KR20130141896A - ORGANIC PHOTOVOLTAIC π-π CONJUGATED POLYMER AND MANUFACTURING METHOD THEREOF - Google Patents

Abstract

The present invention relates to novel organic photovoltaic π-π conjugated polymers, a manufacturing method thereof and an organic photovoltaic device (OPV device) using the polymers as an active layer. The present invention provides organic photovoltaic polymers which exhibit excellent solubility and oxidative stability, have high charge mobility due to stacking between molecules and show excellent photovoltaic efficiency, and the OPV device using the polymers as the active layer. Accordingly, the present invention can produce the OPV device which exhibits excellent photovoltaic efficiency and uses the polymers as the active layer with a simple method such as spin coating etc. and can apply the OPV device to a highest occupied molecular orbital (HOMO) and lowest occupied molecular orbital (LUMO) by selecting stable electron donors and electron acceptors and using intermolecular interactions.

Description

ORGANIC PHOTOVOLTAIC π-π CONJUGATED POLYMER AND MANUFACTURING METHOD THEREOF}

The present invention relates to a novel organic photoelectric conversion pi-pi conjugated polymer, a method for preparing the same, and an organic photovoltaic device (OPV device) employing the polymer as an active layer, and more particularly, a quinacridone derivative 5, Molecules with flexible alkyl and alkoxy chains in the 12-position increase the solubility and improve the transport properties of the carriers through effective stacking of the planar molecular sieves The present invention relates to a photoelectric conversion polymer, a manufacturing method thereof, and a bulk heterojuction type photoelectric conversion device using the polymer.

Recently, as high oil prices and environmental pollution problems arise, the demand for low-cost, environmentally 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 inorganic solar cells using silicon wafers are commercially available (Journal of Nanoscience and Nanotechnology 10 (7), 99-105, 2010). ).

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. Therefore, researches on solar cells using organic semiconductors are being actively conducted (European Polymer Journal, 48, 532-540, 2012).

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 Occupied 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. Photoelectric conversion efficiency of% was first reported (Tang et al., CW Tang, CW, 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, high efficiency photoelectric conversion efficiency requires a photon harvesting characteristic capable of absorbing a wide range of sunlight, and effective stacking between molecules 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.

Accordingly, the present inventors use a quinacridone derivative having excellent solubility, oxidative stability, and charge mobility as an active layer of an organic photoelectric device having a push-pull structure, and thus, various electron donors and electron attracting molecules. The present invention was completed by polymerizing and developing a new photoelectric conversion polymer and an organic photoelectric device using the same.

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

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

In order to achieve the above object, the present invention forms an electron p-type or electron acceptor (n-type) pair with a molecule containing a flexible alkyl and alkoxy chain at the 5,12-position of the quinacridone derivative. An organic photoelectric conversion polymer represented by the following general formula (1) or (2) is provided using a copolymer of molecules as a main chain.

[Formula 1]

(2)

 With the proviso that n is an integer from 1 to 10,000 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.

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

The photoactive layer can be formed by a conventional solution process, the thickness is characterized in that 10 to 10,000 kPa.

In addition, the photoactive layer is an organic photoelectric conversion polymer represented by the formula (1) or (2) and PC61BM (phenyl C61-butyric acid methyl ester) or PC71BM (phenyl C71-butyric acid methyl ester) and various fullerene derivatives (PCBM) It is characterized in that it is formed as a bulk heterojunction type.

In addition, the present invention comprises the steps of (1) adding a quinacridone derivative to the organic solvent and stirring; (2) 0.5 to 10 moles of aqueous solution of K ₂ CO ₃ or Na ₂ CO ₃ as base, Aliquat 336 as a small amount of surfactant, and tetrakis (triphenylphosphine) palladium Adding more mol% and stirring for 5 to 15 minutes; (3) stirring the material stirred in step (2) at 90 ° C. for 24 to 72 hours; (4) adding bromothiophene to the stirred material 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 having excellent solubility and oxidation stability and high charge mobility by stacking between molecules, the photoelectric conversion efficiency employing the polymer as an active layer is It is possible to manufacture an excellent organic photoelectric device.

In addition, the organic photoelectric device may be manufactured by a relatively simple process such as spin coating, and stable HOMO (High Occupied Molecular Orbital), LUMO ( Lowest Occupied Molecular Orbital) can be applied to organic photoelectric devices.

In addition, the organic photoelectric device shows a stable photoelectric conversion efficiency, and excellent conversion efficiency, it can be usefully used as a next-generation organic photoelectric device.

1 is an H-NMR graph of a compound represented by Chemical Formula 5 according to the present invention.
2 is a UV absorption spectrum graph of the compound represented by Formula 5 according to the present invention.
3 is a cyclic voltammetry (CV) graph evaluating the electrochemical properties of the compound represented by Formula 5 according to the present invention.
4 is a cross-sectional view illustrating a structure of an organic photoelectric device manufactured to measure photoelectric conversion characteristics of a compound represented by Chemical Formula 5 according to the present invention.
5 is a graph of efficiency of the organic photoelectric device of the compound represented by the formula (5) according to the present invention.

Hereinafter, the present invention will be described in detail.

The present invention is a main chain copolymerized with a quinacridone derivative and a molecule forming a p-type molecular or n-type molecular pair having an electron acceptor property. It provides an organic photoelectric conversion polymer represented by the formula (2).

With the proviso that n is an integer from 1 to 10,000 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.

In the present invention, the quinacridone derivative preferably comprises a flexible alkyl and alkoxy chain at the 5,12-position.

In addition, the molecule having the electron donor property is preferably at least one selected from the following formula (3), the molecule having the electron acceptor is preferably at least one selected from the formula (4).

However, in Chemical Formula 3, R ₁ to R ₅₂ , and in Chemical Formula 4, R ₁ to R _{118 are} independently a hydrogen atom; Halogen 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 selected from the group consisting of aryl groups having 10 to 24 carbon atoms having a fused aromatic ring compound.

More preferably, the organic photoelectric conversion polymer of the present invention may be represented by the following formula (5).

On the other hand, the organic photoelectric conversion polymer of the present invention can be prepared using the Suzuki coupling reaction.

In this case, xylene, toluene, dimethylformamide (DMF), or the like may be used as a solvent, and a 1-10 mol% aqueous solution of K ₂ CO ₃ or Na ₂ CO ₃ may be used as a base. It can be used, and the polymer can be obtained using 0.5 to 10 mol% of tetrakis (triphenylphosphine) palladium (tetrakistriphenylphosphinepalladium) as a catalyst.

According to a preferred embodiment, the organic photoelectric conversion polymer of the present invention is 5,12-bis (2-octyldodecyl) -2,9-bis (4,4,5,5, -tetramethyl) in toluene. -1,3,2-dioxaborolan-2-yl) quinolino [2,3-b] acridin-7,14 (5H, 2H) -dione {5,12-bis (2 -octyldodecyl) -2,9-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) quinolino [2,3-b] acridine-7,14 (5H, 12H) -dione} and 4,7-bis (5-bromothiophen-2-yl) -5,6-bis (octyloxy) benzo [C] {1,2,5} thiadiazole {4,7-bis (5-bromothiophen-2-yl) -5,6-bis (octyloxy) benzo [c] [1,2,5] thiadiazole} was added and stirred; 1.5 mol% of tetrakis (triphenylphosphine) palladium (tetrakistriphenylphosphinepalladium), 2 mol% of an aqueous K ₂ CO ₃ solution, and Aliquat 336, a surfactant, were stirred for 10 minutes; Stirring at 90 ° C. for 48 hours; 0.1 ml of bromothiophene is dropped and reacted for 12 hours.

After completion of the TLC reaction, the reaction may be quenched with HCl, extracted with chloroform, washed with distilled water to remove water, and purified by column purification.

In the present invention, a method of manufacturing the organic photoelectric conversion polymer has been described as described above, but the method of preparing the polymer compound is not particularly limited, and any method may be used as long as it is a conventional synthetic method.

The organic photoelectric conversion polymer of Chemical Formula 5 according to the present invention can confirm a gentle peak than the solution phase on the film as shown in the UV spectrum (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.

In addition, the present invention provides an organic photoelectric conversion device employing the organic photoelectric conversion polymer represented by Formula 1 or Formula 2, preferably the organic photoelectric conversion polymer represented by Formula 5 as an active layer.

The polymer 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 to which the polymer is applied is as follows.

First, an anode electrode material is coated on the substrate. In this case, a substrate used in a conventional organic photoelectric conversion device is used, and it is preferable to use a glass substrate or a transparent plastic substrate excellent in transparency, surface smoothness, ease of handling, and waterproofness. 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. In this case, the photoelectric conversion layer may be formed by spin coating, the thickness thereof is preferably in the range of 10 ~ 10,000 Å. 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 ~ 10,000 kPa.

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. The electron transport layer and the hole transport layer may be used 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 polymer synthesized in the structure of Formula 1 or Formula 2, preferably Formula 5 and PC61BM (phenyl C61-butyric acid methyl ester) or PC71BM (phenyl C71-butyric acid methyl ester) and various It is formed as a bulk heterojunction type with a fullerene derivative. In this case, the polymer and the fullerene derivative (PCBM) are preferably mixed in a ratio (w / w) in the range of 1:10 to 10: 1, and after mixing, 1 at a temperature of 50 to 300 ° C. to exhibit maximum properties. It is preferred to anneal for seconds to 24 hours.

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

The organic photoelectric conversion polymer according to the present invention was prepared as in Scheme 1 below.

[Reaction Scheme 1]

Wherein n is an integer of 1 to 10,000.

First, as starting material, 5,12-bis (2-octyldodecyl) -2,9-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) quinolino [2,3 -b] acridine-7,14 (5H, 12H) -dione and 4,7-bis (5-bromothiophen-2-yl) -5,6-bis (octyloxy) benzo [c] [1,2,5] thiadiazole was synthesized with reference to the following literature (Advanced Materials, 19, 2295-2300, 2007; Macromolecules, 41, 4, 2008; Journal of America Chemical Society, 129, 3472-3474, 2007).

5,12-bis (2-octyldodecyl) -2,9-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) quinolino [2,3-b] acridine-7 0.3 g of 14 (5H, 12H) -dione and 0.19 g of 4,7-bis (5-bromothiophen-2-yl) -5,6-bis (octyloxy) benzo [c] [1,2,5] thiadiazole Dissolve in 20 ml of toluene, add 15 ml of 2M K ₂ CO ₃ base, add several drops of surfactant Aliquit336, and then use tetrakistriphenylphosphinepalladium (II) dichloride as a catalyst. 0.009 g of Aldrich) was added and stirred for 10 minutes, followed by stirring at 90 ° C. for 48 hours.

Finally, 0.1 ml of bromothiophene (Aldrich) was added as an end capper, stirred for 12 hours, and purified to obtain 0.36 g of the organic photoelectric conversion polymer of Scheme 1 (yield: 46%).

¹ H-NMR (400 MHz, CDCl 3, δ) 8.10 (S, 2H), 4.69 (S, 1H), 4.20 (br, 8H), 3.53 (br, 5H), 2.43-0.48 (br)

Example  2. Fabrication of organic photoelectric conversion device

The device was manufactured under the following conditions using the polymer prepared in Example 1.

Specifically, PEDOT: PSS was filtered using a 0.45 ㎛ PTFE syringe filter, and stirred in a shaker to prevent phase separation of 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, 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.

After spin coating, PEDOT: PSS for 20 minutes at 110 ° C, AedotronTMC for 20 minutes at 140 ° C, and the polymer and fullerene active layer were heat-treated at 120 ° C for 1 hour to remove residual solvent. 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, all of BaF ₂ (0.1 Å / s, 2 ㎚) / Ba (0.2 Å / s , 2 nm) / Al (5 mA / s, 100 nm) in order to form an electrode.

The results of the photoelectric conversion characteristics of the device manufactured as described above are shown in Table 1 and FIG. 5.

No. Active layer Voc (V) Jsc (mA / cm 2) FF PCE (%) One PQB: PC61BM (1: 1) 0.76 4.4 47 1.6 2 PQB: PC61BM (1: 3) 0.76 3.1 54 1.3 3 PQB: PC71BM (1: 1) 0.78 6.2 47 2.3 4 PQB: PC71BM (1: 3) 0.78 4.9 46 1.8

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 (10)

A copolymer obtained by copolymerizing a quinacridone derivative with a molecule forming a p-type molecular or n-type molecular pair having an electron acceptor property as a main chain and represented by the following Chemical Formula 1 or Formula 2 Organic photoelectric conversion polymer.
[Chemical Formula 1]

(2)

The method of claim 1,
The quinacridone derivative is an organic photoelectric conversion polymer, characterized in that it comprises an alkyl and alkoxy chain in the 5,12-position.
The method of claim 1,
The molecule having an electron donor property is an organic photoelectric conversion polymer, characterized in that at least one selected from the formula (3).
(3)

Provided that R ₁ to R _{52 are} independently a hydrogen atom; Halogen 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 selected from the group consisting of aryl groups having 10 to 24 carbon atoms having a fused aromatic ring compound.
The method of claim 1,
The molecule having the electron accepting characteristic is an organic photoelectric conversion polymer, characterized in that at least one selected from the formula (4).
[Chemical Formula 4]

Provided that R ₁ to R _{118 are} independently a hydrogen atom; Halogen 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 selected from the group consisting of aryl groups having 10 to 24 carbon atoms having a fused aromatic ring compound.
The method of claim 1,
The organic photoelectric conversion polymer is an organic photoelectric conversion polymer, characterized in that represented by the formula (5).
[Chemical Formula 5]

However, n is an integer of 1-10,000 in the above.
An organic photoelectric device employing the organic photoelectric conversion polymer of claim 1 as a photoactive layer.
An organic photoelectric device employing the organic photoelectric conversion polymer of claim 5 as a photoactive layer.
8. The method according to claim 6 or 7,
The photoactive layer is formed by spin coating (spin coating), the thickness of the organic photoelectric device, characterized in that 10 to 10,000 kPa.
8. The method according to claim 6 or 7,
The photoactive layer is an organic photoelectric device, characterized in that formed of fullerene derivative (PCBM) and bulk heterojunction type (bulk heterojunction type).
(1) adding a quinacridone derivative to an organic solvent and stirring;
(2) 0.5 to 10 mol of an aqueous solution of K ₂ CO ₃ or Na ₂ CO ₃ as a base, Aliquat 336 as a surfactant, and tetrakis (triphenylphosphine) palladium Adding more% and stirring for 5 to 15 minutes;
(3) stirring the material stirred in step (2) at 90 ° C. for 24 to 72 hours;
(4) adding bromothiophene to the stirred material 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 the immersion according to the step (5) and then removing the water and column purification; organic photoelectric conversion polymer manufacturing method comprising a.

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