KR101815755B1 - Phenazine derivatives with the extended conjugated structure and applied to the organic photovoltaic polymers - Google Patents
Phenazine derivatives with the extended conjugated structure and applied to the organic photovoltaic polymers Download PDFInfo
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- KR101815755B1 KR101815755B1 KR1020160030388A KR20160030388A KR101815755B1 KR 101815755 B1 KR101815755 B1 KR 101815755B1 KR 1020160030388 A KR1020160030388 A KR 1020160030388A KR 20160030388 A KR20160030388 A KR 20160030388A KR 101815755 B1 KR101815755 B1 KR 101815755B1
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- 0 C**c1c(*)c(*)c(*C)c2c1nc(c(CCCCC1)c1c1c3CCCCCCC1)c3n2 Chemical compound C**c1c(*)c(*)c(*C)c2c1nc(c(CCCCC1)c1c1c3CCCCCCC1)c3n2 0.000 description 2
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Abstract
The present invention relates to a novel organic photoelectric conversion polymer and / or monomolecule, a method for producing the same, and an organic photovoltaic device (OPV device) employing a novel organic photoelectric conversion polymer as an active layer. According to the present invention, The introduction of a compound improves the light absorption characteristics to a long wavelength and enables a series of manufacturing processes of an organic photoelectric conversion polymer and / or a single molecule having excellent photoelectric conversion efficiency having charge transfer characteristics through effective electron transfer by effective stacking between molecules And provides an organic photovoltaic device (OPV device) employing the organic photoelectric conversion polymer as a photoactive layer, it can be used as a next generation organic photoelectric device exhibiting stable photoelectric conversion efficiency and excellent in conversion efficiency Have an effect
Description
The present invention relates to an organic photoelectric conversion polymer and an organic photoelectric device including the same.
In order to solve the problem of global warming, the demand for environmentally friendly energy sources using sunlight, wind power, water power, wave power, geothermal power, etc. is rapidly increasing. Solar power generation using dual solar power is an unlimited source of energy without the risk of environmental pollution. For example, the actual amount of solar energy available on the planet is 600TW (1TW = 1 × 1,012 Watts), which is a tremendous amount that is estimated at 60 times the energy used today. For this reason, research on photoelectric devices using solar light has been conducted for several decades, and inorganic solar cells using silicon wafers are now commercially available for power generation. Unlike inorganic solar cells, energy sources for low-cost electronic products, flexible solar cells combined with flexible displays, or organic photovoltaic devices that can be worn are attracting attention as next-generation solar cells.
Photovoltaic (PV) of an organic photoelectric device is a phenomenon that a photon is separated into an electron and a hole in an organic active layer which receives sunlight to form an exciton, It means that it moves to the interface of the acceptor material and is separated by the difference of each LUMO level to produce electricity. In 1987, Tang et al. Of Eastman Kodak Co. produced a device with the structure of ITO / CuPc (30 nm) / PV (50 nm) / Ag and formed a 0.95% Of the photoelectric conversion efficiency of the photoelectric conversion device. Recently, the efficiency of 10% has been achieved.
In general, for high efficiency photoelectric conversion efficiency, photon harvesting characteristics capable of absorbing a wide range of sunlight must be preceded. In order to prevent recombination of excitons, effective electron and hole of the photoactive layer and electrode, polymer and fullerene It is necessary to design the structure of the polymer and to effectively stack the molecules to enable transport. For this purpose, a molecular structure capable of providing effective molecular stacking to the main chain of the polymer is introduced to increase the charge mobility by inducing stacking between the polymers.
Therefore, a novel photoelectric conversion polymer using a phenazine derivative having a heterocycle-bonded property having excellent photon harvesting and charge mobility as an active layer of an organic photoelectric device of a push-pull structure And development of an organic photoelectric device using the same.
It is an object of the present invention to provide an organic photoelectric conversion polymer having excellent photoelectric conversion efficiency and having high charge mobility due to effective stacking between molecules by expanding a conjugated structure and an organic photoelectric conversion device including a photoelectric conversion layer containing the same, An organic photovoltaic device (OPV device).
In order to solve the above problems,
There is provided a polymer for organic photoelectric conversion comprising a phenazine derivative represented by the following formula (1).
[Chemical Formula 1]
In Formula 1,
Y represents a cyclic structure containing X 1 and X 2 respectively in the structure,
X 1 and X 2 are independently of each other C, O, S or Se,
Any one of X 1 and X 2 is C and the other is O, S or Se,
T is a p-type molecule or an n-type molecule having electron accepting properties,
A is a 5 to 20-membered heteroarylene group containing at least one heteroatom selected from the group consisting of N, O, S and Se,
R 1 and R 2 are independently of each other hydrogen; An alkyl group having 1 to 25 carbon atoms; An alkoxy group having 1 to 25 carbon atoms; An aryl group having 5 to 30 carbon atoms; Thiophene group; A cellonopene group; A roll roll; Or a thiazole group,
At least one of the hydrogen atoms present in the aryl group, thiophene group, cyclophenylene group, pyrrole group and thiazole group is an alkyl group having 1 to 25 carbon atoms, an alkoxy group having 1 to 25 carbon atoms, or an aryl group having 1 to 30 carbon atoms Substituted or unsubstituted,
m and n are each independently an integer of 10 to 100,000.
Further, according to the present invention,
A first electrode, a hole transport layer, a photoelectric conversion layer, and a second electrode,
Wherein the photoelectric conversion layer comprises an organic photoelectric conversion polymer represented by the following formula (1).
[Chemical Formula 1]
In Formula 1,
Y represents a cyclic structure containing X 1 and X 2 respectively in the structure,
X 1 and X 2 are independently of each other C, O, S or Se,
Any one of X 1 and X 2 is C and the other is O, S or Se,
T is a p-type molecule or an n-type molecule having electron accepting properties,
A is a 5 to 20-membered heteroarylene group containing at least one heteroatom selected from the group consisting of N, O, S and Se,
R 1 and R 2 are independently of each other hydrogen; An alkyl group having 1 to 25 carbon atoms; An alkoxy group having 1 to 25 carbon atoms; An aryl group having 5 to 30 carbon atoms; Thiophene group; A cellonopene group; A roll roll; Or a thiazole group,
At least one of the hydrogen atoms present in the aryl group, thiophene group, cyclophenylene group, pyrrole group and thiazole group is an alkyl group having 1 to 25 carbon atoms, an alkoxy group having 1 to 25 carbon atoms, or an aryl group having 1 to 30 carbon atoms Substituted or unsubstituted,
m and n are each independently an integer of 10 to 100,000.
The present invention provides an organic photoelectric conversion polymer having excellent photoelectric conversion efficiency with high photon harvesting characteristics and high charge mobility due to stacking between molecules, thereby making it possible to employ the polymer as a photoelectric conversion layer The organic photoelectric device can be easily manufactured by a relatively simple process such as spin coating, and by selecting an appropriate electron donor or electron acceptor material and using the intermolecular interaction, HOMO level and LUMO level show stable photoelectric conversion efficiency and can be usefully used as a next generation organic photoelectric device having excellent photoelectric conversion efficiency.
1 is a cross-sectional view of an organic photoelectric device according to Examples 3 and 4 of the present invention.
2 is a light absorption spectrum of Examples 1 and 2 and Comparative Example 1 according to the present invention.
3 is a cyclic voltammetry (CV) graph in which electrochemical characteristics of Examples 3 and 4 were evaluated.
4 is a graph showing the efficiencies of organic optoelectronic devices according to Examples 3 and 4 and Comparative Example 2. FIG.
Fig. 5 is a graph of external quantum efficiency (EQE) of organic optoelectronic devices according to Examples 3 and 4 and Comparative Example 2. Fig.
6 is a compound represented by the general formula (7) contained in the polymer for organic photoelectric conversion of the present invention.
While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail.
It should be understood, however, that the invention is not intended to be limited to the particular embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.
The terms first, second, etc. may be used to describe various elements, but the elements should not be limited by terms. Terms are used only for the purpose of distinguishing one component from another.
The terminology used in this application is used only to describe a specific embodiment and is not intended to limit the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise.
In the present application, the terms "comprises" or "having" and the like are used to specify that there is a feature, a number, a step, an operation, an element, a component or a combination thereof described in the specification, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.
Therefore, the configurations shown in the embodiments described herein are merely the most preferred embodiments of the present invention and are not intended to represent all of the technical ideas of the present invention. Therefore, various equivalents And variations.
The present invention relates to an organic photoelectric conversion device having excellent photoelectric conversion efficiency with charge transfer characteristics through efficient electron transfer by alternately arranging two materials having different electron affinities around a heterocyclic compound having improved absorption characteristics and effective stacking An organic photovoltaic device (OPV device) that provides a series of processes for producing a polymer and / or a single molecule and employs the organic photoelectric conversion polymer as a photoactive layer.
Hereinafter, the organic photoelectric conversion polymer according to the present invention will be described in detail.
The organic photoelectric conversion polymer according to the present invention may include a phenazine derivative represented by the following formula (1).
[Chemical Formula 1]
In Formula 1,
Y represents a cyclic structure containing X 1 and X 2 respectively in the structure,
X 1 and X 2 are independently of each other C, O, S or Se,
Any one of X 1 and X 2 is C and the other is O, S or Se,
T is a p-type molecule or an n-type molecule having electron accepting properties,
A is a 5 to 20-membered heteroarylene group containing at least one heteroatom selected from the group consisting of N, O, S and Se,
R 1 and R 2 are independently of each other hydrogen; An alkyl group having 1 to 25 carbon atoms; An alkoxy group having 1 to 25 carbon atoms; An aryl group having 5 to 30 carbon atoms; Thiophene group; A cellonopene group; A roll roll; Or a thiazole group,
At least one of the hydrogen atoms present in the aryl group, thiophene group, cyclophenylene group, pyrrole group and thiazole group is an alkyl group having 1 to 25 carbon atoms, an alkoxy group having 1 to 25 carbon atoms, or an aryl group having 1 to 30 carbon atoms Substituted or unsubstituted,
m and n are each independently an integer of 10 to 100,000.
In formula (1) according to the present invention, A may be a spacer, and A is a spacer, which may be a simple bond, a substituted or unsubstituted alkylene having 1 to 20 carbon atoms, a substituted or unsubstituted C2- Substituted or unsubstituted cycloalkylene having 3 to 13 carbon atoms, substituted or unsubstituted arylene having 6 to 40 carbon atoms, substituted or unsubstituted arylene having 7 to 15 carbon atoms, A substituted or unsubstituted aralkylene having 2 to 20 carbon atoms, and a heteroarylene having 5 to 20 atoms, and is not limited thereto. Specifically, in the present invention, A may be a heteroarylene having 5 to 20 atoms, and more specifically, A is a heteroarylene having 5 to 20 atoms including at least one heteroatom selected from the group consisting of N, O, S and Se Or a heteroarylene group.
As one example, the phenazine derivative represented by the formula (1) may be any one or more of the compounds represented by the following formulas (2) and (3).
(2)
(3)
In the
X < 3 > is O, S or Se,
T is a p-type molecule or an n-type molecule having electron accepting properties,
A is a 5 to 20-membered heteroarylene group containing at least one heteroatom selected from the group consisting of N, O, S and Se,
R 1 and R 2 are independently of each other hydrogen; An alkyl group having 1 to 25 carbon atoms; An alkoxy group having 1 to 25 carbon atoms; An aryl group having 5 to 30 carbon atoms; Thiophene group; A cellonopene group; A roll roll; Or a thiazole group,
At least one of the hydrogen atoms present in the aryl group, thiophene group, cyclophenylene group, pyrrole group and thiazole group is an alkyl group having 1 to 25 carbon atoms, an alkoxy group having 1 to 25 carbon atoms, or an aryl group having 1 to 30 carbon atoms Substituted or unsubstituted,
m and n are each independently an integer of 10 to 100,000.
As an example, in the general formulas (2) and (3) according to the present invention, X 3 is S,
R 1 and R 2 are independently of each other hydrogen; An alkyl group having 1 to 25 carbon atoms; Or an alkoxy group having 1 to 25 carbon atoms.
As one example, the p-type molecular according to the present invention is not particularly limited as long as it has electron-donating properties. For example, it may be one or more kinds selected from compounds represented by the following general formula (4) .
[Chemical Formula 4]
In the compound represented by the general formula (4)
R 1 to R 108 independently from each other are hydrogen; halogen; An alkyl group having 1 to 25 carbon atoms; An alkoxy group having 1 to 25 carbon atoms; An aryl group having 5 to 30 carbon atoms; Thiophene group; A cellonopene group; A roll roll; Or a thiazole group,
At least one of the hydrogen atoms present in the aryl group, thiophene group, cyclophenylene group, pyrrole group and thiazole group is an alkyl group having 1 to 25 carbon atoms, an alkoxy group having 1 to 25 carbon atoms, or an aryl group having 1 to 30 carbon atoms Substituted or unsubstituted.
As an example, the n-type molecule having the electron accepting property according to the present invention is not particularly limited as long as it has an electron accepting property. For example, it may be one or more kinds selected from the compounds represented by the following general formula (5) .
[Chemical Formula 5]
In the compound represented by Formula 5,
R 1 to R 55 independently from each other are hydrogen; halogen; An alkyl group having 1 to 25 carbon atoms; An alkoxy group having 1 to 25 carbon atoms; An aryl group having 5 to 30 carbon atoms; Thiophene group; A cellonopene group; A roll roll; Or a thiazole group,
At least one of the hydrogen atoms present in the aryl group, thiophene group, cyclophenylene group, pyrrole group and thiazole group is an alkyl group having 1 to 25 carbon atoms, an alkoxy group having 1 to 25 carbon atoms, or an aryl group having 1 to 30 carbon atoms Substituted or unsubstituted.
As an example, A in the formulas (1) to (3) according to the present invention may mean a spacer, and the kind thereof is not particularly limited, but specifically, in the present invention, A (spacer) And the like.
[Chemical Formula 6]
In the compound represented by Formula 6,
R 1 to R 26 independently of one another are hydrogen; halogen; An alkyl group having 1 to 25 carbon atoms; An alkoxy group having 1 to 25 carbon atoms; An aryl group having 5 to 30 carbon atoms; Thiophene group; A cellonopene group; A roll roll; Or a thiazole group,
At least one of the hydrogen atoms present in the aryl group, thiophene group, cyclophenylene group, pyrrole group and thiazole group is an alkyl group having 1 to 25 carbon atoms, an alkoxy group having 1 to 25 carbon atoms, or an aryl group having 1 to 30 carbon atoms Substituted or unsubstituted.
As one example, the phenazine derivative represented by the formula (1) according to the present invention may be a compound represented by the following formula (7) or (8).
(7)
[Chemical Formula 8]
In the above formulas (7) and (8)
and a is an integer of 10 to 100,000.
Specifically, the phenazine derivative according to the present invention may be alkoxydiocyanophenazine, and more specifically alkoxy-dithieno [3,2-a: 2 ', 3'-c} phenazine and alkoxy-dithieno [ 3-a: 3 ', 2'-c} phenazine.
Further, the present invention provides a method for producing a monomolecular and / or polymer for organic photoelectric conversion.
The method for producing an organic photoelectric conversion polymer according to the present invention is not particularly limited as long as it is a method for producing a polymer compound in the field to which this technology belongs, but it may specifically include the processes of the following
[Reaction Scheme 1]
[Reaction Scheme 2]
Synthesis of 4,7-bis (5-bromothiophene-2-yl) -5,6-bis (octyloxy) -benzo [c] (1,2,5) thiadiazole (2 mmol) of 4,7-bis (5-bromothiophene-2-yl) -5,6-bis (octyloxy) -benzo [ ml, added with zinc powder as a catalyst, and stirred at 120 ° C for 24 hours. After completion of the reaction, the reaction mixture was extracted with chloroform and washed with distilled water to remove moisture. Then, 50 ml of acetic acid was added thereto, (Benzo- [2,1-b: 3,4-b '] dithiophene-4,5-dione or Benzo [1,2-b: 4,3-b'] -dithiophene -4,5-dione) may be added and stirred at 120 ° C for 48 hours. Thereafter, when the reaction is completed after confirming the TLC, the reaction mixture is extracted with chloroform, washed with distilled water to remove water, and then subjected to column purification to obtain 1.0 g of a halogenated alkyl heterocyclic compound of Scheme 1.
Referring to
More specifically, it is preferable to add 10,13-bis (5-bromothiophene-2-yl) -11,12-bis (octyloxy) dithieno [3,2- Bis- (5-bromo thiophene-2-yl) -11,12-bis (octyloxy) dithieno [2,3-a: 3 ', 2'- ) -4,5-di (ethylhexyloxy) benzo [2,1-b: 3,4-b '] dithiophene were added to the solution and stirred. Tris (dibenzylideneacetone) -dipalladium (0)) and 1.0-40.0 mol% of tri- (o-tolyl) phosphine, stirring for 5 to 15 minutes, Lt; RTI ID = 0.0 > 90 C. < / RTI > Then, 0.1 ml of 2-bromothiophene is added, and the reaction can be carried out for 3 to 14 hours. The TLC can then be quenched with HCl after the reaction is complete. Then, it can be extracted with chloroform and washed with distilled water, followed by removing water and performing column purification.
Hereinafter, the organic photoelectric device according to the present invention will be described in detail.
In the organic photoelectric device according to the present invention,
A first electrode, a hole transport layer, a photoelectric conversion layer, and a second electrode,
The photoelectric conversion layer may include an organic photoelectric conversion polymer represented by the following formula (1).
[Chemical Formula 1]
In Formula 1,
Y represents a cyclic structure containing X 1 and X 2 respectively in the structure,
X 1 and X 2 are independently of each other C, O, S or Se,
Any one of X 1 and X 2 is C and the other is O, S or Se,
T is a p-type molecule or an n-type molecule having electron accepting properties,
A is a 5 to 20-membered heteroarylene group containing at least one heteroatom selected from the group consisting of N, O, S and Se,
R 1 and R 2 are independently of each other hydrogen; An alkyl group having 1 to 25 carbon atoms; An alkoxy group having 1 to 25 carbon atoms; An aryl group having 5 to 30 carbon atoms; Thiophene group; A cellonopene group; A roll roll; Or a thiazole group,
At least one of the hydrogen atoms present in the aryl group, thiophene group, cyclophenylene group, pyrrole group and thiazole group is an alkyl group having 1 to 25 carbon atoms, an alkoxy group having 1 to 25 carbon atoms, or an aryl group having 1 to 30 carbon atoms Substituted or unsubstituted,
m and n are each independently an integer of 10 to 100,000.
Specifically, the organic photoelectric device according to the present invention may include any one of the polymers represented by Formulas 1 to 3 according to the present invention as a photoelectric conversion layer material.
The structure of the organic photoelectric device of the present invention may further include a hole transport layer and / or an electron transport layer as well as the most general device structure including the anode, the photoelectric conversion layer and the cathode. Herein, the anode may mean the first electrode of the present invention, and the cathode may mean the second electrode of the present invention. In addition, the organic photoelectric device of the present invention may be manufactured in the order of an anode, a hole transporting layer, a photoelectric conversion layer, an electron transporting layer, and a cathode, and the order of reversing the order of the cathode, the electron transporting layer, the photoelectric conversion layer, the hole transporting layer, May be prepared in this order. At this time, the photoelectric conversion layer may be formed by spin coating, and its thickness may be in the range of 10 to 10,000 angstroms. The hole transport layer may be formed on the anode electrode by vacuum evaporation or spin coating, and the electron transport layer may be formed on the photoelectric conversion layer before forming the cathode. The electron transport layer may be a conventional material for forming an electron transport layer, and the thickness of the hole transport layer and the electron transport layer may be in the range of 1 to 10,000 angstroms.
In the present invention, the first electrode may be an anode electrode, and the first electrode may further include a transparent substrate. The transparent substrate may be any substrate as long as it is used in a conventional organic photoelectric device and has excellent transparency, surface smoothness, ease of handling, and waterproofness. However, the transparent substrate may be a transparent substrate, Or polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polypropylene (PP), polyimide (PI), triacetyl cellulose (TAC) A transparent resin substrate can be used, and more specifically, a transparent glass substrate can be used. In addition, the anode electrode according to the present invention may be formed by coating an anode electrode material on the transparent substrate. The anode electrode material may include transparent indium tin oxide (ITO), transparent conductive oxide annotations may include a (SnO2), zinc oxide (ZnO), SnO 2 -Sb 2 O 3 and the like.
In the present invention, the hole transporting layer and the electron transporting layer may have a function of controlling the interface energy between the first electrode and the photoelectric conversion layer to smoothly induce the charge flow and improve the mobility. The hole transporting layer and the electron transporting layer material are not particularly limited, but specific examples of the hole transporting layer material include poly (3,4-ethylenedioxy-thiophene) doped with poly (styrenesulfonic acid) Bis (3-methylphenyl) -N, N-diphenyl- [1,1'-biphenyl] -4,4'- diamine (TPD) can be used, and as the electron transport layer material, aluminum trihydroxyquinoline trihydroxyquinoline; Alq 3 ), 1,3,4-oxadiazole derivative PBD (2- (4-biphenylyl) -5-phenyl-1,3,4-oxadiazole, quinoxaline derivative TPQ -tris [(3-phenyl-6-trifluoromethyl) quinoxaline-2-yl] benzene) and triazole derivatives can be used. The electron transport layer and the hole transport layer efficiently transport electrons and holes to the photoelectric conversion polymer It is possible to increase the probability of movement of charges generated by applying the voltage to the electrodes.
The photoelectric conversion layer according to the present invention may be a bulk heterojunction structure or a double layer junction structure as an active layer which substantially performs the function of generating electrical energy. The bulk heterojunction structure may be a bulk heterojunction (BHJ) junction type and the bilayer junction structure may be a bi-layer junction type. The BJJ (bulk jitter junction) photoactive unit may include a photoactive layer in which an n-type semiconductor and a p-type semiconductor are blended. In addition, the bi-layer p-n junction type photoactive unit may include a photoactive layer composed of two layers of a p-type semiconductor thin film and an n-type semiconductor thin film. Specifically, in the photoelectric conversion layer, a p-type semiconductor forms an exciton paired with electrons and holes by photoexcitation, and the exciton is separated into electrons and holes at the 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. At this time, the photoelectric conversion layer may include an electron donating material which is a p-organic semiconductor compound and an electron accepting material which is an n-organic semiconductor material as a photoactive material. In the photoelectric conversion layer, the electron donor material forms an exciton paired with electrons and holes by photoexcitation, and the exciton is separated into electrons and holes at the interface of the electron donor / electron acceptor. The separated electrons and holes are respectively transferred to the electron donating material and the electron accepting material, 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.
As such a photoactive substance, the present invention may include a phenazine derivative represented by the following Formula 1:
[Chemical Formula 1]
In Formula 1,
Y represents a cyclic structure containing X 1 and X 2 respectively in the structure,
X 1 and X 2 are independently of each other C, O, S or Se,
Any one of X 1 and X 2 is C and the other is O, S or Se,
T is a p-type molecule or an n-type molecule having electron accepting properties,
A is a 5 to 20-membered heteroarylene group containing at least one heteroatom selected from the group consisting of N, O, S and Se,
R 1 and R 2 are independently of each other hydrogen; An alkyl group having 1 to 25 carbon atoms; An alkoxy group having 1 to 25 carbon atoms; An aryl group having 5 to 30 carbon atoms; Thiophene group; A cellonopene group; A roll roll; Or a thiazole group,
At least one of the hydrogen atoms present in the aryl group, thiophene group, cyclophenylene group, pyrrole group and thiazole group is an alkyl group having 1 to 25 carbon atoms, an alkoxy group having 1 to 25 carbon atoms, or an aryl group having 1 to 30 carbon atoms Substituted or unsubstituted,
m and n are each independently an integer of 10 to 100,000.
In addition, the photoelectric conversion layer according to the present invention can be produced by reacting a polymer synthesized with the structure of Formula 1 with a PC 60 BM (phenyl C 61 -butyric acid methyl ester) or PC 70 BM (phenyl C 71 -butyric acid methyl ester) a fullerene derivative or a bulk heterojunction type with a phyconated organic compound. In this case, the polymer and PCBM may be mixed in a ratio (w / w) ranging from 1:10 to 10: 1 and, after mixing, Annealed for a period of time.
In the present invention, the second electrode may be a cathode electrode or an electrode containing a metal. At this time, the cathode electrode may be made of a metal having a small work function. Examples of the cathode electrode include gold (Au), silver (Ag), lithium (Li), magnesium (Mg) Or an aluminum / lithium alloy (Al: Li), an aluminum / barium fluoride alloy (Al: BaF 2 ), an aluminum / barium fluoride / barium alloy (Al: BaF 2 : Ba) ), A magnesium / silver alloy (Mg: Ag), and an aluminum / lithium fluoride alloy (Al: LiF).
Best Mode for Carrying Out the Invention Hereinafter, the present invention will be described in more detail with reference to examples and drawings based on the above description. The following examples are intended to illustrate the invention and are not intended to limit the scope of the invention.
Example 1: Manufacture of polymer for organic photoelectric conversion 1
Bis (5-bromothiophene-2-yl) -11,12-bis (octyloxy) dithieno [3,2- Synthesis of 4,5-di (ethylhexyloxy) benzo - {2,1 - b: 3,4 - b '] dithiophene was carried out according to the following reference 1 (J. Org. Chem. 14 (2012) 4718-4721, J Mater. Chem, 22 (2012) 12523-12531). Bis (5-bromothiophene-2-yl) -11,12-bis (octyloxy) dithieno [3,2-a: 2 ', 3'-c] phenazine or 10,13- bis Bis (octyloxy) dithieno [2,3-a: 3 ', 2'-c] phenazine and 2,7-bis (trimethyltin) -4,5-di ethylhexyloxy) benzo (2,1-b: 3,4-b '] dithiophene (0.16 g) was dissolved in 9 ml of toluene and added to the solution of tris (dibenzylideneacetone) dipalladium (0) Aldrich) and 7 mg of tri (o-tolyl) phosphine, Aldrich) were added to the mixture, and the mixture was stirred for 10 minutes and then at 90 ° C for 72 hours. Finally, 0.1 ml of 2-bromothiophene was added, and the mixture was stirred for 12 hours and purified to prepare a photoelectric conversion polymer represented by the following formula (7) (yield: about 0.18 g).
(7)
Example
2: Manufacture of polymer for organic
Bis (5-bromothiophene-2-yl) -11,12-bis (octyloxy) dithieno- [2,3-a: 3 ', 2'- Synthesis of 4,5-di (ethylhexyloxy) benzo- {2,1-b: 3,4-b '] dithiophene was carried out according to the following reference 1 (J. Org. Chem. 14 (2012) 4718-4721, J. Mater. Chem., 22 (2012) 12523-12531). Bis (5-bromothiophene-2-yl) -11,12-bis (octyloxy) dithieno [3,2-a: 2 ', 3'-c] phenazine or 10,13- bis Bis (octyloxy) dithieno [2,3-a: 3 ', 2'-c] phenazine and 2,7-bis (trimethyltin) -4,5-di ethylhexyloxy) benzo (2,1-b: 3,4-b '] dithiophene (0.16 g) was dissolved in 9 ml of toluene and added to the solution of tris (dibenzylideneacetone) dipalladium (0) Aldrich) and 7 mg of tri (o-tolyl) phosphine, Aldrich) were added to the mixture, and the mixture was stirred for 10 minutes and then at 90 ° C for 72 hours. Finally, 0.1 ml of 2-bromothiophene was added, and the mixture was stirred for 12 hours and purified to prepare a photoelectric conversion polymer represented by the following formula (8) (yield: about 0.18 g).
[Chemical Formula 8]
Example 3: Organic photoelectric device Manufacturing 1
An organic photoelectric device was fabricated using the organic photoelectric conversion polymer prepared in Example 1 under the following conditions.
The surface of the substrate on which the ITO layer was formed on the transparent glass substrate was continuously ultrasonically irradiated and cleaned under acetone and isopropanol, dried at 100 캜 under vacuum for 1 hour, and then treated in a UV-ozone cleaner for 15 minutes.
The commercially available PEDOT: PSS (Heraeus Clevios ™ P VP AI 4083) was filtered using a 0.45 μm PTFE syringe filter and stirred in a shaker to prevent phase separation of PEDOT and PSS.
The organic photoelectric conversion polymer and fullerene according to Example 1 were dissolved in dichlorobenzene at various concentrations, stirred for 24 hours, and filtered using a 5 탆 PTFE syringe filter. Coated on the previously prepared ITO layer at a speed of 2000 rpm for 40 seconds.
The prepared substrate and samples were transferred to a glove box and spin-coated on the previously prepared ITO layer at a rate of 2000 rpm for 40 seconds. Then, PEDOT: PSS was subjected to heat treatment at 110 ° C for 20 minutes, AedotronTMC at 140 ° C for 20 minutes, and the polymer and fullerene active layer at 120 ° C for 1 hour to remove residual solvent. gave. Subsequently, the EIL and the electrode material were transferred to a high vacuum chamber (1 × 10 -6 torr or less) of a thermal evaporator for depositing an electrode material. All the BaF 2 (0.1 Å / s, 2 nm) / Ba , 2 nm) / Al (5 Å / s, 100 nm).
Example
4:
Organic
Was prepared in the same manner as in Example 1, except that Example 2 was used as a polymer for organic photoelectric conversion.
FIG. 1 is a cross-sectional view of the organic optoelectronic device manufactured in Examples 3 and 4.
Comparative Example 1: Manufacture of polymer for organic photoelectric conversion
Bis (5-bromothiophene-2-yl) -11,12-bis (octyloxy) dithieno [3,2- bromothiophene-2-yl) -11,12-bis (octyloxy) dibenzo [a, c] phenazine was used to prepare a photoelectric conversion polymer represented by the following
[Chemical Formula 9]
Comparative Example 2: Organic photoelectric device Produce
Was prepared in the same manner as in Example 3, except that Comparative Example 1 was used as a polymer for organic photoelectric conversion.
Experimental Example One
The following experiments were conducted to evaluate the absorbance of Examples 1 and 2 and Comparative Example 1.
The light absorption spectra were measured in the wavelength range of 250 to 600 nm using the UV spectrum, and the results are shown in FIG. 2, where A is Example 1, B is Example 2, and C is Comparative Example 1. Referring to FIG. 2, the organic photoelectric conversion polymer according to the present invention has a longer wavelength absorption characteristic than that of Comparative Example 1.
Experimental Example 2
The electric potential curves of the organic photoelectric devices of Examples 3 and 4 were measured using a cyclic voltammetry at a scan rate of 1 / s. The results are shown in FIG. In Fig. 3, A is Embodiment 3, and B is
Experimental Example 3
The following experiments were conducted to evaluate the energy efficiency of the organic photoelectric device according to the present invention.
The organic photoelectric devices prepared in Examples 3 and 4 and Comparative Example 2 were tested under standard conditions (Air Mass 1.5 Global, 100 mW) using a Keithley 2400 source meter and a solar simulator (Oriel 150W solar simulator) A short circuit current density (J SC ), an open circuit voltage (V OC ), a fill factor (FF), and a power conversion efficiency (PCE ) Were measured. At this time, the artificial solar cell was tested with a Si solar cell (Mono-Si + KG filter, Certificate No. C-ISE 269) and the active area of the organic photoelectric device was controlled to 12
In Table 1, the fill factor (FF) is a voltage value at the maximum power point (V max) X current density (J max) / (J SC XV oc) , and the energy conversion efficiency (PCE) is FF X (J SC XV oc ) / Pin, and Pin is 100 [mW / cm < 2 >].
Table 1 shows that the organic photoelectric device according to the present invention has improved energy conversion efficiency. Specifically, it is confirmed that the energy conversion efficiency of the organic photoelectric device can be improved by about 9% or more, which can be adjusted close to the HOMO level (about 5.13 ± 0.1 eV).
4 is a graph showing the efficiency of organic optoelectronic devices according to Examples 3 and 4 and Comparative Example 2, showing a short circuit current density (J SC ) and an open circuit voltage (V OC ) . FIG. 4 shows that Examples 3 and 4 show higher efficiency than Comparative Example 2.
Experimental Example 4
The external quantum efficiency (EQE) according to the wavelengths of the organic photoelectric devices according to Examples 3 and 4 and Comparative Example 2 was evaluated. The external quantum efficiency was measured using the IPCE measurement system (McScience, K3100). First, the equipment is calibrated using an Si photodiode (ORIEL, CELL POSITION), and the organic photoelectric device according to Examples 3 and 4 and Comparative Example 2 is installed in the equipment, Quantum efficiency was measured. The results are shown in Fig. 5, it can be seen that the external quantum efficiency of the organic photoelectric device according to Examples 3 and 4 is much improved as compared with Comparative Example 2. [
Claims (8)
(7)
[Chemical Formula 8]
In the above formulas (7) and (8)
and a is an integer of 10 to 100,000.
Wherein the photoelectric conversion layer comprises an organic photoelectric conversion polymer represented by Chemical Formula 7 or 8:
(7)
[Chemical Formula 8]
In the above formulas (7) and (8)
and a is an integer of 10 to 100,000.
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