KR20190103062A - Three component copolymers for semiconductor, Preparation method thereof and Organic semiconductor device comprising the same - Google Patents

Abstract

The present invention relates to a three component copolymer for organic semiconductors, a preparation method thereof and an organic semiconductor device comprising the same. The three component copolymer introduces an electron donative material (D) or an electron accepting material (A) on a BDT-BDD basic main chain at a proper ratio, thereby minimizing steric hindrance and having excellent solubility and oxidative stability. In addition, an organic solar cell comprising the three component copolymer shows high photoelectric transformation efficiency and has excellent atmospheric stability.

Description

Three component copolymers for organic semiconductors, a method of manufacturing the same and an organic semiconductor device comprising the same

The present invention relates to a ternary powder copolymer for organic semiconductor, a method for preparing the same, and an organic semiconductor device including the same.

As the pollution problem caused by high oil prices and fossil fuels is raised all over the world, the demand for sustainable eco-friendly energy sources is rapidly increasing. Eco-friendly energy sources are solar, wind, hydro, wave, and geothermal, and solar cells that can generate electricity using dual solar are attracting attention as the fewest places and infinite electric energy sources. From the 1.7 x 105 TW of solar energy reaching the earth's surface, it is estimated that the amount of solar energy actually available is 600 TW. At this time, if a solar power plant with 10% efficiency is available, it can supply about 60TW of power. This is an enormous amount that meets future demand for sustainable energy sources compared to the global energy demand of 28 TW in 2050.

Currently, the first generation crystalline silicon solar cells using inorganic materials account for 90% of the solar power market. However, this is more than 5 ~ 20 times higher than the fossil fuel, so it is only used for long-term medium and large power generation, and its application value is low. As a result, second-generation thin-film solar cell technology (CdTe, CIGS, etc.), which replaces silicon, has rapidly emerged and occupies the remaining 10% of the market. However, second-generation solar cell technology also requires expensive equipment because some materials are classified as precious metals and semiconductor thin films are formed through vacuum and high temperature processes during device fabrication. There is an organic solar cell as a low-cost solar cell to solve these problems. Since organic materials are used, the solution process is possible, which lowers the unit cost of solar cells, and is widely used as a next-generation solar cell because of its potential for applications such as clothing and portable electric and electronic products due to its mechanical flexibility, ease of design, and variety.

For practical application of organic solar cells, improvement of efficiency, long life, large area, development of printable materials, and securing transparent electrodes are the first choices. By far, the efficiency of organic solar cells must be improved. The development of high resolution (high efficiency and high stability) materials capable of low temperature solution process can significantly lower production costs and solve technical problems in a chain. Recently, organic solar cells are classified into fullerene-based and non-fullerene-based organic solar cells according to the type of photoactive layer electron acceptor material. Currently, organic solar cell efficiency is 11.5% based on the National Renewable Energy Laboratory (NREL) certification for fullerene and 13.1% for non-fullerene. Fullerene-based organic solar cells take more than 15 years to develop to the present level, while non-fullerene-based organic solar cells take less than five years. In addition, in terms of stability of the organic solar cell, the non-fullerene system is generally reported to be superior to the fullerene system. The typical derivative, the world's highest efficiency in the fullerene-based organic solar cell, PCE11, has burn-in decomposition after 5 days of aging in the air, resulting in a 39% reduction in efficiency. have. On the other hand, in the case of non-fullerene, the efficiency was not reduced by 15% even after 5 days of aging.

Accordingly, the present inventors describe a method for designing and synthesizing a wide bandgap copolymer for electron donors that can have high performance in a non-fullerene system having excellent efficiency and stability. The designed copolymers were adjusted in proportion to the copolymer constituents to have the appropriate crystallinity, solubility and relative electron acceptor material and optimal High Ocuupied Molecular Orbital (HOMO) offset energy levels. In addition, the structural, optical, and electrochemical properties of these materials were systematically studied, and organic solar cell devices were fabricated to evaluate their performance and stability. Horizontal benzodithiophene (BDT, benzo [1,2-b: 4,5-b '] dithiophene) having excellent planarity, oxidative stability, and mobility is converted to D1 and benzodithiophenedione (BDD, benzo [ 1,2-c: 4,5-c '] dithiophene-4,8-dione) as A1 and the push-pull form of D1-A1 as the main chain. Considering the curvature of the main chain polymer, D2 or A2 having various properties was introduced at an appropriate ratio. Through this ternary copolymer system, material synthesis with higher performance than existing D1-A1 polymer was successfully achieved. In particular, M (BDD-T) S = 0.5 of the synthesized new copolymer is used at a relatively low cost since 30% less than the raw material, and low temperature solution process is possible because no heat treatment is required. In addition, the energy conversion efficiency of the ITIC-Th combination is up to 11.63%, 3.6% higher than that of the existing D1-A1 polymer. Therefore, the present invention is ideal for demonstrating the excellence and effectiveness of the copolymer design method.

SUMMARY OF THE INVENTION An object of the present invention is to provide an optimized structure having a suitable crystallinity, solubility and excellent oxidation stability by introducing an electron donor material or electron acceptor material having various properties into the BDT-BDD basic backbone at an appropriate ratio. It is.

In addition, an object of the present invention is to provide a high-performance organic semiconductor device at room temperature, normal humidity by including the novel ternary copolymer as an electron donor compound.

The present invention provides a ternary copolymer comprising at least one repeating unit selected from the group consisting of Formula 1 and Formula 2 below:

[Formula 1]

[Formula 2]

In the above formulas 1 and 2,

D is one type of regular resin selected from the group consisting of benzodithiophene (BDT, benzodithiophene), benzodithienothiophene (BDTT, benzodithienothiophene), naphthodithiophene (NDT), and bithiophene (BiT, bithiophene). (Regioregular) electron donor molecule that is a derivative,

A is benzodithiophendione (BDD, benzodithiophene-dione), thienopyrrolidione (TPD, thienopyrroledione), phthalimide (PT, phthalimide), diketopyrrolopyrrole (DPP, diketopyrrolopyrrole), indigo (ID, Indigo), Naphthothiophene dimide (NDI, naphthothiophene dimide), perylene diimide (PDI, perylene dimide), benzocyadiazole (BT, benzothiadiazole), benzotriazole (BTz, benzotriazole), quinoxaline (Qu, quinoxaline), Phenazine (Pz, phenazine), benzothiadiazole-dicarboxylic imide (BTI), benzobistriazole (BBTz, benzobistriazole), naphthobenzobistriazole (NBTz) An electron acceptor molecule that is a derivative,

R ₁ and R ₂ are independently hydrogen; Substituted or unsubstituted alkyl group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted alkynyl group; Substituted or unsubstituted aryl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted fluorenyl group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted aryl sulfoxy group; Or a substituent selected from the group consisting of a substituted or unsubstituted heterocyclic group containing one or more of N, P, S, Se, Te atoms,

l is independently a real number 0≤ l <1,

m is independently a real number 0 <m ≤ 1,

l + m is 1,

n is an integer from 1 to 10,000.

The present invention also provides an organic solar cell, a perovskite solar cell, a field effect transistor, or an organic light emitting diode comprising the above-mentioned three minutes copolymer.

The ternary copolymer according to the present invention is polymerized by introducing an electron donor material (D) or an electron acceptor material (A) into the BDT-BDD basic backbone. In this case, by introducing D or A in an appropriate ratio, steric hindrance can be minimized, and a ternary copolymer having excellent solubility and oxidation stability can be provided. Therefore, the ternary powder copolymer of the present invention may be used as a photoactive layer material by forming a bulk heterojunction with a non-fullerene derivative, and may provide a high performance organic solar cell.

In addition, a relatively small amount of copolymer is used in the sambunbun copolymer according to the present invention when the photoactive layer mixed solution is prepared, and a pretreatment and posttreatment process is carried out when the thin film is formed by spin coating or slot die. This is not necessary. This is an advantage that can be usefully used for the next generation of organic solar cells as a material suitable for a roll-to-roll process.

In addition, the organic solar cell exhibits high photoelectric conversion efficiency and excellent atmospheric stability. It is possible to provide a high performance organic solar cell as a material having excellent stability as well as efficiency.

1 to 4 are diagrams for the synthesis design and synthesis mechanism of the ternary copolymer according to the present invention.
5 is a diagram for 1H NMR of Example 1 [M (BDD-T) S = 0.5].
6 is a diagram for 1H NMR of Example 2 [M (BDD-T) 4F = 0.5].
7 is a diagram for 1 H NMR of Example 3 [M (BDD-T) T = 0.1].
8 is a diagram for 1H NMR of Example 4 [M (BDD-T) N = 0.1].
FIG. 9 is a coverage image simulating a three-dimensional solid structure of a ternary powder according to one embodiment: (a) is a top view, and (b) is a side view.
Figure 10 shows the UV-Vis absorption spectrum of the ternary copolymer according to one embodiment: (a) is in the chloroform solution, (b) is the result in the film state.
FIG. 11 illustrates a cyclic voltammetry (CV) graph and an energy band diagram of a ternary powder according to an embodiment. FIG. (a) a CV graph; (b) Inverted energy band diagram.
12 shows the evaluation results of the organic solar cell device according to the inverse structure of the ternary powder copolymer according to an embodiment. (a) current density-voltage (JV) graph; (b) IPCE graph;
Figure 13 shows the device evaluation certificate measured in Daegu Nano Fusion Chamber of Example 1 [M (BDD-T) S = 0.5].
14 shows a graph of long-term stability evaluation of Example 1 [M (BDD-T) S = 0.5].
15 is a schematic view (101: ITO, 102: ZnO, 103: photoactive layer, 104: MoO ₃ , 105: Ag) of the organic solar cell device according to the present invention.
16 is a photograph of the reverse structure flexible organic solar cell module of the present invention.

As the invention allows for various changes and numerous embodiments, particular embodiments will be illustrated in the drawings and described in detail in the written description.

However, this is not intended to limit the present invention to specific embodiments, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention. In the following description of the present invention, if it is determined that the detailed description of the related known technology may obscure the gist of the present invention, the detailed description thereof will be omitted.

The present invention provides a ternary copolymer comprising at least one repeating unit selected from the group consisting of Formula 1 and Formula 2 below:

[Formula 1]

[Formula 2]

In the above formulas 1 and 2,

D is one type of regular resin selected from the group consisting of benzodithiophene (BDT, benzodithiophene), benzodithienothiophene (BDTT, benzodithienothiophene), naphthodithiophene (NDT), and bithiophene (BiT, bithiophene). (Regioregular) electron donor molecule that is a derivative,

A is benzodithiophendione (BDD, benzodithiophene-dione), thienopyrrolidione (TPD, thienopyrroledione), phthalimide (PT, phthalimide), diketopyrrolopyrrole (DPP, diketopyrrolopyrrole), indigo (ID, Indigo), Naphthothiophene dimide (NDI, naphthothiophene dimide), perylene diimide (PDI, perylene dimide), benzocyadiazole (BT, benzothiadiazole), benzotriazole (BTz, benzotriazole), quinoxaline (Qu, quinoxaline), Phenazine (Pz, phenazine), benzothiadiazole-dicarboxylic imide (BTI), benzobistriazole (BBTz, benzobistriazole), naphthobenzobistriazole (NBTz) An electron acceptor molecule that is a derivative,

R ₁ and R ₂ are independently hydrogen; Substituted or unsubstituted alkyl group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted alkynyl group; Substituted or unsubstituted aryl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted fluorenyl group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted aryl sulfoxy group; Or a substituent selected from the group consisting of a substituted or unsubstituted heterocyclic group containing one or more of N, P, S, Se, Te atoms,

l is independently a real number 0≤ l <1,

m is independently a real number 0 <m ≤ 1,

l + m is 1,

n is an integer from 1 to 10,000.

As an example, D in Structural Formula 1 may be any one of repeating units represented by Formulas 1-1 to 1-6:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

In Formula 1-1 to Formula 1-6,

R ₃ and R ₄ are independently hydrogen; Substituted or unsubstituted alkyl group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted alkynyl group; Substituted or unsubstituted aryl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted fluorenyl group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted aryl sulfoxy group; Or a substituent selected from the group consisting of a substituted or unsubstituted heteroring group including one or more of N, P, S, Se, and Te atoms.

Specifically, in Formula 1, D may include one or more repeating units selected from the group consisting of Formulas 4-1 and 4-2:

[Formula 4-1]

[Formula 4-2]

In Chemical Formulas 4-1 and 4-2,

X is the same as or different from each other, and independently, is nitrogen, oxygen, sulfur, selenium or tellurium,

R- ₅ to R ₇ are independently hydrogen; Cyano groups; Halogen group; Alkylthio groups having 1 to 20 carbon atoms; An alkyl group having 1 to 20 carbon atoms; It is a C1-C20 thionyl group or a C1-C20 alkoxy group.

For example, R ₅ to R ₇ are independently hydrogen, an alkoxy group substituted with a linear or branched alkyl group having 1 to 20 carbon atoms; A thionyl group substituted with a linear or branched alkyl group having 1 to 20 carbon atoms; The linear or branched alkyl group having 1 to 20 carbon atoms may be an ester group, and at least one may be an alkoxy group, a thionyl group, or an ester group other than hydrogen.

In addition, in Structural Formula 2, A may be any one of repeating units represented by Formulas 2-1 to 2-3:

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

In Chemical Formulas 2-1 to 2-3,

L or one of the substituted or unsubstituted heterocyclic groups containing one or more of N, P, S, Se, Te atoms or two adjacent substituents form a condensed ring,

R ₃ and R ₄ are independently hydrogen; Substituted or unsubstituted alkyl group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted alkynyl group; Substituted or unsubstituted aryl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted fluorenyl group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted aryl sulfoxy group; Or a substituent selected from the group consisting of a substituted or unsubstituted heteroring group including one or more of N, P, S, Se, and Te atoms.

Specifically, in Formulas 2-1 to 2-3, L may be a repeating unit represented by Formulas 3-1 to 3-17:

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

[Formula 3-5]

[Formula 3-6]

[Formula 3-7]

[Formula 3-8]

[Formula 3-9]

[Formula 3-10]

[Formula 3-11]

[Formula 3-12]

[Formula 3-13]

[Formula 3-14]

[Formula 3-15]

[Formula 3-16]

[Formula 3-17]

In Chemical Formulas 3-1 to 3-17,

X is the same as or different from each other, and independently, is nitrogen, oxygen, sulfur, selenium or tellurium,

R ₃ and R ₄ are independently hydrogen; Substituted or unsubstituted alkyl group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted alkynyl group; Substituted or unsubstituted aryl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted fluorenyl group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted aryl sulfoxy group; Or a substituent selected from the group consisting of a substituted or unsubstituted heteroring group including one or more of N, P, S, Se, and Te atoms.

More specifically, in Formula 2, A may include one or more repeating units selected from the group consisting of Formulas 5-1 and 5-2:

[Formula 5-1]

[Formula 5-2]

In Chemical Formulas 5-1 and 5-2,

R ₅ is independently hydrogen; Cyano groups; Halogen group; Alkylthio groups having 1 to 20 carbon atoms; An alkyl group having 1 to 20 carbon atoms; It is a C1-C20 thionyl group or a C1-C20 alkoxy group.

For example, R ₅ is an alkoxy group substituted with a linear or branched alkyl group having 1 to 20 carbon atoms; A thionyl group substituted with a linear or branched alkyl group having 1 to 20 carbon atoms; It may be an ester group substituted with a linear or branched alkyl group having 1 to 20 carbon atoms.

As one example, when the ternary copolymer according to the present invention includes a repeating unit represented by Structural Formula 1, the value of l may be 0.1 to 0.7. Specifically, the value of l is 0.1 to 0.6, 0.1 to 0.55, 0.1 to 0.5, 0.2 to 0.7, 0.2 to 0.6, 0.2 to 0.55, 0.2 to 0.5, 0.3 to 0.7, 0.3 to 0.6, 0.3 to 0.55, 0.3 to 0.5 , 0.4 to 0.7, 0.4 to 0.6, 0.4 to 0.55, 0.4 to 0.5 or 0.45 to 0.55.

As another example, when the third-minute copolymer according to the present invention includes a repeating unit represented by Structural Formula 2, the value of l may be 0.5 to 0.95. Specifically, the value of l is 0.5 to 0.95, 0.5 to 0.9, 0.1 to 0.5, 0.2 to 0.7, 0.2 to 0.6, 0.2 to 0.55, 0.2 to 0.5, 0.3 to 0.7, 0.3 to 0.6, 0.3 to 0.55, 0.3 to 0.5 , 0.4 to 0.7, 0.4 to 0.6, 0.4 to 0.55, 0.4 to 0.5 or 0.45 to 0.55.

The number average molecular weight of the ternary copolymer according to the present invention may be 30 kDa to 1,000 kDa. Specifically, the number average molecular weight of the ternary copolymer is 30 kDa to 1,000 kDa, 40 kDa to 1,000 kDa, 50 kDa to 1,000 kDa, 60 kDa to 1,000 kDa, 70 kDa to 1,000 kDa, 100 kDa to 1,000 kDa, 30 kDa To 800 kDa, 40 kDa to 800 kDa, 50 kDa to 800 kDa, 60 kDa to 800 kDa, 70 kDa to 800 kDa, 100 kDa to 800 kDa, 30 kDa to 500 kDa, 40 kDa to 500 kDa, 50 kDa to 500 kDa, 60 kDa to 500 kDa, 70 kDa to 500 kDa, 100 kDa to 500 kDa, 30 kDa to 250 kDa, 40 kDa to 250 kDa, 50 kDa to 250 kDa, 60 kDa to 250 kDa, 70 kDa to 250 kDa, 100 kDa to 250 kDa, 30 kDa to 150 kDa, 40 kDa to 150 kDa, 50 kDa to 150 kDa, 60 kDa to 150 kDa, 70 kDa to 150 kDa or 50 kDa to 100 kDa.

The ternary copolymer according to the present invention comprises an organic conductor such as a charge transport layer of a field effect transistor and a perovskite solar cell; Charge injection layers in organic light emitting diodes, flat screens, and touch screens; ITO planarization layer; Antistatic film; Printed circuits; And a capacitor, but is not limited thereto.

Specifically, the ternary copolymer is 1) preparing a mixed solution by dissolving the compound represented by Formula 2 and the compound represented by Formula 3 in a solvent; 2) preparing a mixture by adding a complex catalyst and a promoter to the mixed solution; 3) heating the mixture to polymerize; 4) terminating the polymerization reaction using an end-capping agent; 5) purifying the impurities and oligomers of the copolymer formed through the Soxhlet extractor; 6) removing and purifying the catalyst of the copolymer through solid phase extraction (SPE); It can be prepared via.

The solvent of step 1) may be at least one selected from toluene, benzene, ethylbenzene, toluene and dimethylformamide (1:10 vol%), chlorobenzene and dichlorobenzene.

The complex catalyst of step 2) may be at least one selected from Pd (PPh ₃ ) ₄ , Pd (dba) _2, and Pd ₂ (dba) ₃ . The promoter may be at least one selected from P (o-tolyl) ₃ , pph ₃ , and Pcy ₃ HBF ₄ .

The heating temperature of step 3) may be carried out at a temperature of 80 to 180 ℃.

The end capping agent of step 4) may be at least one selected from 2-bromothiophene and 2- (taxetylstannyl) thiophene.

Soxhlet extraction of step 5) may be performed in the order of methanol, acetone, hexane, ethyl acetate, dichloromethane, dichloropropane, chloroform and chlorobenzene.

SPE purification of step 6) may not be performed depending on solubility.

In addition, the present invention provides an organic semiconductor device comprising the above-mentioned three minutes copolymer in the charge transport layer. The organic semiconductor device may include an organic solar cell, a perovskite solar cell, a field effect transistor, or an organic light emitting diode. Specifically, the ternary copolymer is an organic conductor, for example, a charge transport layer of a field effect transistor and a perovskite solar cell; Charge injection layers in organic light emitting diodes, flat screens, and touch screens; ITO planarization layer; Antistatic film; Printed circuits; And a capacitor, but is not limited thereto.

As one example, the organic solar cell according to the present invention may include the above-mentioned ternary powder copolymer in the photoactive layer. The organic solar cell may include the above-mentioned Samsung powder copolymer as an electron donor material. Specifically, the organic solar cell of the present invention may include the ternary copolymer and the non-fullerene derivative in the photoactive layer.

Specifically, the photoactive layer may include a ternary copolymer and a non fullerene derivative. More specifically, the non-fullerene derivative may include inindacenothiothiophene (indacenodithiophene) or indacenothithienothiophene (indacenodithienothiophene). For example, the non-fullerene derivative is ITIC (3,9-bis (2-methylene- (3- (1,1-dicyanomethylene) -indanone))-5,5,11,11-tetrakis (4-hexylphenyl) -dithieno [2,3-d: 2 ', 3'-d']-s-indaceno [1,2-b: 5,6-b '] dithiophene, ITIC-Th (3,9-bis (2 -methylene- (3- (1,1-dicyanomethylene) -indanone))-5,5,11,11-tetrakis (5-hexylthienyl) -dithieno [2,3-d: 2 ', 3'-d'] -s-indaceno [1,2-b: 5,6-b '] dithiophene), ITIC-M (3,9-bis (2-methylene-((3- (1,1-dicyanomethylene) -6/7 -methyl) -indanone))-5,5,11,11-tetrakis (4-hexylphenyl) -dithieno [2,3-d: 2 ', 3'-d']-s-indaceno [1,2-b : 5,6-b '] dithiophene), IDIC (2,2'-((2Z, 2'Z)-((4,4,9,9-tetrahexyl-4,9-dihydro-s-indaceno [1 , 2-b: 5,6-b '] dithiophene-2,7-diyl) bis (methanylylidene)) bis (3-oxo-2,3-dihydro-1H-indene-2,1-diylidene)) dimalononitrile) , ITIC-4F (3,9-bis (2-methylene-((3- (1,1-dicyanomethylene) -6,7-difluoro) -indanone))-5,5,11,11-tetrakis (4- hexylphenyl) -dithieno [2,3-d: 2 ', 3'-d']-s-indaceno [1,2-b: 5,6-b '] dithiophene), IEICO-4F ((2,2' -((2Z, 2'Z)-(((4,4,9,9-tetrakis (4-hexylphenyl) -4,9-dihydro-s-indaceno [1,2-b: 5,6-b ' ] dithiophene-2,7-diyl) bis (4-((2-ethylhexyl) oxy) thiophene-5,2-diyl)) bis (methanylylidene)) bis (5,6-difluoro-3-oxo-2,3 -dihydro-1H-indene-2,1-diylidene)) dimalononitrile) and IEICO-4Cl (2,2 '-((2Z, 2'Z)-(((4,4,9-tris (4-hexylphenyl)) -9- (4-pentylphenyl) -4,9-dihydro-s-indaceno [1,2-b: 5,6-b dithiophene-2,7-diyl) bis (4-((2-ethylhexyl) oxy) thiophene-5,2-diyl)) bis (methanylylidene)) bis (5,6-dichloro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene)) dimalononitrile) It may include one or more kinds. More specifically, ITIC (3,9-bis (2-methylene- (3- (1,1-dicyanomethylene) -indanone))-5,5,11,11-tetrakis (4-hexylphenyl) -dithieno [2, 3-d: 2 ', 3'-d']-s-indaceno [1,2-b: 5,6-b '] dithiophene), ITIC-Th (3,9-bis (2-methylene- (3 -(1,1-dicyanomethylene) -indanone))-5,5,11,11-tetrakis (5-hexylthienyl) -dithieno [2,3-d: 2 ', 3'-d']-s-indaceno [ 1,2-b: 5,6-b '] dithiophene), IDIC (2,2'-((2Z, 2'Z)-((4,4,9,9-tetrahexyl-4,9-dihydro- s-indaceno [1,2-b: 5,6-b '] dithiophene-2,7-diyl) bis (methanylylidene)) bis (3-oxo-2,3-dihydro-1H-indene-2,1- diylidene)) dimalononitrile), ITIC-4F (3,9-bis (2-methylene-((3- (1,1-dicyanomethylene) -6,7-difluoro) -indanone))-5,5,11,11 -tetrakis (4-hexylphenyl) -dithieno [2,3-d: 2 ', 3'-d']-s-indaceno [1,2-b: 5,6-b '] dithiophene), IEICO-4F ( (2,2 '-((2Z, 2'Z)-(((4,4,9,9-tetrakis (4-hexylphenyl) -4,9-dihydro-s-indaceno [1,2-b: 5 , 6-b '] dithiophene-2,7-diyl) bis (4-((2-ethylhexyl) oxy) thiophene-5,2-diyl)) bis (methanylylidene)) bis (5,6-difluoro-3- oxo-2,3-dihydro-1H-indene-2,1-diylidene)) dimalononitrile) or IEICO-4Cl (2,2 ′-((2Z, 2 ′) Z)-(((4,4,9-tris (4-hexylphenyl) -9- (4-pentylphenyl) -4,9-dihydro-s-indaceno [1,2-b: 5,6-b dithiophene- 2,7-diyl) bis (4-((2-ethylhexyl) oxy) thiophene-5,2-diyl)) bis (methanylylidene)) bis (5,6-dichloro-3-oxo-2,3-dihydro- 1H-indene-2,1-diylidene)) dimalononitrile).

In addition, the photoactive layer may include a ternary powder copolymer and a fullerene derivative. Specifically, the fullerene derivative may include a C ₆₀ fullerene derivative or a C ₇₀ fullerene derivative. For example, the fullerene derivative is PC ₆₁ BM ([6,6] -Phenyl-C61-butyric acid methyl ester), PC ₇₁ BM ([6,6] -Phenyl-C71-butyric acid methyl ester), IC60BA ( 1 ', 1'',4', 4 ''-tetrahydro-di [1,4] methanonaphthaleno [5,6] fullerene-C60), Bis-PC-- ₆₀ BM (Bis (1- [3- (methoxycarbonyl) ) propyl] -1-phenyl)-[6,6] C62) and Bis-PC ₇₀ BM, Bis-PC ₇₀ BM (Bis (1- [3- (methoxycarbonyl) propyl] -1-phenyl)-[6, 6] C72) may include one or more selected from the group consisting of. Specifically, the fullerene derivative is PC ₆₁ BM ([6,6] -Phenyl-C61-butyric acid methyl ester), PC ₇₁ BM ([6,6] -Phenyl-C71-butyric acid methyl ester), IC60BA (1 ', 1'',4', 4 ''-tetrahydro-di [1,4] methanonaphthaleno [5,6] fullerene-C60), Bis-PC-- ₆₀ BM (Bis (1- [3- (methoxycarbonyl) propyl] -1-phenyl)-[6,6] C62) or Bis-PC70BM, Bis-PC ₇₀ BM (Bis (1- [3- (methoxycarbonyl) propyl] -1-phenyl)-[6,6] C72 May be).

The photoactive layer is an electron acceptor compound including a non-fullerene or a fullerene derivative; And the above-mentioned ternary powder copolymer. Specifically, the ternary powder copolymer may include 0 to 5wt% based on the total weight. In addition, the electron acceptor compound including a non fullerene or a fullerene derivative may include 0 to 0 wt% based on the total weight. More specifically, the photoactive layer is a mixture ratio of the three-minute copolymer and the electron acceptor compound 1: 0.5 to 1: 2, 1: 0.8 to 1: 2, 1: 0.9 to 1: 2, 1: 1.0 to 1: 2, 1: 1.1 to 1: 2, 1: 1.2 to 1: 2, 1: 1.25 to 1: 2, 1: 1.3 to 1: 2, 1: 1.4 to 1: 2, 1: 1.5 to 1: 2, 1: 0.5 to 1: 1.5, 1: 0.8 to 1: 1.5, 1: 0.9 to 1: 1.5, 1: 1.0 to 1: 1.5, 1: 1.1 to 1: 1.5, 1: 1.2 to 1: 1.5, 1: 1.25 to 1: 1.5, 1: 1.3 to 1: 1.5, 1: 1.4 to 1: 1.5, 1: 0.5 to 1: 1.3, 1: 0.8 to 1: 1.3, 1: 0.9 to 1: 1.3, 1: 1.0 to 1: 1.3, 1: 1.1 to 1: 1.3, 1: 1.2 to 1: 1.3, 1: 1.25 to 1: 1.3, 1: 0.5 to 1: 1.2, 1: 0.8 to 1: 1.2, 1: 0.9 to 1: 1.2, 1: 1.0 to 1: 1.2, 1: 1.1 to 1: 1.2 or 1: 0.5 to 1: 0.8.

For example, the organic solar cell according to the present invention may be a typical structure or an inverted structure. Specifically, the organic solar cell is a substrate; A first buffer layer; Photoactive layer containing the above-mentioned polymer; It may include a second buffer layer and an electrode.

Specifically, the substrate is aluminum (Al), indium tin oxide (ITO), gold (Au), silver (Ag), fluorine doped tin oxide (FTO), aluminum doped Aluminum doped zinc oxide (AZO), indium zinc oxide (IZO), indium zinc tin oxide (IZTO) ZnO-Ga ₂ O ₃ , ZnO-Al ₂ O ₃ and anti It may include one or more selected from the group consisting of antimony tin oxide (ATO). More specifically, the substrate may be aluminum (Al), indium tin oxide (ITO), indium zinc oxide (IZO), or indium zinc tin oxide (IZTO).

In addition, the first buffer layer and the second buffer layer may each independently include one or more selected from the group consisting of zinc oxide, titanium oxide, molybdenum oxide, nickel oxide and tungsten oxide. Specifically, the first buffer layer and the second buffer layer may each independently include zinc oxide, titanium oxide, or molybdenum oxide. More specifically, the first buffer layer and the second buffer layer may each independently be zinc oxide or molybdenum oxide.

The organic solar cell according to the present invention may provide a flexible organic solar cell by including a ternary copolymer in the photoactive layer as described above.

In addition, the perovskite solar cell according to the present invention may include the above-described Samsung powder copolymer in the hole transport layer as an electron donor material. Specifically, the perovskite solar cell may be a samsung copolymer may be used as the hole transport layer, spiro-OMeTAD (2,2 ', 7,7'-tetrakis- (N, N-di-4-methoxyphenylamino) -9,9'-spirobifluorene) can be substituted.

Furthermore, the field effect transistor according to the present invention may include the above-mentioned ternary powder copolymer in the organic semiconductor layer. Specifically, the field effect transistor may be a ternary copolymer may be used as the active semiconductor layer, it may be replaced with an organic material silicon or metal oxide inorganic semiconductor.

In addition, the organic light emitting diode according to the present invention may include the above-described Samsung powder copolymer in the hole transport layer or the hole injection layer. Specifically, the organic light emitting diode may be a samsung copolymer may be used as a hole transport layer or a hole injection layer, it may replace a single molecule.

As one example, an organic solar cell according to the present invention comprises the steps of 1) preparing a first electrode; 2) preparing a mixed solution by adding a copolymer and a non-fullerene-based derivative prepared according to the method for preparing a ternary copolymer in an organic solvent; 3) coating and mixing the mixed solution on the first electrode to form a photoactive layer; And 4) forming a second electrode on the photoactive layer. Between steps 1) and 2); And between 3) and 4) step may comprise the steps of preparing and coating the hole transport layer and the electron transport layer and drying to form a layer. The organic solar cell device structure may be either a conventional structure or an inverted structure.

The photoactive layer of step 2) is a ternary powder represented by the formula 1 and 2; It is characterized by being formed as a bulk heterojunction (Bulkheterojunction) comprising a non-fullerene derivative or a fullerene derivative, but is not limited thereto.

EMBODIMENT OF THE INVENTION Hereinafter, based on the above-mentioned content, this invention is demonstrated in detail with reference to an Example and drawing. The following examples are intended to illustrate the invention and are not intended to limit the scope of the invention.

Example 1 Synthesis of M (BDD-T) S = 0.5 Copolymer

1.1: Preparation of 2- (2-ethylhexylthio) thiophene (1)

The 100 mL three neck flask is vacuum and nitrogen replaced. In a nitrogen atmosphere, 5.0 g (59.5 mmol) of thiophene and 30 mL of anhydrous tetrahydrofuran (THF) are added thereto, and the mixture is cooled to 0 ° C while stirring. After maintaining the temperature for 30 minutes, 23.8 mL (59.5 mmol) of n-butyllithium (2.5M hexane solution) was added to the dropping funnel and slowly added dropwise for about 10 minutes. After 30 min temperature hold, cool to −78 ° C. and add 1.9 g (59.5 mmol) of sulfur in one portion. After maintaining the temperature for 30 minutes, the reaction is performed at room temperature for 3 hours. Add 11.5 g (59.5 mmol) of 2-ethylhexyl bromide at once and stir for 24 hours. 34.5% aqueous hydrochloric acid solution, water and hexane are added to terminate the reaction. Extract three times with water and hexane and remove the organic layer with magnesium sulfate (Magnesium sulfate, MgSO ₄ ). The solvent is removed and purified by silica gel column chromatography. 8.5 g (37,21 mmol, 62.5%) of a colorless oil are obtained. ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.32-7.29 (m, 1H), 7.10-7.07 (m, 1H), 6.96-6.92 (m, 1H), 2.81 (d, 2H), 1.67-1.65 (m , 1H), 1.58-1.16 (m, 8H), 0.90-0.79 (m, 6H).

1.2: Preparation of 4,8-bis (5- (2-ethylhexylthio) thiophen-2-yl) benzo [1,2-b: 4,5-b '] dithiophene (2)

The 100 mL three neck flask is vacuum and nitrogen replaced. In a nitrogen atmosphere, 5.0 g (17.61 mmol) of Compound (1) and 35 mL of anhydrous tetrahydrofuran were added and cooled to -78 ° C while stirring. After maintaining the temperature for 30 minutes, 8.1 mL (19.4 mmol) of n-butyllithium (2.5M hexane solution) was added to the dropping funnel and slowly added dropwise for about 5 minutes. Reaction at room temperature for 2 hours 30 minutes. Add 0.97 g (4.45 mmol) of benzo [1,2-b: 4,5-b '] dithiophene-4,8-dione at once and stir at 50 ° C. for 2 hours. After cooling to room temperature, 7.73 g (34.5 mmol) of tin (II) chloride dihydrate is dissolved in 17 mL of 10% hydrochloric acid, and reacted for 1 hour 30 minutes. Extract three times with water and ether and remove the organic layer with magnesium sulfate. After removing the solvent, the residue was purified by silica gel column chromatography using hexane. 1.35 g (2.10 mmol, 47.2%) of yellow sticky oil are obtained. ¹ H NMR (400 MHz, CDCl 3): δ 7.62-7.61 (d, 2H), 7.48-7.47 (d, 2H), 7.34-7.33 (d, 2H), 7.23-7.22 (d, 2H), 2.94-2.93 (m, 4H), 1.70-1.68 (m, 2H), 1.65-0.90 (m, 16H), 0.85-0.60 (m, 12H).

1.3: 2,6-bis (trimethyltin) -4,8-bis (5- (2-ethylhexylthio) thiophen-2-yl) benzo [1,2-b: 4,5-b '] Preparation of Dithiophene (3)

The 50 mL two neck flask is vacuum and nitrogen replaced. In a nitrogen atmosphere, 1.0 g (1.34 mmol) of Compound (2) and 17 mL of anhydrous tetrahydrofuran were added and cooled to -78 ° C while stirring. After maintaining the temperature for 30 minutes, 1.4 mL (3.37 mmol) of n-butyllithium (2.5M hexane solution) was slowly added dropwise for 2 minutes. After maintaining the temperature at -78 ° C for 1 hour, the reaction is performed at room temperature for 1 hour. After cooling to −78 ° C. and maintaining the temperature for 30 minutes, 4.0 mL of trimethyltin chloride (1.0M hexane solution) was added at once and stirred at room temperature for 24 hours. The reaction was terminated by adding a saturated aqueous solution of sodium bicarbonate (NaHCO ₃ ). Add water and ether three times or more and remove the organic layer with magnesium sulfate. The solvent is removed and then recrystallized from ethanol. 1.21 g (1.25 mmol, 93.3%) of yellow particles are obtained. ¹ H NMR (400 MHz, CDCl 3): δ 7.64-7.63 (s, 2H), 7.34-7.33 (d, 2H), 7.23-7.22 (d, 2H), 2.95-2.94 (m, 4H), 1.70-1.68 (m, 2H), 1.65-0.90 (m, 16H), 0.85-0.60 (m, 12H), 0.52-0.40 (m, 18H).

1.4: Polymerization of M (BDD-T) S = 0.5

Prepare 10-20 mL vials. Add 153.4 mg (0.20 mmol) of 1 (EH-2DBDT), 90.5 mg (0.10 mmol) of Formula 2 (EH-DTBDD) and 96.9 mg (0.10 mmol) of Compound (3). Then 16 mg (0.01385 mmol, 6.925 mol%) of Pd (PPh ₃ ) ₄ is added and the cap is capped. Stir under vacuum for 1 hour. After nitrogen replacement, 7 mL of anhydrous toluene is added and vacuumed for about 10 minutes until no bubbling occurs. After nitrogen substitution, the reaction is carried out at 110 ° C. for 3 hours. Monitor the change of color from yellow to red, purple and blue during the reaction. When shaking, if bubbling and precipitates are found, immediately add 0.1 mL of 2-bromothiophene and endcap for 1 hour and 30 minutes. Then add 0.2 mL of 2- (taxetylstannyl) thiophene and endcap for 1 hour 30 minutes. Lower the temperature and add 3 mL of chlorobenzene at room temperature. Heated with a heat gun (Heating gun) to completely dissolve the polymer and precipitate in methanol. The polymer is added to thimble and purified by Soxhlet extraction in the order of methanol, acetone, hexane, ethyl acetate, dichloromethane, dichloropropene and chloroform. The filtrate in each fraction is concentrated under reduced pressure, in particular the material dissolved in chloroform is SPE purified and reprecipitated with cold methanol. M (BDD-T) S = 0.5 is dried in a vacuum oven at 50 ° C. for 24 hours. 184 mg (0.15 mmol, 75.1%) of dark blue powder are obtained. ¹ H NMR (400 MHz, CDCl ₃ ) was shown in FIG. 5. In addition, the process of synthesizing the ternary copolymer [M (BDD-T) S = 0.5] of Example 1 is shown in detail in FIG. 1.

Example 2 Synthesis of M (BDD-T) 4F = 0.5 Copolymer

2.1: Preparation of 4,8-dihydroxybenzo [1,2-b: 4,5-b '] dithiophene (1)

The 250 mL two neck flask is vacuum and nitrogen replaced. In a nitrogen atmosphere, 6.94 g (31.5 mmol) of benzo [1,2-b: 4,5-b '] dithiophene-4,8-dione and 100 mL of anhydrous ethanol were added and cooled to 0 ° C while stirring. After holding for 30 minutes, 2.64 g (69.5 mmol) of sodium borohydride (NaBH ₄ ) are added in one portion. Stir at 85 ° C. for 12 hours. The reaction is terminated with 25 mL of 1M aqueous hydrochloric acid solution. Filter with water and dry for 24 hours at 70 ° C. in a vacuum oven. 6.96 g (31,3 mmol, 99.4%) of a colorless oil are obtained. ¹ H NMR (400 MHz, DMSO-d 6): δ 9.80 (s, 2H), 7.60-7.59 (d, 2H), 7.54-7.53 (d, 2H).

2.2: Preparation of 4,8-bis (trifluoromethanesulfonyloxy) benzo [1,2-b: 4,5-b '] dithiophene (2)

The 500 mL three neck flask is vacuum and nitrogen replaced. In a nitrogen atmosphere, 6.0 g (27.0 mmol) of Compound (1), 6.6 mL of anhydrous pyridine and 150 mL of anhydrous dichloromethane are added and cooled to 0 ° C while stirring. After maintaining the temperature for 30 minutes, 13.6 mL (80.0 mmol) of tricyclic anhydride is added to the dropping funnel and slowly added dropwise for about 10 minutes. Stir at 0 ° C. for 12 hours. The reaction is terminated with 100 mL of 1M aqueous hydrochloric acid solution. Water and dichloromethane are added three times or more, and the organic layer is removed with magnesium sulfate. After removing the solvent, the mixture was purified by silica gel column chromatography using ethyl acetate and hexane mixed solution. 8.93 g (18,36 mmol, 68.0%) of a white solid are obtained. ¹ H NMR (400 MHz, DMSO-d 6): δ 8.22-8.21 (d, 2H), 7.57-7.56 (d, 2H).

2.3: Preparation of 5-bromo-2- (2-ethylhexyloxy) -1,3-difluorobenzene (3)

The 100 mL two neck flask is vacuum and nitrogen replaced. 2.5 g (11.96 mmol) of 4-bromo-2,6-difluorophenol, 3.0 g (15.55 mmol) of 2-ethylhexyl bromide, 6.6 g (47.84 mmol) of potassium carbonate (K) under nitrogen atmosphere ₂ CO ₃ ) and 30 mL of dimethylformamide (DMF) are added and stirred. Vacuum and nitrogen replacement for about 10 minutes until no bubbling occurs. Stir at 100 ° C. for 2 hours in a 300 W microwave oven. Water and chloroform are extracted three times or more, and the organic layer is removed with magnesium sulfate. After removing the solvent, the residue was purified by silica gel column chromatography using hexane. 3.25 g (10.12 mmol, 84.6%) of a colorless liquid are obtained. ¹ H NMR (400 MHz, CDCl 3): δ 7.07-7.04 (s, 2H), 4.00-3.99 (d, 2H), 1.68-1.63 (m, 1H), 1.51-1.41 (m, 4H), 1.34-1.29 (m, 4H), 0.94-0.91 (m, 6H), ¹³ C NMR (100 MHz, CDCl 3): δ 157.4, 154,89, 135,77, 116.06, 115.96, 113.50, 40.21, 30.05, 28.96, 23.43, 23.01, 14.05, 10.97.

2.4: Preparation of 2- (4- (2-ethylhexyloxy) -3,5-difluorophenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane ( 4)

The 100 mL two neck flask is vacuum and nitrogen replaced. 1.73 g (5.39 mmol) of compound (3), 1.64 g (6.46 mmol) of bis (pinacolato) diboron, 1.59 g (16.20 mmol) of potassium acetate and 25 mL of anhydrous dioxal under a nitrogen atmosphere Add dixane and stir. Add 132 mg (0.162 mmol) of Pd (dppf) Cl ₂ · CH ₂ Cl ₂ with strong nitrogen and stir at 80 ° C for 12 hours (keep dark). The mixture is filtered by passing through Celite. After removing the solvent, the mixture was purified by silica gel column chromatography using ethyl acetate and hexane mixed solution. 1.36 g (3.68 mmol, 68.2%) of a yellow liquid are obtained. ¹ H NMR (400 MHz, CDCl 3): δ 7.31-7.29 (s, 2H), 4.07-4.05 (d, 2H), 1.67-1.66 (m, 1H), 1.52-1.42 (m, 4H), 1.35-1.29 (m, 16 H), 0.94-0.90 (m, 6 H).

2.5: Preparation of 4,8-bis (4- (2-ethylhexyloxy) -3,5-difluorophenyl) benzo [1,2-b: 4,5-b '] dithiophene (5)

Prepare 10-20 mL vials. 0.4 g (0.82 mmol) of compound (2), 0.91 g (2.46 mmol) of compound (4), 55 mg (0.0476 mmol, 5.80 mol%) of Pd (PPh ₃ ) ₄ and 10 mL of anhydrous toluene Insert the cap and cap it. The vacuum is held for about 30 minutes until no bubbling occurs. After nitrogen replacement, 5 mL of 2M aqueous potassium carbonate solution is added. Then two drops of Aliquat 336 are added. It reacts at 100 degreeC for 24 hours. Water and chloroform are extracted three times or more, and the organic layer is removed with magnesium sulfate. After removing the solvent, the residue was purified by silica gel column chromatography using hexane. 0.44 g (0.65 mmol, 79.3%) of a colorless oil is obtained. ¹ H NMR (400 MHz, CDCl 3): δ 7.47-7.46 (d, 2H), 7.33-7.32 (d, 2H), 7.24-7.23 (s, 4H), 4.18-4.16 (m, 4H), 1.77-1.76 (m, 2H), 1.65-1.48 (m, 8H), 1.39-1.36 (m, 8H), 0.94-0.91 (m, 12H).

2.6: 2,6-bis (trimethyltin) -4,8-bis (4- (2-ethylhexyloxy) -3,5-difluorophenyl) benzo [1,2-b: 4,5-b Production of dithiophene (6)

Prepare 10-20 mL vials. 0.2 g (0.30 mmol) of compound (5) and 5 mL of anhydrous tetrahydrofuran are added, and the cap is capped. The vacuum is held for about 10 minutes until no bubbling occurs. After nitrogen substitution, it is cooled to -78 ° C and held for 30 minutes. 0.4 mL (0.96 mmol) of n-butyllithium (2.5M hexane solution) was slowly added dropwise for 1 minute. After maintaining the temperature for 1 hour, 1.0 mL of trimethyltin chloride (1.0M hexane solution) was added at once and stirred at room temperature for 24 hours. The reaction is terminated by adding saturated aqueous sodium bicarbonate solution. Add water and ether three times or more and remove the organic layer with magnesium sulfate. The solvent is removed and then recrystallized from ethanol. 0.26 g (0.26 mmol, 86.7%) of yellow particles are obtained. ¹ H NMR (400 MHz, CDCl 3): δ 7.31 (s, 2H), 7.24 (s, 4H), 4.19-4.18 (m, 4H), 1.78-1.77 (m, 2H), 1.65-1.48 (m, 8H ), 1.39-1.36 (m, 8H), 1.02-0.93 (m, 12H), 0.46-0.32 (m, 18H).

2.7: polymerization of M (BDD-T) 4F = 0.5

Prepare 10-20 mL vials. Add 76.7 mg (0.10 mmol) of 1 (EH-2DBDT), 45.2 mg (0.05 mmol) of Formula 2 (EH-DTBDD) and 49.8 mg (0.05 mmol) of Compound (6). Subsequently 8 mg (0.006925 mmol, 6.925 mol%) of Pd (PPh ₃ ) ₄ is added and the cap is capped. Stir under vacuum for 1 hour. After nitrogen replacement, 3.5 mL of anhydrous toluene is added and vacuumed for about 10 minutes until no bubbling occurs. After nitrogen substitution, the reaction is carried out at 110 ° C. for 3 hours. Monitor the change of color from yellow to red, purple and blue during the reaction. When shaking, if bubbling and precipitates are found, immediately add 0.1 mL of 2-bromothiophene and endcap for 1 hour and 30 minutes. Then add 0.2 mL of 2- (taxetylstannyl) thiophene and endcap for 1 hour 30 minutes. Lower the temperature and add 3 mL of chlorobenzene at room temperature. Heated with a heat gun (Heating gun) to completely dissolve the polymer and precipitate in methanol. The polymer is added to thimble and purified by Soxhlet extraction in the order of methanol, acetone, hexane, ethyl acetate, dichloromethane, dichloropropene and chloroform. The filtrate in each fraction is concentrated under reduced pressure, in particular the material dissolved in chloroform is SPE purified and reprecipitated with cold methanol. M (BDD-T) 4F = 0.5 was dried in a vacuum oven at 50 ° C. for 24 hours. 90.4 mg (0.073 mmol, 73.0%) of dark blue powder are obtained. ¹ H NMR (400 MHz, CDCl 3) was as shown in FIG. 6. In addition, the process of synthesizing the ternary copolymer [M (BDD-T) 4F = 0.5] of Example 2 was specifically illustrated in FIGS. 2A and 2B.

Example 3 Synthesis of M (BDD-T) T = 0.1 Copolymer

3.1: Preparation of 5-octyl-1,3-di (thiophen-2-yl) -4H-thieno [3,4-c] pyrrole-4,6 (5H) -dione (1)

Prepare 10-20 mL vials. 1.5 g (3.545 mmol) of 1,3-dibromo-5-octyl-4H-thieno [3,4-c] pyrrole-4,6 (5H) -dione and 3.4 g (9.111 mmol) of 2- Add thiophene. Then 288 mg (0.245 mmol, 6.91 mol%) of Pd (PPh ₃ ) ₄ is added and the cap is capped. Stir under vacuum for 1 hour. Add 20 mL of anhydrous toluene and hold for about 10 minutes until no bubbling occurs. After nitrogen substitution, the mixture was stirred at 110 ° C. for 24 hours. The mixture is filtered by passing through Celite. After removing the solvent, the mixture was purified by silica gel column chromatography using dichloromethane and hexane mixed solution. 1.40 g (3.25 mmol, 91.7%) of yellow powder are obtained. ¹ H NMR (400 MHz, CDCl 3): δ 8.01-8.00 (d, 2H), 7.44-7.43 (d, 2H), 7.13-7.12 (m, 2H), 3.66-3.64 (m, 2H), 1.72-1.64 (m, 2H), 1.35-1.26 (m, 10H), 0.87-0.85 (m, 3H).

3.2: Preparation of 1-3-bis (5-bromothiophen-2-yl) -5-octyl-4H-thieno [3,4-c] pyrrole-4,6 (5H) -dione (2)

The 100 mL two neck flask is vacuum and nitrogen replaced. 1.2 g (2.793 mmol) of Compound (1) were added under a nitrogen atmosphere, and 20 mL of anhydrous chloroform-acetic acid (10: 1) was added thereto. Add 1.243 g (6.983 mmol) of N-Bromosuccinimide (NBS) several times with strong nitrogen loading. Stir at room temperature for 3 hours (keep dark). Thin layer chromatography (TLC) monitors the progress of the reaction. The reaction was terminated by adding a saturated aqueous solution of sodium bicarbonate (NaHCO ₃ ). Water and chloroform are extracted three times or more, and the organic layer is removed with magnesium sulfate. After removing the solvent, the mixture was purified by silica gel column chromatography using dichloromethane and hexane mixed solution. The final product is recrystallized from ethanol. 1.23 g (2.09 mmol, 75.0%) of yellow powder are obtained. ¹ H NMR (400 MHz, CDCl 3): δ 7.64-7.63 (d, 2H), 7.06-7.05 (d, 2H), 3.64-3.62 (m, 2H), 1.68-1.64 (m, 2H), 1.33-1.25 (m, 10 H), 0.87-0.85 (m, 3 H).

3.3: Polymerization of M (BDD-T) T = 0.1

Prepare 10-20 mL vials. 52.4 mg (0.0684 mmol) of 1 (EH-2DBDT), 68.7 mg (0.076 mmol) of Formula 2 (EH-DTBDD) and 4.5 mg (0.0076 mmol) of Compound (2) are added. Then 6 mg (0.0051 mmol, 6.72 mol%) of Pd (PPh ₃ ) ₄ are added and the cap is capped. Stir under vacuum for 1 hour. After nitrogen replacement, 2.7 mL of anhydrous toluene is added and vacuumed for about 10 minutes until no bubbling occurs. After nitrogen substitution, the reaction is carried out at 110 ° C for 3 hours. Monitor the change of color from yellow to red, purple and blue during the reaction. When shaking, if bubbling and precipitates are found, immediately add 0.1 mL of 2-bromothiophene and endcap for 1 hour and 30 minutes. Then add 0.2 mL of 2- (taxetylstannyl) thiophene and endcap for 1 hour 30 minutes. Lower the temperature and add 3 mL of chlorobenzene at room temperature. Heated with a heat gun (Heating gun) to completely dissolve the polymer and precipitate in methanol. The polymer is added to thimble and purified by Soxhlet extraction in the order of methanol, acetone, hexane, ethyl acetate, dichloromethane, dichloropropene and chloroform. The filtrate in each fraction is concentrated under reduced pressure, in particular the material dissolved in chloroform is SPE purified and reprecipitated with cold methanol. M (BDD-T) T = 0.1 is dried at 50 ° C. in a vacuum oven for 24 hours. 74.5 mg (0.068 mmol, 89.5%) of dark blue powder are obtained. ¹ H NMR (400 MHz, CDCl 3) was shown in FIG. 7. In addition, a process of synthesizing the ternary copolymer [M (BDD-T) T = 0.1] of Example 3 is shown in detail in FIG. 3.

Example 4 Synthesis of M (BDD-T) N = 0.1 Copolymer

4.1: 2,7-bis (2-ethylhexyl) -4,9-di (thiophen-2-yl) benzo [lmn] [3,8] phenanthroline-1,3,6,8 (2H, 7H)-Preparation of Tetraon (1)

Prepare 10-20 mL vials. 1.0 g (1.54 mmol) of 4,9-dibromo-2,7-bis (2-ethylhexyl) benzo [lmn] [3,8] phenanthroline-1,3,6,8 (2H, 7H Add 1.724 g (4.62 mmol) of 2- (taxetylstannyl) thiophene with) -tetraone. Subsequently, 88 mg (0.077 mmol, 5.0 mol%) of Pd (PPh ₃ ) ₄ is added thereto and the cap is capped. Stir under vacuum for 1 hour. Add 20 mL of anhydrous toluene and hold for about 10 minutes until no bubbling occurs. After nitrogen substitution, the mixture was stirred at 110 ° C. for 24 hours. The mixture is filtered by passing through Celite. After removing the solvent, the mixture was purified by silica gel column chromatography using dichloromethane and hexane mixed solution. 0.91 g (1.39 mmol, 90.3%) of red powder are obtained. ¹ H NMR (400 MHz, CDCl 3): δ 8.76-8.75 (s, 2H), 7.57-7.56 (d, 2H), 7.31-7.30 (d, 2H), 7.21-7.20 (d, 2H), 4.08-4.07 (m, 4H), 1.94-1.92 (m, 2H), 1.42-1.23 (m, 16H), 0.95-0.83 (m, 12H).

3.2: 4,9-bis (5-bromothiophen-2-yl) -2,7-bis (2-ethylhexyl) benzo [lmn] [3,8] phenanthroline-1,3,6,8 Preparation of (2H, 7H) -tetraon (2)

The 50 mL two neck flask is vacuum and nitrogen replaced. Add 0.658 g (1.005 mmol) of compound (1) under nitrogen atmosphere and add 20 mL of anhydrous chloroform-dimethylformamide (1: 2). Add 0.423 g (2.38 mmol) of N-Bromosuccinimide (NBS) several times with strong filling of nitrogen. Stir at room temperature for 3 hours (keep dark). Thin layer chromatography (TLC) monitors the progress of the reaction. The reaction was terminated by adding a saturated aqueous solution of sodium bicarbonate (NaHCO ₃ ). Water and chloroform are extracted three times or more, and the organic layer is removed with magnesium sulfate. After removing the solvent, the mixture was purified by silica gel column chromatography using dichloromethane and hexane mixed solution. The final product is recrystallized from ethanol. 0.731 g (0.90 mmol, 89.6%) of red powder are obtained. ¹ H NMR (400 MHz, CDCl 3): δ 8.73-8.72 (s, 2H), 7.16-7.15 (d, 2H), 7.10-7.08 (d, 2H), 4.08-4.07 (m, 4H), 1.92-1.90 (m, 2H), 1.40-1.21 (m, 16H), 0.95-0.83 (m, 12H).

4.3: Polymerization of M (BDD-T) N = 0.1

Prepare 10-20 mL vials. Add 52.4 mg (0.0684 mmol) of 1 (EH-2DBDT), 68.7 mg (0.076 mmol) of Formula 2 (EH-DTBDD) and 6.2 mg (0.0076 mmol) of Compound (2). Then 6 mg (0.0051 mmol, 6.72 mol%) of Pd (PPh 3) 4 is added and the cap is capped. Stir under vacuum for 1 hour. After nitrogen replacement, 2.7 mL of anhydrous toluene is added and vacuumed for about 10 minutes until no bubbling occurs. After nitrogen substitution, the reaction is carried out at 110 ° C for 3 hours. If the reaction is too slow, add 0.27 mL of dimethylformamide and monitor the reaction. When shaking, if blue, bubbling and precipitated areas are found, immediately add 0.1 mL of 2-bromothiophene and endcap for 1 hour and 30 minutes. Then add 0.2 mL of 2- (taxetylstannyl) thiophene and endcap for 1 hour 30 minutes. Lower the temperature and add 3 mL of chlorobenzene at room temperature. Heated with a heat gun (Heating gun) to completely dissolve the polymer and precipitate in methanol. The polymer is added to thimble and purified by Soxhlet extraction in the order of methanol, acetone, hexane, ethyl acetate, dichloromethane, dichloropropene and chloroform. The filtrate in each fraction is concentrated under reduced pressure, in particular the material dissolved in chloroform is SPE purified and reprecipitated with cold methanol. M (BDD-T) N = 0.1 is dried at 50 ° C. in a vacuum oven for 24 hours. 74.5 mg (0.068 mmol, 89.5%) of dark blue powder are obtained. 1 H NMR (400 MHz, CDCl 3) was shown in FIG. 8. In addition, the process of synthesizing the ternary copolymer [M (BDD-T) N = 0.1] of Example 4 is shown in detail in FIG.

Example 5 Fabrication of Organic Solar Cell Device of Samsung Copolymers

Coverage calculations, physical and optical and electrochemical characterization of the synthesized ternary copolymers were carried out. Based on this, the reverse structure organic solar cell device of the copolymer was manufactured to evaluate the performance (see FIG. 15). The reverse structure organic solar cell was fabricated with ITO / ZnO / copolymer: ITIC-Th = 1: 1.25 / MoO3 / Ag. The patterned ITO glass substrates were first washed in the order of cleaning agents (Alconox), acetone, isopropanol (IPA) and ultrapure water. After drying, the surface was modified with Hydrodrophilic properties by UV-ozone treatment. A ZnO precursor solution was then prepared by the sol-gel method to form a ZnO thin film having a thickness of about 30-40 nm. The thin film was heated to 200 in air for 1 hour. Subsequent procedures were performed under nitrogen atmosphere in the glovebox. The photoactive layer was spin coated to a thickness of 90-100 nm depending on the conditions of each solution. More details are given in 6.1 and 6.2 below. Finally, the MoO _3/100 nm Ag film of 5 nm and an upper electrode were thermally deposited in a vacuum (less than 10-6 Torr). The photoactive area of the manufactured device was 0.04 to 0.12 cm ² . The solar simulator (Newport Oriel, 1000 W) was characterized by an air mass (AM) 1.5G filter. Intensity of solar simulators using a 100 mW · cm AIST- authenticated silicon based devices ^- was set to ^2. Current-voltage behavior was measured using a Keithley 2400 SMU. External quantum efficiency (EQE) behavior was measured using the Polaronix K3100 IPCE measurement system (McScience Inc.).

Example 6 Fabrication of Large Area Flexible Organic Solar Cell Module with M (BDD-T) S = 0.5

Through collaboration with Kolon Industries of M (BDD-T) S = 0.5, the roll-to-roll large area (module size ≧ 100 cm 2 photoactive layer area: 72.8 cm 2) was fabricated to evaluate the performance of the inverse structure organic solar cell flexible module. (Refer to FIG. 15) A large-area reverse structure organic solar cell flexible module was manufactured in the air by using a roll-to-roll sub-pilot equipment for the entire solution process of Kolon Industries, and its structure is ITO (PET) / ZnO / M (BDD-T). ) S = 0.5: ITIC-Th = 1: 1.25 / PEDOT: PSS (+ @) / Ag First, the PET substrate coated with patterned ITO was pretreated by simple wet method in order of Alconox, acetone, isopropanol (IPA) and ultrapure water. After drying, a ZnO solution capable of solution processing was mounted on a roll to form a ZnO thin film while heating with hot air at 110-140 ° C. in a slot-die manner. (Thickness: about 40-60 nm) The photoactive layer material is dissolved in a total of 0.6 g of donor-acceptor in 35 mL CB (DIO0.5%) solution, mounted on a roll without any pretreatment, and heated by hot air at 90-110 ° C. Coating in a slot-die manner. (Thickness: about 100-120 nm) More details are described in 6.3 below. Subsequently, the PEDOT: PSS (+ @) solution was coated in a slot-die manner while heating with hot air at 110-140 ° C. (Total thickness: 300 nm) Finally, the electrode was formed using a patterned stripe mask using an Ag solution for UV curing. The fabricated flexible organic solar cell module for a dedicated liquid process, module size ≥ 100 cm ² , The length was 100 m ² and the photoactive area was 72.8 cm ² . The solar simulator (Newport Oriel, 1000 W) was characterized by an air mass (AM) 1.5G filter. Intensity of solar simulators using a 100 mW · cm AIST- authenticated silicon based devices ^- was set to ^2. Current-voltage behavior was measured using a Keithley 2400 SMU.

Comparative example

An electron donor compound including a repeating unit represented by the following Chemical Formula 6 was obtained and used commercially.

[Formula 6]

Experimental Example 1 Characterization of Ternary Copolymers

1) Design and Coverage Calculation of Copolymers

Before synthesizing the synthesized copolymers, the coverage was predicted through molecular structure design and computing simulation calculation as follows. D or A was selected to maintain the planarity and rigid structure of the parent copolymers BDT (D1) -BDD (A1) and maximize the properties. In consideration of steric hindrance and coverage, 1) 50% by mol of 2DBDT-EH with sulfur introduced into BDT (D1) -BDD (A1) was supplied as D with M (BDD-T) S = 0.5. As a result, it may have improved absorbance and better oxidation stability than BDT (D1) -BDD (A1). By limiting the molar supply ratio of D to 50%, the molecular weight and solubility of the BDT (D1) -BDD (A1) polymer were ensured, and the sulfur introduction effect appeared. 2) As D (M (BDD-T) 4F = 0.5), 50 mol% of BDT having 2-ethylhexyloxy-3,5-difluorophenyl introduced into 4,8 positions of BDT was supplied to the electron donor. The introduction of four fluorine elements can improve intra- and intermolecular packing and improve absorbance, mobility and oxidation safety. In addition, by limiting the molar supply ratio of D to 50%, the molecular weight and solubility of the BDT (D1) -BDD (A1) polymer were ensured, and the fluorine introduction effect appeared. 3) As A of M (BDD-T) T = 0.1, 10 mol% of 1-octyl TPD in which thiophene spacer was introduced to enable non-covalent interaction between adjacent molecules such as BDD (A1) with electron acceptor. Supplied. As a result, better planarity and absorbance can be expected. By limiting the molar feed rate of A to 10%, the molecular weight and solubility of the BDT (D1) -BDD (A1) polymer were ensured, and the TPD effect appeared. Finally, 4) A (M (BDD-T) N = 0.1 A was introduced with thiophene spacers to enable non-covalent interactions between adjacent molecules, and 10 mol% of 2-ethylhexyl NDI was supplied to the electron acceptor instead of TPD. It was. As a result, better planarity and high mobility can be expected. By limiting the mole feed rate of A to 10%, the NDI effect was obtained while ensuring the molecular weight and solubility of the BDT (D1) -BDD (A1) polymer.

To predict the effect of ternary incorporation of the designed copolymers, the MMFF94 (Merck Molecular Force Field 94) and the intermolecular dihedral tool (Chembio3D Ultra 11.0, CambridgeSoft) were used in repeating unit 2 (n = 2). Coverages were calculated for each. The calculation method is [Polym. Chem., 2017, 8, 2979-2989. The coverage of the calculated copolymers was almost similar to the BDT (D1) -BDD (A1) polymer of Macromolecules 2012, 45, 9611-9617. All four structural copolymers had linear coverage in the plane, as seen from the top view. (See Fig. 9-a) In the case of the coverr in which the TPD and the NDI are introduced, the TPD forms a curve as shown in the side view, and the NDI has a large tilting of more than 90 degrees to the coverr. It was predicted that this could interfere with intra- and inter-molecular packing. (See Fig. 9-b)

2) Physical Properties of Copolymers

The physical properties were analyzed according to the structural change of the synthesized ternary copolymer. Molecular weight analysis, such as number average molecular weight (Mn), weight average molecular weight (Mw), and polydispersity index (PDI), is carried out by measurement of gel permeation chromatography (GPC) using chloroform. It became. Thermal decomposition temperature (Td) was performed by thermogravimetric analysis (TGA) measurement (NETZSCH 209 F3) (see Table 1).

Mn [Da] Mw [Da] PDI Td [° C] M (BDD-T) S = 0.5 81,000 153,900 1.90 395 M (BDD-T) 4F = 0.5 41,200 91,464 2.22 433 M (BDD-T) T = 0.1 72,500 131,225 1.81 415 M (BDD-T) N = 0.1 58,900 101,308 1.72 422 (BDD-TT) = 0.5 ^a 24,800 - 2.50 -

^a Ref. Adv. Energy. Mater. 2017, 1702166 copolymer (comparative).

3) Optical and Electrochemical Properties of Copolymers

Optical and electrochemical characteristics of the synthesized ternary copolymers according to structural changes were analyzed. Analyzes such as HOOC (highest occupied molecular orbital), LUMO (Lowest occupied molecular orbital) and bandgap (Egopt) were performed with HP (Agilent 8453 UV-Vis spectrophotometer) and UV (Znahner IM6eX electrochemical workstation) measurements. The bandgap of the ternary copolymers was calculated through 1239 / λ _onset , and the ferrocene half-wave level (E _1/2 , ferrocene) was measured at 0.55 when M (BDD-T) N = 0.1. The ferrocene halfwave level of was measured at 0.50. The HOMO energy levels of the polymers were obtained by introducing the same with the oxidized onset energy (E _onset ) measured in the following electrochemical formula [E _HOMO = -4.8- (E _onset -E _1/2 , ferrocene)]. 2).

HOMO [eV] LUMO [eV] ^E _g ^{opt  ( eV )} M (BDD-T) S = 0.5 -5.44 -3.66 1.78 M (BDD-T) 4F = 0.5 -5.60 -3.77 1.83 M (BDD-T) T = 0.1 -5.40 -3.60 1.80

Experimental Example 2 . High efficiency reverse structure organic solar cell characterization

The organic solar cell device having the reverse structure was manufactured and evaluated based on the analysis of the properties of the ternary copolymers synthesized according to the structural change. In order to optimize the efficiency, 0.5% of Diiodooctane (DIO) was added to Chlorobeznene (CB), and 0.5-0.7 wt% concentration was used. The results are shown in Table 3, FIGS. 12-a, 12-b and 13 is shown.

Copolymer V _oc [V] J _sc [mA / cm ² ] FF [%] PCE [%] M (BDD-T) S = 0.5 ^a 0.899 17.3 72.6 11.3 ^a Certified data 0.883 19.277 68.325 11.63 M (BDD-T) 4F = 0.5 0.920 16.4 67.0 10.1 M (BDD-T) T = 0.1 0.879 15.8 65.4 9.1 M (BDD-T) N = 0.1 0.879 15.7 70.0 9.7 PBDB-TT5 ^b 0.913 17.53 69.79 11.17

^b Ref. Adv. Energy. Mater. 2017, 1702166, Copolymer (Comparative Example)

Table 3 shows the solar cell results of the copolymers measured by the solar simulator, FIG. 12-a is the current-voltage curve measured at this time, and FIG. 12-b is the current measured by the solar simulator by measuring the EQE of the copolymers. This curve shows the external quantum efficiency that can be seen as FIG. 13 is a certificate obtained by measuring M (BDD-T) S = 0.5 at Daegu Nano Fusion Chamber. FIG. Looking at the results, it can be seen by comparing the voltage, current density, filling and efficiency of the present copolymers, of which Example 1 [M (BDD-T) S = 0.5] shows a high efficiency of 11.3% This is superior to the comparative technology PBDB-TT5. Even Example 1 [M (BDD-T) S = 0.5] shows the results of the authentication measured at the Daegu Nano Fusion Practicalization Center in Table 3 and FIG. 13, and recorded the highest efficiency of 11.63%.

Experimental Example 3 . Characterization of high stability reverse structure organic solar cell device

In particular, Example 1 [M (BDD-T) S = 0.5] was applied to the photoactive layer in the air to evaluate the stability when applying a roll-to-roll process that is not spin coating. An inverse structure organic solar cell device was fabricated and evaluated for performance. The fabricated device showed similar performance to the device fabricated in the glove box under nitrogen atmosphere. Encapsulation was performed to continuously evaluate the performance and durability at room temperature / humidity, and the results are shown in Table 4 and FIG. 14.

V _oc [V] J _sc [mA / cm ² ] FF [%] PCE [%] M (BDD-T) S = 0.5_Glove Box 0.899 17.5 69.9 11.0 M (BDD-T) S = 0.5_Air 0.899 17.2 67.8 10.5 M (BDD-T) S = 0.5_Glove Box
(Af 2248h) 0.879 17.4 66.1 10.1 M (BDD-T) S = 0.5_Air (Af 2455h) 0.859 17.2 63.4 9.4

Table 4 shows the solar cell of Example 1 [M (BDD-T) S = 0.5] measured by the solar simulator and the long-term stability after the initial and 2000 hours of the device fabricated in the atmospheric environment and the device fabricated in the atmospheric environment. FIG. 14 shows the efficiency-time curve based on the results of solar cells evaluating long-term stability after the initial and 2000 hours of a device manufactured in a glove box (nitrogen atmosphere) and an atmospheric environment with M (BDD-T) S = 0.5. It is shown.

Referring to Table 4 and FIG. 14, M (BDD-T) S = 0.5 of Example 1 shows excellent long-term stability with an efficiency of 10.1% even after 2248 hours compared to an initial 11.0% efficiency for a device manufactured in a glove box environment. Even in the case of M (BDD-T) S = 0.5 of Example 1 in the air environment, the device exhibited high atmospheric stability with an efficiency of 9.4% after 2455 hours compared to an initial 10.5% efficiency. Through this, the organic semiconductor device comprising a samsung powder copolymer according to the present invention means that the present material is very suitable for the roll-to-roll process required by the industry, which means that not only high efficiency but also high stability shows the industry of the present technology. It is advantageous for the application.

Experimental Example 4 . Inverse Structure Organic Solar Cell Flexible Module for Special Liquid Process

In particular, the M (BDD-T) S = 0.5 was compared with the donor polymer supplied by Merck, Germany, and evaluated the performance of the reverse structure organic solar cell flexible module manufactured by roll-to-roll for a dedicated liquid process in the air, respectively. The results are shown in Table 5 and FIG. 16.

V _oc [V] J _sc [mA / cm ² ] FF [%] PCE [%] M (BDD-T) S = 0.5_Air_Module 8.80 1.12 53.1 5.2 Merck (D) _Air_Module_Ref 7.49 1.48 41.8 4.7

Table 5 shows the results of solar cells evaluating modules manufactured based on M (BDD-T) S = 0.5 and each of Merck (D) materials supplied by Merck of Germany in the atmosphere of Kolon Industries. 16 shows a picture of the actual flexible organic solar cell module of M (BDD-T) S = 0.5. As can be seen in Table 5 and FIG. 16, the ternary copolymer according to the present invention, for example, M (BDD-T) S = 0.5 has better open voltage (Voc) and fill factor (FF) characteristics than Merck (D). Due to the change in energy efficiency (PCE) of 0.5% module efficiency was recorded, through which, the organic semiconductor device comprising a samseongbun copolymer according to the present invention is proved that it can be applied to the actual roll-to-roll process, localized material That means you can contribute.

101: cathode / anode; Indium Tin Oxide (ITO) Glass Substrates
102: cathode / anode buffer layer; ZnO
103: photoactive layer
104: anode / cathode buffer layer; MoO3
105: anode / cathode; Ag

Claims (15)

Ternary copolymer comprising one or more repeating units selected from the group consisting of the following structural formulas (1) and (2):
[Formula 1]

[Formula 2]

In the above formulas 1 and 2,
D is one type of regular resin selected from the group consisting of benzodithiophene (BDT, benzodithiophene), benzodithienothiophene (BDTT, benzodithienothiophene), naphthodithiophene (NDT), and bithiophene (BiT, bithiophene). (Regioregular) electron donor molecule that is a derivative,
A is benzodithiophendione (BDD, benzodithiophene-dione), thienopyrrolidione (TPD, thienopyrroledione), phthalimide (PT, phthalimide), diketopyrrolopyrrole (DPP, diketopyrrolopyrrole), indigo (ID, Indigo), Naphthothiophene dimide (NDI, naphthothiophene dimide), perylene diimide (PDI, perylene dimide), benzocyadiazole (BT, benzothiadiazole), benzotriazole (BTz, benzotriazole), quinoxaline (Qu, quinoxaline), Phenazine (Pz, phenazine), benzothiadiazole-dicarboxylic imide (BTI), benzobistriazole (BBTz, benzobistriazole), naphthobenzobistriazole (NBTz) An electron acceptor molecule that is a derivative,
R ₁ and R ₂ are independently hydrogen; Substituted or unsubstituted alkyl group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted alkynyl group; Substituted or unsubstituted aryl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted fluorenyl group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted aryl sulfoxy group; Or a substituent selected from the group consisting of a substituted or unsubstituted heterocyclic group containing one or more of N, P, S, Se, Te atoms,
l is independently a real number 0≤ l <1,
m is independently a real number 0 <m ≤ 1,
l + m is 1,
n is an integer from 1 to 10,000. The method of claim 1,
In the formula 1, D is a ternary copolymer, characterized in that any one of the repeating units of the formula 1-1 to 1-6:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

In Formula 1-1 to Formula 1-6,
R ₃ and R ₄ are independently hydrogen; Substituted or unsubstituted alkyl group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted alkynyl group; Substituted or unsubstituted aryl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted fluorenyl group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted aryl sulfoxy group; Or a substituent selected from the group consisting of a substituted or unsubstituted heteroring group including one or more of N, P, S, Se, and Te atoms. The method of claim 1,
In the formula 2, A is a ternary copolymer, characterized in that any one of the repeating units of the formula 2-1 to 2-3:
[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

In Chemical Formulas 2-1 to 2-3,
L or one of the substituted or unsubstituted heterocyclic groups containing one or more of N, P, S, Se, Te atoms or two adjacent substituents form a condensed ring,
R ₃ and R ₄ are independently hydrogen; Substituted or unsubstituted alkyl group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted alkynyl group; Substituted or unsubstituted aryl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted fluorenyl group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted aryl sulfoxy group; Or a substituent selected from the group consisting of a substituted or unsubstituted heteroring group including one or more of N, P, S, Se, and Te atoms. The method of claim 3,
In Chemical Formulas 2-1 to 2-3, L is a ternary copolymer, wherein L is a molecule represented by Chemical Formulas 3-1 to 3-17:
[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

[Formula 3-5]

[Formula 3-6]

[Formula 3-7]

[Formula 3-8]

[Formula 3-9]

[Formula 3-10]

[Formula 3-11]

[Formula 3-12]

[Formula 3-13]

[Formula 3-14]

[Formula 3-15]

[Formula 3-16]

[Formula 3-17]

In Chemical Formulas 3-1 to 3-17,
X is the same as or different from each other, and independently, is nitrogen, oxygen, sulfur, selenium or tellurium,
R ₃ and R ₄ are independently hydrogen; Substituted or unsubstituted alkyl group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted alkynyl group; Substituted or unsubstituted aryl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted fluorenyl group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted aryl sulfoxy group; Or a substituent selected from the group consisting of a substituted or unsubstituted heteroring group including one or more of N, P, S, Se, and Te atoms. The method of claim 1,
D in Structural Formula 1 is a ternary copolymer comprising at least one repeating unit selected from the group consisting of Formulas 4-1 and 4-2:
[Formula 4-1]

[Formula 4-2]

In Chemical Formulas 4-1 and 4-2,
X is the same as or different from each other, and independently, is nitrogen, oxygen, sulfur, selenium or tellurium,
R- ₅ to R ₇ are independently hydrogen; Cyano groups; Halogen group; Alkylthio groups having 1 to 20 carbon atoms; An alkyl group having 1 to 20 carbon atoms; It is a C1-C20 thionyl group or a C1-C20 alkoxy group. The method of claim 1,
In the formula 2, A is a ternary copolymer comprising at least one repeating unit selected from the group consisting of Formulas 5-1 and 5-2:
[Formula 5-1]

[Formula 5-2]

In Chemical Formulas 5-1 and 5-2,
R ₅ is independently hydrogen; Cyano groups; Halogen group; Alkylthio groups having 1 to 20 carbon atoms; An alkyl group having 1 to 20 carbon atoms; It is a C1-C20 thionyl group or a C1-C20 alkoxy group. The method of claim 1,
In Structural Formula 1, l is a ternary copolymer, characterized in that 0.1 to 0.7. The method of claim 1,
In Structural Formula 2, l is a ternary copolymer, characterized in that 0.5 to 0.95. The method of claim 1,
The number average molecular weight of the copolymer is 30 kDa to 1,000 kDa, characterized in that the three minutes copolymer. An organic solar cell comprising the ternary copolymer according to any one of claims 1 to 9 as a photoactive layer. The method of claim 10,
The photoactive layer is an organic solar cell comprising a ternary powder copolymer and a non fullerene derivative. The method of claim 10,
The photoactive layer is an organic solar cell comprising a ternary powder copolymer and a fullerene derivative. 10. A perovskite solar cell comprising the ternary copolymer according to any one of claims 1 to 9 as a charge transport layer. A field effect transistor comprising a ternary powder copolymer according to any one of claims 1 to 9. An organic light emitting diode comprising a ternary powder copolymer according to any one of claims 1 to 9.

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