KR101328526B1 - Organic photovoltain polymer and manufacturing method thereof - Google Patents

Abstract

The present invention increases the solubility by using a molecule having a flexible alkoxy chain in the quinoxaline derivative 6,7-position or the phenanthracene quinoxaline derivative 11,12-position to increase the solubility, and provides effective intermolecular stacking of planar molecular sieves. The present invention relates to an organic photoelectric conversion polymer and a method of manufacturing the same, and a bulk heterojunction type photoelectric conversion device using the polymer and the PCBM.
The present invention provides an organic photoelectric conversion polymer having an excellent photoelectric conversion efficiency and an organic photoelectric conversion device employing the organic photoelectric conversion polymer as an active layer. By providing an organic photovoltaic device (OPV device), it can be usefully used as a next-generation organic photoelectric device showing a stable photoelectric conversion efficiency and excellent conversion efficiency.

Description

Organic photoelectric conversion polymer and its manufacturing method {ORGANIC PHOTOVOLTAIN POLYMER AND MANUFACTURING METHOD THEREOF}

The present invention relates to a novel organic photoelectric conversion polymer and a preparation method thereof, and more particularly, a molecule having a flexible alkoxy chain in the quinoxaline derivative 6,7-position or phenanthracene quinoxaline derivative 11,12-position as a main chain. Organic photoelectric conversion polymer and its manufacturing method and photoelectric conversion polymer exhibiting high efficiency photoelectric conversion characteristics by increasing the solubility of the planar molecular sieves and the effective transport of carriers through the effective stacking of planar molecular sieves It relates to a bulk heterojunction type photoelectric conversion device.

Recently, with high oil prices and environmental pollution, the demand for low-cost eco-friendly energy sources is rapidly increasing. Eco-friendly energy sources include solar, wind, hydro, wave, and geothermal energy. Solar power generation, which can generate electricity using solar power, is an endless energy source without the risk of environmental pollution.

For example, the actual amount of solar energy available on Earth is 600 TW (1 TW = 1 × 012 Watts), a massive amount estimated at 60 times all the energy currently in use.

For this reason, research on photovoltaic devices using solar light has been conducted for several decades, and now inorganic solar cells using silicon wafers are commercially available. However, inorganic solar cells are used for long-term, large-scale power generation due to high raw material costs, and are not suitable for flexible solar cells or wearable solar cells combined with inexpensive energy sources for electronic products or flexible displays. Accordingly, researches on solar cells using organic semiconductors are being actively conducted.

In organic photovoltaic (PV), photons are separated into electrons and holes to form excitons in an organic active layer that receives sunlight, which forms electron excitons and electron acceptor materials. It means moving to the interface and separating by the difference of each low Unoccupied Molecular Orbital (LUMO) level to produce electricity.

In 1987, photoelectric conversion phenomena were made by Eastman Kodak Co.'s Tang et al. In ITO / CuPc (30 nm) / PV (50 nm) / Ag. The photoelectric conversion efficiency of was first reported (Tang et al., Appl. Phys. Lett. 48, 183, 1986). Subsequent to the photoelectric conversion efficiency of less than 1% has made significant progress thanks to the introduction of fullerene and the development of its derivative PCBM.

In general, for high efficiency photoelectric conversion efficiency, photon harvesting characteristics that can absorb a wide range of sunlight should be preceded, and effective stacking between molecules is required to enable efficient electron and hole transport. To this end, by introducing a molecular structure that can provide effective molecular stacking to the polymer main chain can be induced to stack between the polymers to increase the charge mobility.

Therefore, the present inventors use phenazine derivatives having excellent solubility, oxidative stability, and charge mobility, and use them as active layers of organic photoelectric devices having a push-pull structure, and thus attract various electron donors and electron attractors. Polymerization with molecules has resulted in the development of new photoelectric conversion polymers and organic photoelectric devices using the same.

After all, the main object of the present invention is to provide an organic photoelectric conversion polymer having excellent solubility and oxidation stability, high solubility, and excellent photoelectric conversion efficiency with high charge mobility by stacking between molecules.

Another object of the present invention is to provide an organic photovoltaic device (OPV device) employing the organic photoelectric conversion polymer as a photoactive layer.

In addition, another object of the present invention to provide a method for producing an organic photoelectric conversion polymer excellent in the photoelectric conversion efficiency.

In order to achieve the above object, the present invention provides a copolymer having a p-type molecular having an electron donor property including a phenazine derivative and an n-type molecular having an electron attracting property including a phenazine derivative. Co-polymerized) as a main chain, to provide an organic photoelectric conversion polymer represented by the formula (1) or (2).

[Formula 1]

(2)

In the above formula, n is an integer of 1 to 100,000, R is a hydrogen atom; An alkyl group having 1 to 25 carbon atoms; An alkoxy group having 1 to 25 carbon atoms; A hydrogen atom, a phenyl substituted with an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; Pyrrole substituted with a hydrogen atom, an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; An arylene group substituted with a hydrogen atom and an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; An aryl group substituted with a hydrogen atom and an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; It is selected from the group consisting of aryl groups having 10 to 24 carbon atoms having a fused aromatic ring compound, R ₁ to R ₄ is a hydrogen atom; It has a C1-C25 alkyl group. In addition, Ar is a hydrogen atom, phenyl substituted with an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; Thiophene substituted with an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; Pyrrole substituted with a hydrogen atom, an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; An arylene group substituted with a hydrogen atom and an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; An aryl group substituted with a hydrogen atom and an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; It is preferably selected from the group consisting of aryl groups having 10 to 24 carbon atoms having a fused aromatic ring compound.

In addition, the molecule having an electron donor property (p-type molecular) including the phenazine derivative is preferably one or more selected from compounds represented by the following formula (3),

(3)

Provided that R ₁ to R _{24 are} independently a hydrogen atom; An alkyl group having 1 to 25 carbon atoms; An alkoxy group having 1 to 25 carbon atoms; Thiophene substituted with a hydrogen atom, an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; Selenophene substituted with a hydrogen atom, an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; Pyrrole substituted with a hydrogen atom, an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; An arylene group substituted with a hydrogen atom and an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; An aryl group substituted with a hydrogen atom and an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; Thiazoles substituted with a hydrogen atom and an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; It is preferably selected from the group consisting of aryl groups having 10 to 24 carbon atoms having a fused aromatic ring compound.

It is preferable that the molecule having an electron attracting property (n-type molecular) including the phenazine derivative is a quinoxaline or a phenanthracene quinoxaline derivative.

The present invention also provides an organic photoelectric device employing the organic photoelectric conversion polymer as a photoactive layer.

In the present invention, the photoactive layer is formed by spin coating, the thickness is preferably 10 to 10,000 kPa.

In addition, the photoactive layer of the organic photoelectric conversion polymer represented by the general formula (1) or (2) and PC61BM (phenyl C61-butyric acid methyl ester) or PC71BM (phenyl C71-butyric acid methyl ester) and various fullerene (fullerene) derivatives It is preferable to form a bulk heterojunction type.

In addition, the present invention comprises the steps of: (1) toluene (p-type molecular) and the quinoxaline or phenanthracene quinoxaline derivatives having an electron donor property including a phenazine derivative in toluene; (2) adding 0.5 to 10 mol% of tetrakis (triphenylphosphine) palladium (tetrakistriphenylphosphinepalladium) and stirring for 5 to 15 minutes; (3) stirring the material stirred in step (2) at 80 to 100 ° C. for 24 to 72 hours; (4) adding 0.1 ml of bromothiophene to the material stirred by step (3) and reacting for 10 to 14 hours; (5) quenching with HCl when the reaction is terminated after confirmation of thin layer chromatography (TLC); And (6) extracting with chloroform and washing with distilled water after quenching according to step (5), removing water and purifying the column, thereby providing an organic photoelectric conversion polymer.

According to the present invention as described above, by providing an organic photoelectric conversion polymer of excellent photoelectric conversion efficiency excellent in solubility and oxidation stability and having a high charge mobility by stacking the residue glass, photoelectric conversion efficiency employing the polymer as an active layer This excellent organic photoelectric device can be manufactured.

In addition, the method for manufacturing an organic photoelectric device according to the present invention is easy to manufacture by a relatively simple process such as spin coating, and stable HONO (Highest Occupied Molecular Orbital), LUMO ( Lowest Unoccupied Molecular Orbital) can be applied to organic photoelectric devices.

In addition, the organic photoelectric device of the present invention exhibits stable photoelectric conversion efficiency, and is excellent in the conversion efficiency, and thus may be usefully used as a next-generation organic photoelectric device.

1 is a ¹ H-NMR spectrum of an organic photoelectric conversion polymer prepared according to an embodiment of the present invention.
2 is a UV absorption spectrum of the organic photoelectric conversion polymer prepared according to an embodiment of the present invention.
3 is a cyclic voltammetry (CV) graph and a band diagram of the compounds evaluating the electrochemical properties of the organic photoelectric conversion polymer prepared according to the embodiment of the present invention.
4 is a cross-sectional view showing the structure of an organic photoelectric conversion device manufactured to measure the photoelectric conversion characteristics of the organic photoelectric conversion polymer prepared according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

The present invention provides an organic photoelectric conversion polymer which is excellent in solubility and oxidation stability, has high solubility, and has excellent photoelectric conversion efficiency having high charge mobility by stacking between molecules.

In the organic photoelectric conversion polymer of the present invention, a molecule having an electron donor property including a phenazine derivative and an n-type molecular having an electron attracting property including a phenazine derivative are copolymerized (co It is characterized in that the organic photoelectric conversion polymer represented by the following formula (1) or (2) as a main chain.

[Formula 1]

(2)

In the above formula, n is an integer of 1 to 100,000, R is a hydrogen atom; An alkyl group having 1 to 25 carbon atoms; An alkoxy group having 1 to 25 carbon atoms; A hydrogen atom, a phenyl substituted with an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; Pyrrole substituted with a hydrogen atom, an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; An arylene group substituted with a hydrogen atom and an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; An aryl group substituted with a hydrogen atom and an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; It is selected from the group consisting of aryl groups having 10 to 24 carbon atoms having a fused aromatic ring compound, R ₁ to R ₄ is a hydrogen atom; A phenyl having an alkyl group having 1 to 25 carbon atoms, Ar being a hydrogen atom, a substituted alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; Thiophene substituted with an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; Pyrrole substituted with a hydrogen atom, an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; An arylene group substituted with a hydrogen atom and an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; An aryl group substituted with a hydrogen atom and an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; It is preferably selected from the group consisting of aryl groups having 10 to 24 carbon atoms having a fused aromatic ring compound.

In addition, in the present invention, the molecule having an electron donor property including the phenazine derivative (p-type molecular) is preferably one or more selected from the compounds represented by the following formula (3).

(3)

Provided that R ₁ to R _{24 are} independently a hydrogen atom; An alkyl group having 1 to 25 carbon atoms; An alkoxy group having 1 to 25 carbon atoms; Thiophene substituted with a hydrogen atom, an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; Selenophene substituted with a hydrogen atom, an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; Pyrrole substituted with a hydrogen atom, an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; An arylene group substituted with a hydrogen atom and an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; An aryl group substituted with a hydrogen atom and an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; Thiazoles substituted with a hydrogen atom and an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; It may be selected from the group consisting of aryl groups having 10 to 24 carbon atoms having a fused aromatic ring compound, more preferably 2,5-bis (trimethylstannyl) thiophene.

In addition, in the present invention, the molecule having an electron attracting property including the phenazine derivative (n-type molecular) is preferably a quinoxaline or phenanthracene quinoxaline derivative, more preferably the n-type molecular is 6 Quinoxaline or phenanthracene quinoxaline derivatives comprising alkoxy chains flexible in the 7- and 11,12-positions, and most preferably 10,13-dibromo-11,12-bis (octyloxy) dibenzo [ a, c] phenazine is preferable.

In the present invention, the organic photoelectric conversion polymer may be prepared by the process of Scheme 1 below.

[Reaction Scheme 1]

Specifically, the polymer according to the present invention can be prepared using a steel coupling reaction. In this case, xylene, toluene, dimethylformamide (DMF), etc. may be used as a solvent, and tetrakis (triphenylphosphine) palladium (tetrakistriphenylphosphinepalladium) may be used in a polymer of 0.5 to 10 mol%. Can be obtained.

In a preferred embodiment, (a) 10,13-dibromo-11,12-bis (octyloxy) dibenzo [a, c] phenazine and 2,5-bis (trimethylstannyl) thiophene are added to toluene and stirred. after; (b) adding 0.5-10 mol% of tetrakis (triphenylphosphine) palladium and stirring for 10 minutes; (c) Stir 48 hours at 90 ° C. (d) 0.1 ml of bromothiophene is added dropwise to react for 12 hours. (e) After TLC confirmation, the reaction is quenched with HCl. Finally, (f) it is possible to manufacture the organic photoelectric conversion polymer of the present invention by the step of extracting with chloroform and washing with distilled water to remove water and purify the column.

In the present invention, a method of manufacturing the photoelectric conversion polymer has been described as described above. However, the method of preparing the polymer compound is not particularly limited, and any method of preparing the polymer compound satisfying Scheme 1 may be used.

As shown in the UV spectrum, the organic photoelectric conversion polymer prepared in the present invention can confirm a gentle peak than the solution phase (see FIG. 2). This is due to pi (π) -pi (π) stacking, which shows the possibility of effective charge transfer in the organic photoelectric device.

The present invention also provides an organic photoelectric device employing the organic photoelectric conversion polymer represented by Formula 1 or Formula 2 as an active layer.

The polymer of Chemical Formula 1 or Chemical Formula 2 according to the present invention may be used as a photoelectric conversion layer material of an organic photoelectric device, and a method of manufacturing the organic photoelectric conversion device applying the same is as follows.

First, an anode electrode material is coated on the substrate. In this case, the substrate used in the conventional organic photoelectric conversion device is used, it is preferable to use a glass substrate or a transparent plastic substrate excellent in transparency, surface smoothness, ease of handling and waterproof. In addition, it is preferable to use indium tin oxide (ITO), tin oxide (SnO ₂ ), zinc oxide (ZnO), or the like, which is transparent and has excellent conductivity as an anode electrode material, and a work function (Work It is preferable to use lithium (Li), magnesium (Mg), aluminum (Al), Al: Li, Al: BaF ₂ , Al: BaF ₂ : Ba and the like having a small function).

The organic photoelectric conversion device of the present invention may further include a hole transport layer and / or an electron transport layer, as well as the most common device configuration of the anode / photoelectric conversion layer / cathode. At this time, the photoelectric conversion layer may be formed by spin coating, the thickness thereof is preferably in the range of 10 ~ 10,0001.

In addition, the hole transport layer may be formed by vacuum deposition or spin coating on the anode, and the electron transport layer is formed on the photoelectric conversion layer before forming the cathode. In addition, the electron transport layer may use a conventional material for forming an electron transport layer, the thickness of the hole transport layer and the electron transport layer is preferably in the range of 1 ~ 10,000Å.

In the present invention, the hole transport layer and the electron transport layer material is not particularly limited. Preferably, the hole transport layer material is PEDOT: PSS (Poly (3,4-ethylenediocy-thiophene) doped with poly (styrenesulfonic acid)), N, It is preferable to use N'-bis (3-methylphenyl) -N, N-diphenyl- [1,1'-biphenyl] -4,4'-diamine (TPD), and as the electron transport layer material, aluminum trihydride. Aluminum trihydroxyquinoline (Alq ₃ ), 1,3,4-oxadiazole derivative PBD (2- (4-biphenylyl) -5-phenyl-1,3,4-oxadiazole, quinoxaline derivative TPQ (1 , 3,4-tris [(3-phenyl-6-trifluoromethyl) quinoxaline-2-yl] benzene), triazole derivatives, etc. It is preferable to use the electron transport layer and the hole transport layer as photoelectric conversion polymers. It effectively increases the probability of transfer of generated charges to the electrodes.

In addition, the photoelectric conversion layer is a bulk hetero with a polymer synthesized in the same structure as in Chemical Formula 1 with PC61BM (phenyl C61-butyric acid methyl ester) or PC71BM (phenyl C71-butyric acid methyl ester) and various fullerene derivatives. It is formed as a junction type. In this case, the polymer and the PCBM are preferably mixed in a ratio (w / w) in the range of 1:10 to 10: 1, and after mixing, 1 second to 24 hours at a temperature of 50 to 300 ° C. so as to exhibit maximum properties. Annealing is preferred.

In addition, the organic electroluminescent device of the present invention may be manufactured in the order of anode / hole transporting layer / photoelectric conversion layer / electron transporting layer / cathode as described above, and vice versa, that is, cathode / electron transporting layer / photoelectric conversion layer / It may be manufactured in the order of the hole transport layer / anode.

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these examples are for illustrative purposes only and that the scope of the present invention is not construed as being limited by these examples.

Example 1. Preparation of organic photoelectric conversion polymer

Synthesis of 2,5-bis (trimethylstannyl) thiophene and 10,13-dibromo-11,12-bis (octyloxy) dibenzo [a, c] phenazine was synthesized with reference to the following literature (Journal of Industrial and Engineering Chemistry , 17, 352-357, 2011; Chem. Mater., 21, 3491-3502, 2009).

0.17 g of 2,5-bis (trimethylstannyl) thiophene and 0.3 g of 10,13-dibromo-11,12-bis (octyloxy) dibenzo [a, c] phenazine were dissolved in 20 ml of toluene, followed by tetrakis (triphenylphosphine). ) Palladium dichloride (tetrakistriphenylphosphinepalladium (II) dichloride, Aldrich) was added 0.009 g and stirred for 10 minutes and then stirred at 90 ℃ for 48 hours.

Finally, 0.5 ml of bromothiophene (Bromothiophene, Aldrich) was added, stirred for 12 hours, and purified to obtain 0.13 g of an organic photoelectric conversion polymer.

Example 2. Fabrication of organic photoelectric conversion device

The device was fabricated under the following conditions using the organic tubular conversion polymer prepared in Example 1.

PEDOT: PSS was filtered using a 0.45 μm PTFE syringe filter and stirred in a shaker to prevent phase separation between PEDOT and PSS. AedotronTMC was filtered using a 5 μm PTFE syringe filter and also stirred on a shaker to help evenly distribute PEDOT-PEG and ClO4-.

The polymer and fullerene were dissolved in dichlorobenzene at various concentrations, stirred for 24 hours, and filtered using a 5 μm PTFE syringe filter.

The prepared substrates and samples were transferred to a glove box and spin coated under various conditions. After spin coating, PEDOT: PSS is 20 minutes at 110 ℃, AedotronTMC is 20 minutes at 140 ℃, and the polymer and fullerene active layer are heat-treated at 120 ℃ for 1 hour to remove residual solvents. gave.

It was transferred to a high vacuum chamber (1 × 10 ^-6 torr or less) of a thermal evaporator for depositing EIL and electrode material, and both BaF ₂ (0.1 μs / s, 2 nm) / Ba (0.2 μs / s, The electrode was formed in the order of 2 nm) / Al (5 μs / s, 100 nm).

Having described specific portions of the present invention in detail, those skilled in the art will appreciate that these specific descriptions are only for the preferred embodiment and that the scope of the present invention is not limited thereby. It will be obvious. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

Claims (11)

Co-polymerized p-type molecule having an electron donor property represented by the following formula (3), and a quinoxaline derivative having an alkoxy chain at a 6,7-position as an n-type molecule having an electron attracting property. An organic photoelectric conversion polymer represented by the following Chemical Formula 1.
[Chemical Formula 1]

However, in Formula 1, n is an integer of 1 to 100,000, R is a hydrogen atom; An alkyl group having 1 to 25 carbon atoms; An alkoxy group having 1 to 25 carbon atoms; A hydrogen atom, a phenyl substituted with an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; Pyrrole substituted with a hydrogen atom, an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; An arylene group substituted with a hydrogen atom and an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; An aryl group substituted with a hydrogen atom and an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; It is selected from the group consisting of aryl groups having 10 to 24 carbon atoms having a fused aromatic ring compound, R1 to R2 is a hydrogen atom; A phenyl having an alkyl group having 1 to 25 carbon atoms, Ar being a hydrogen atom, a substituted alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; Pyrrole substituted with a hydrogen atom, an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; An arylene group substituted with a hydrogen atom and an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; An aryl group substituted with a hydrogen atom and an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; Selected from the group consisting of aryl groups having 10 to 24 carbon atoms having a fused aromatic ring compound.
(3)

However, in Formula 3, R1 to R24 are independently a hydrogen atom; An alkyl group having 1 to 25 carbon atoms; An alkoxy group having 1 to 25 carbon atoms; Thiophene substituted with a hydrogen atom, an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; Selenophene substituted with a hydrogen atom, an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; Pyrrole substituted with a hydrogen atom, an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; An arylene group substituted with a hydrogen atom and an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; An aryl group substituted with a hydrogen atom and an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; Thiazoles substituted with a hydrogen atom and an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; Selected from the group consisting of aryl groups having 10 to 24 carbon atoms having a fused aromatic ring compound.
A p-type molecule having an electron donor property represented by Formula 3 and a phenanthracene quinoxaline derivative having an alkoxy chain in an 11,12-position as an n-type molecule having an electron attracting property are co-polymerized. An organic photoelectric conversion polymer represented by the following formula (2) having one as a main chain.
(2)

In Formula 2, n is an integer of 1 to 100,000, R3 to R4 is a hydrogen atom; A phenyl having an alkyl group having 1 to 25 carbon atoms, Ar being a hydrogen atom, a substituted alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; Pyrrole substituted with a hydrogen atom, an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; An arylene group substituted with a hydrogen atom and an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; An aryl group substituted with a hydrogen atom and an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; Selected from the group consisting of aryl groups having 10 to 24 carbon atoms having a fused aromatic ring compound.
(3)

However, in Formula 3, R1 to R24 are independently a hydrogen atom; An alkyl group having 1 to 25 carbon atoms; An alkoxy group having 1 to 25 carbon atoms; Thiophene substituted with a hydrogen atom, an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; Selenophene substituted with a hydrogen atom, an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; Pyrrole substituted with a hydrogen atom, an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; An arylene group substituted with a hydrogen atom and an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; An aryl group substituted with a hydrogen atom and an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; Thiazoles substituted with a hydrogen atom and an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; Selected from the group consisting of aryl groups having 10 to 24 carbon atoms having a fused aromatic ring compound.
delete delete delete An organic photoelectric device employing the organic photoelectric conversion polymer of claim 1 or 2 as an active layer.
The method according to claim 6,
The photoactive layer is a ratio of the organic photoelectric conversion polymer of claim 1 or 2 and PC61BM (phenyl C61-butyric acid methyl ester) or PC71BM (phenyl C71-butyric acid methyl ester) in a ratio of 1:10 to 10: 1 (w). / w) mixed with the organic photoelectric device.
8. The method of claim 7,
The photoactive layer is an organic photoelectric device, characterized in that formed by the thickness of 10 to 10,000 Å by spin coating.
(1) a p-type molecule having an electron donor property represented by the following formula (3) in toluene, and a quinoxaline derivative having an alkoxy chain at a 6,7-position as an n-type molecule having an electron attracting property, or 11 Adding and stirring a phenanthracene quinoxaline derivative having an alkoxy chain in a 12-position;
(2) adding 0.5 to 10 mol% of tetrakis (triphenylphosphine) palladium (tetrakistriphenylphosphinepalladium) and stirring for 5 to 15 minutes;
(3) stirring the material stirred in step (2) at 80 to 100 ° C. for 24 to 72 hours;
(4) adding bromothiophene to the stirred material in step (3) and reacting for 10 to 14 hours;
(5) quenching with HCl when the reaction is terminated after confirmation of thin layer chromatography (TLC); And
(6) extracting with chloroform and washing with distilled water after quenching according to step (5), and then removing water and purifying the column; manufacturing method of an organic photoelectric conversion polymer represented by the following Chemical Formula 1 or 2.
[Chemical Formula 1]

(2)

However, in Formula 1 and Formula 2, n is an integer of 1 to 100,000, and R is a hydrogen atom; An alkyl group having 1 to 25 carbon atoms; An alkoxy group having 1 to 25 carbon atoms; A hydrogen atom, a phenyl substituted with an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; Pyrrole substituted with a hydrogen atom, an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; An arylene group substituted with a hydrogen atom and an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; An aryl group substituted with a hydrogen atom and an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; It is selected from the group consisting of aryl groups having 10 to 24 carbon atoms having a fused aromatic ring compound, R1 to R4 is a hydrogen atom; A phenyl having an alkyl group having 1 to 25 carbon atoms, Ar being a hydrogen atom, a substituted alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; Pyrrole substituted with a hydrogen atom, an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; An arylene group substituted with a hydrogen atom and an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; An aryl group substituted with a hydrogen atom and an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; Selected from the group consisting of aryl groups having 10 to 24 carbon atoms having a fused aromatic ring compound.
(3)

However, in Formula 3, R1 to R24 are independently a hydrogen atom; An alkyl group having 1 to 25 carbon atoms; An alkoxy group having 1 to 25 carbon atoms; Thiophene substituted with a hydrogen atom, an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; Selenophene substituted with a hydrogen atom, an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; Pyrrole substituted with a hydrogen atom, an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; An arylene group substituted with a hydrogen atom and an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; An aryl group substituted with a hydrogen atom and an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; Thiazoles substituted with a hydrogen atom and an alkoxy group having 1 to 25 carbon atoms substituted with an alkyl group having 1 to 25 carbon atoms; Selected from the group consisting of aryl groups having 10 to 24 carbon atoms having a fused aromatic ring compound.
The method of claim 9,
In step (1), the p-type molecule having an electron donor property is 2,5-bis (trimethylstannyl) thiophene, and the n-type molecule having an electron attracting property is 10,13-dibromo-11,12-bis (octyloxy ) dibenzo [a, c] phenazine is a method for producing an organic photoelectric conversion polymer, characterized in that. delete

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