(2) 3,6- Bis (5- Bromothiophene -2-yl) -2,5-bis (2- Octyldodecyl ) Pirolo ([3,4-c] pyrrole-1,4- (2H, 5H) -dione (3,6- Bis (5- bromothiphen -2- yl Synthesis of 2,5-bis (2-octyldodecyl) pyrrolo ([3,4-c] pyrrole-1,4- (2H, 5H)
The compound (3) of Synthesis Example 1 was synthesized in the same manner except that the compound synthesized in Synthesis Example 3 (1) was used instead of the compound prepared in Synthesis Example 1 (2).
≪ Synthesis Example 4 &
(1) Synthesis of
(5 g, 8.9844 mmol), 2-bromothiophene, 2.19 g, 13.4766 mmol, Pd (PPh 3 ) 4 (0.46, 3 mol%) in a 2-neck round bottom flask, ), a 2M potassium carbonate (K 2 CO 3) (put 10ml) in tetrahydrofuran (the mixture was stirred while placed in THF) is the temperature. magnesium sulfate the extracting organic layer with water and MC after the reaction was conducted (MgSO 4) After drying, the powder was obtained with a silica column (eluent: Hx / MC = 10/3) (yield: 78%).
The well-dried powder (3.0 g, 5.8516 mmol) was added to CF and stirred at room temperature. After light protection using aluminum foil, NBS (1.14 g, 1.05 eq.) Was added and stirred for 18 hours. After confirming with TLC, a silica column (eluent: Hx / MC = 10/3) was used to obtain a powder (yield: 87%).
The well dried powder (3.14 g, 5.3000 mmol) was dissolved in 250 ml of tetrahydrofuran and the temperature was lowered to -70 ° C. to which n-butyllithium (n-BuLi) (2.5 M in hexane, 3.2 ml) Lt; / RTI > 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 1.48 g). After the reaction, a silica column (eluent: Hx / MC = 10/5) was used to obtain a powder (yield: 67%).
(2) Synthesis
(4) was obtained in the same manner as in Synthesis Example 2 (2) except that 2- (4,4,5,6-tetramethyl-1,3,2-dioxaborolane) -9,10-di Was synthesized in the same way except that the compound synthesized in (1) was used.
MS: [M + H] < + > = 1545.1
≪ Synthesis Example 5 &
(4) was obtained in the same manner as in Synthesis Example 2 (2) except that 2- (4,4,5,6-tetramethyl-1,3,2-dioxaborolane) -9,10-di Was synthesized in the same way except that the compound synthesized in (1) was used.
MS: [M + H] < + > = 1769.1
≪ Synthesis Example 6 &
(2) of Synthesis Example 3 was carried out in the same manner as in Synthesis Example 4 (2) except for using 2- (4,4,5,6-tetramethyl-1,3,2-dioxaborolane) -9,10-di Was synthesized in the same way except that the compound synthesized in (1) was used.
MS: [M + H] < + > = 1881.7
<Experimental Example 3>
Preparation and characterization of organic solar cell
As an embodiment using the compound synthesized in the above Synthesis Examples 1-6, respectively, and the electron donor [6, 6] -phenyl -C 60 butyric acid methyl ester ([6,6] - phenyl-
The photoelectric conversion characteristics of the organic solar cell thus prepared were measured and the results are shown in the following table.
* Voc (V): Open voltage, Jsc (mA / cm 2 ): Short circuit current, FF (%): Fill factor, PCE (%
The open-circuit voltage and the short-circuit current are the X-axis and Y-axis intercepts in the fourth quadrant of the voltage-current density curve, respectively. The higher the two values, the higher the efficiency of the solar cell is. The fill factor is the width of the rectangle that can be drawn inside the curve divided by the product of the short-circuit current and the open-circuit voltage. The energy conversion efficiency can be obtained by dividing these three values by the intensity of the irradiated light, and a higher value is preferable.
The compound of the present invention which is an electron donor of the photoactive layer absorbs more light including thiophene and has an appropriate solubility including an alkyl chain, so that energy conversion efficiency is high.
<Experimental Example 4>
Example Current density / voltage curve of 1 to 6
Examples 1 to 6 mean respective organic solar cells using the compounds synthesized in Synthesis Examples 1 to 6, and the results are shown in Fig.
Claims (22)
(3)
In formula (3)
R1, R2, R7 and R8 are naphthyl groups,
R <9> and R <10> are H,
R3 and R6 are H,
R4 and R5 are each independently a linear or branched C 1 to C 20 alkyl group,
l and m are each independently an integer of 0 to 2; o and p are each independently an integer of 0 to 7; r and s are each independently an integer of 0 to 4;
[Chemical Formula 4]
In Formula 4,
R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10, l, m, o and p are as defined in the formula (1).
Wherein at least one layer of the photoactive layer comprises a compound according to any one of claims 1, 7, 9 to 12 and 14.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020130064990 | 2013-06-05 | ||
| KR20130064990 | 2013-06-05 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20140143323A KR20140143323A (en) | 2014-12-16 |
| KR101676526B1 true KR101676526B1 (en) | 2016-11-16 |
Family
ID=52674196
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020140065280A KR101676526B1 (en) | 2013-06-05 | 2014-05-29 | Novel compound and photoelectric conversion device having the same |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR101676526B1 (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010115767A1 (en) | 2009-04-08 | 2010-10-14 | Basf Se | Pyrrolopyrrole derivatives, their manufacture and use as semiconductors |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101008035B1 (en) | 2007-06-14 | 2011-01-13 | 주식회사 엘지화학 | New compound semiconductor material and producing method thereof, and solar cell using the same |
| CA2700713A1 (en) * | 2007-10-09 | 2009-04-16 | Zhimin Hao | Pyrrolopyrrole derivatives, their manufacture and use |
| BRPI1011853A2 (en) * | 2009-05-27 | 2019-09-24 | Basf Se | organic semiconductor polymer, material, layer or component, semiconductor device, processes for preparing an organic semiconductor device, and a polymer, and, use of the organic semiconductor polymer and / or material, layer or component. |
-
2014
- 2014-05-29 KR KR1020140065280A patent/KR101676526B1/en active IP Right Grant
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010115767A1 (en) | 2009-04-08 | 2010-10-14 | Basf Se | Pyrrolopyrrole derivatives, their manufacture and use as semiconductors |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20140143323A (en) | 2014-12-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | The principles, design and applications of fused-ring electron acceptors | |
| KR101677841B1 (en) | Heterocyclic compound and organic solar cell comprising the same | |
| Cui et al. | Naphtho [1, 2-b: 4, 3-b′] dithiophene-based hole transporting materials for high-performance perovskite solar cells: molecular engineering and opto-electronic properties | |
| JP5851268B2 (en) | Material for organic thin film solar cell element and organic thin film solar cell using the same | |
| KR20130090736A (en) | Heteroaromatic compound and organic solar cell comprising the same | |
| KR101713417B1 (en) | Fused ring derivative and organic solar cell comprising the same | |
| JPWO2013035303A1 (en) | Organic thin film solar cell materials | |
| KR101592628B1 (en) | Imidazole compound and organic electronic device using the same | |
| KR101815755B1 (en) | Phenazine derivatives with the extended conjugated structure and applied to the organic photovoltaic polymers | |
| KR101595147B1 (en) | Aromatic compound and organic solar cell comprising the same | |
| KR101749379B1 (en) | Copolymer, manufacturing method the same and organic solar cell comprising the copolymer | |
| JP2014177409A (en) | Anthradithiophene compound, organic thin film solar cell material including the anthradithiophene compound, and organic thin film solar cell using the organic thin film solar cell material | |
| JP6200096B2 (en) | Copolymer and organic solar cell including the same | |
| Bhat et al. | Versatile aza‐BODIPY‐based low‐bandgap conjugated small molecule for light harvesting and near‐infrared photodetection | |
| KR101552756B1 (en) | Copolymer and organic solar cell using the same | |
| KR101562426B1 (en) | Heterofused-ring compound and organic solar cell comprising the same | |
| KR101660086B1 (en) | Aromatic compound and organic solar cell comprising the same | |
| KR101716035B1 (en) | Fused ring derivative and organic solar cell comprising the same | |
| KR101676526B1 (en) | Novel compound and photoelectric conversion device having the same | |
| KR102560363B1 (en) | Polymer, composition comprising the same and organic solar cell comprising the same | |
| KR101676904B1 (en) | Copolymer and organic solar cell comprising the same | |
| KR101930279B1 (en) | Preparation of phenazine derivatives with increased solubility and conjugated polymers consisting of phenazine derivatives for organo photoelectric conversion device | |
| KR102069409B1 (en) | Copolymer and organic solar cell comprising the same | |
| KR20190055727A (en) | Heterocyclic compound and organic photovoltaic device comprising the same | |
| KR101514819B1 (en) | organic semiconductor compound, manufacturing method thereof, and organic electronic device that contains it |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| AMND | Amendment | ||
| E601 | Decision to refuse application | ||
| AMND | Amendment | ||
| X701 | Decision to grant (after re-examination) | ||
| GRNT | Written decision to grant |