Organic semiconductor compounds with high transmittance in the visible light region

Abstract

The present invention relates to an organic semiconductor compound having high transmittance in the visible light region and uses thereof.

Description

[Technical Field]

[0001] The present invention relates to an organic semiconductor compound having high transmittance in the visible light region and uses thereof. [Background technology]

[0002] Amid the global rise in crude oil prices and the growing problem of environmental pollution caused by the use of fossil fuels, demand for sustainable, environmentally friendly energy sources is rapidly increasing. Representative environmentally friendly energy sources include solar, wind, hydroelectric, wave, and geothermal power. Of these, solar cells, which can generate electricity using sunlight, are attracting attention as an unlimited source of electrical energy because they have the fewest restrictions on installation location. 1.7 x 10 solar energy reaching the Earth's surface 5 The amount of solar energy that can be effectively extracted from a TW is estimated to be 600 TW. If a 10% efficient solar power plant were available, it could provide approximately 60 TW of electricity. This is a huge amount, more than enough to meet the future demand for sustainable energy sources, compared to the Earth's projected energy demand of 28 TW in 2050. Currently, first-generation crystalline silicon solar cells, which use inorganic materials, account for 90% of the solar power generation market. However, the cost of generating electricity is 5 to 20 times higher than that of fossil fuels, and they are mainly used for medium to large-scale power generation over a long period of time. The limited availability of materials limits their application value. As a result, second-generation thin-film solar cell technologies (CdTe, CIGS, etc.) that replace silicon have rapidly emerged, accounting for more than half of the remaining 10% of the market. However, second-generation solar cell technologies also require expensive equipment because some materials are classified as precious metals and semiconductor thin films are formed through vacuum and high-temperature processes when manufacturing elements. One solar cell technology that could solve these problems is organic solar cells. Because they use organic materials, they can be mass-produced using a solution process, reducing the cost of solar cells. Their mechanical flexibility, ease of design, and versatility mean they have limitless potential applications in clothing, portable electrical and electronic products, and are attracting attention as next-generation solar cells. For the practical application of organic solar cells, the development of printable photoactive layer materials that can realize high efficiency, high stability, large area, and modularization of solar cells is an extremely important prerequisite. Among these, the improvement of the efficiency of organic solar cells is particularly essential. The development of highly soluble, high-performance (high efficiency and high stability) materials that can be processed in low-temperature solutions alone can significantly reduce production costs and gradually resolve technical issues. In recent years, organic solar cells have been classified into fullerene-based and non-fullerene-based organic solar cells depending on the type of electron acceptor material in the photoactive layer. As of December 2019, the efficiency of fullerene-based organic solar cells is the world's highest at 11.5%, certified by HKUST under the certification standards of the National Renewable Energy Laboratory (NREL), while the efficiency of non-fullerene-based organic solar cells is 18.2%, certified by SJTU / BUAA, which is the world's highest efficiency, surpassing that of fullerene-based organic solar cells. While it took more than 15 years for fullerene-based organic solar cells to reach their current level of development, non-fullerene-based organic solar cells were achieved in just under five years. Furthermore, it has been reported that non-fullerene-based organic solar cells are superior to fullerene-based organic solar cells in terms of stability, and the development of high-performance non-fullerene-based organic solar cells is progressing rapidly (Nature Communications, 2016, 7, 11585; Nature Materials, 2017, 16, 363-369). In the case of PCE11, a similar derivative that is a representative example of fullerene-based organic solar cells and has the world's highest efficiency, it was confirmed that after aging in the atmosphere for five days, a burn-in phenomenon occurred, causing a rapid decrease in efficiency of approximately 39%.In contrast, in the case of non-fullerene-based solar cells, the decrease in efficiency was less than 15% even after five days of aging. Recent studies have reported an efficiency of 20.2% for tandem organic solar cell elements (https: / / doi.org / 10.1016 / j.joule.2021.12.017), and an efficiency of nearly 19% for single-structure organic solar cell elements (Advanced Materials 2021, 2102420). Despite exceeding the efficiency of currently commercially available silicon solar cells, the field of organic solar cells has yet to be commercialized. This suggests that simply pursuing higher efficiency cannot be the standard for commercialization of organic solar cells. Therefore, going forward, it will be important to develop materials tailored to the target, from the perspective of the end product / industry that can maximize the advantages of organic solar cells (which are preferable for indoor power generation or transparent solar cells rather than outdoor power generation, where silicon solar cells and perovskite solar cells have various advantages). [Prior art documents] [Non-patent literature]

[0003] Non-patent document 1: Nature Communication, 2016, 7, 11585 Non-patent document 2: Nature Materials, 2017, 16, 363-369 Summary of the Invention [Problem to be solved by the invention]

[0004] Therefore, based on the cost-effectiveness that organic solar cell materials should have, the inventors synthesized a new module that has a stable high efficiency of 14 to 16.5% or more and at the same time a high transmittance of 40 to 30% over the entire visible light range of 380 to 780 nm, making it applicable to Internet of Things (IoT) sensors, Building Integrated Photovoltaics (BIPVs), Automobile Integrated Photovoltaics (AIPVs), etc., and completed the present invention. Therefore, an object of the present invention is to provide an organic semiconductor compound having high transmittance in the visible light region and an organic semiconductor material incorporating the same. [Means for solving the problem]

[0005] In order to achieve the above object, the present invention provides a compound represented by the following chemical formula (1): [ka] In the chemical formula (1), Ligands are reactive ligands, which may be the same or different, and each independently represent H, a halogen, or a pseudohalogen, wherein the halogen is selected from the group consisting of Cl, Br, and I, and the pseudohalogen is selected from the group consisting of OTf, OPO(OR)2), and an acetoxy group; X and Y are the same or different and each independently represent a chalcogen, the chalcogen being selected from the group consisting of N, NR, C, O, S, and Se; The EWG is selected from the group consisting of the following structures: [ka] In the above chemical formula, R and R1 to R4 are the same or different and are each independently selected from the group consisting of hydrogen, a cyano group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted arylsulfoxy group, a substituted or unsubstituted boron group, a substituted or unsubstituted alkylamine group, a substituted or unsubstituted aralkylamine group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted heteroarylamine group, a substituted or unsubstituted aryl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted carbazole group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted thionyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted ester group, a substituted or unsubstituted aromatic group, and a substituted or unsubstituted heterocyclic group containing one or more elements selected from the group consisting of N, O, S, and Se, or two adjacent substituents may form a fused ring.

[0006] The present invention also provides an organic semiconductor compound represented by the following chemical formula (2-1): [ka] In the chemical formula (2-1), A is an electron acceptor unit which is a compound represented by the chemical formula (1) according to the present invention, n is an integer of 1 to 10,000, and D is an electron donor selected from compounds represented by the following structures: [ka] In the above structure, X and Y are the same or different and each independently represent a chalcogen, the chalcogen being selected from the group consisting of N, NR, C, O, S, and Se, and R are the same or different and each independently represent a hydrogen atom; a cyano group; a halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted arylsulfoxy group; a substituted or unsubstituted boron group; a substituted or unsubstituted alkylamine group; a substituted or unsubstituted aralkylamine group; a substituted or unsubstituted aryl substituted or unsubstituted alkoxy groups; substituted or unsubstituted thionyl groups; substituted or unsubstituted silyl groups; substituted or unsubstituted alkenyl groups; substituted or unsubstituted ester groups; substituted or unsubstituted aromatic groups; and substituted or unsubstituted heterocyclic groups containing one or more elements selected from the group consisting of N, O, S, and Se, or two adjacent substituents may form a fused ring.

[0007] The present invention also provides an organic semiconductor compound represented by the following chemical formula (4-1): [ka] In the chemical formula (4-1), A is an electron acceptor unit which is a compound represented by the chemical formula (1) according to the present invention, n is an integer of 1 to 10,000, and A' is the following: an electron acceptor selected from compounds having the structure [ka] In the above structure, X and Y are the same or different and each independently represent a chalcogen, the chalcogen being selected from the group consisting of N, NR, C, O, S, and Se, and R are the same or different and each independently represent a hydrogen atom; a cyano group; a halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted arylsulfoxy group; a substituted or unsubstituted boron group; a substituted or unsubstituted alkylamine group; a substituted or unsubstituted aralkylamine group; a substituted or unsubstituted aryl substituted or unsubstituted alkoxy groups; substituted or unsubstituted thionyl groups; substituted or unsubstituted silyl groups; substituted or unsubstituted alkenyl groups; substituted or unsubstituted ester groups; substituted or unsubstituted aromatic groups; and substituted or unsubstituted heterocyclic groups containing one or more elements selected from the group consisting of N, O, S, and Se, or two adjacent substituents may form a fused ring.

[0008] The present invention also provides an organic semiconductor compound selected from the compounds represented by the following chemical formulas (6-1) to (6-5): [ka] In the chemical formulas (6-1) to (6-5), D1, D2, and D3 are the same or different and are electron donors selected from compounds represented by the following structures: [ka] A1, A2, and A3 are the same or different, at least one of which is an electron acceptor unit that is a compound represented by chemical formula (1) according to the present invention, and the rest are relative electron acceptors selected from compounds represented by the following structures: [ka] k is a mole fraction and is a real number where 0 ≦ k < 1, l is a mole fraction and is a real number where 0 ≦ l < 1, m is a mole fraction and is a real number where 0 < m ≦ 1, k + l + m = 1, and n is an integer from 1 to 10,000.

[0009] The present invention also provides an organic semiconductor compound selected from among compounds represented by the following chemical formulas (8-1) to (8-4):

Chemical formula

Chemical formula

Chemical formula

[0010] The present invention also provides an organic solar cell comprising the organic semiconductor compound according to the present invention.

[0011] The present invention also provides an organic electronic device comprising the organic semiconductor compound according to the present invention. [Effects of the Invention]

[0012] The organic semiconductor compound of the present invention has a stable high efficiency of 14 to 16.5% or more from a cost-effective viewpoint, and at the same time has a high transmittance of 40 to 30% over the entire visible light range of 380 to 780 nm, making it applicable to Internet of Things (IoT) sensors, Building Integrated Photovoltaics (BIPVs), Automobile Integrated Photovoltaics (AIPVs), etc., and can be provided as an effective organic solar cell element. [Brief explanation of the drawings]

[0013] [Figure 1] The synthesis process of the monomers (1 to 18) is shown. [Figure 2] 1H NMR of Monomer 1 is shown. [Figure 3] GC-MS of Monomer 1 is shown. [Figure 4] 1H NMR of Monomer 2 is shown. [Figure 5] GC-MS of Monomer 2 is shown. [Figure 6] 1H NMR of Monomer 3 is shown. [Figure 7] GC-MS of Monomer 3 is shown. [Figure 8] 1H NMR of Monomer 4 is shown. [Figure 9] GC-MS of Monomer 4 is shown. [Figure 10] 1H NMR of Monomer 5 is shown. [Figure 11] GC-MS of Monomer 5 is shown. [Figure 12] 1H NMR of Monomer 6 is shown. [Figure 13] 13C NMR of monomer 6 is shown. [Figure 14] GC-MS of Monomer 6 is shown. [Figure 15] The MALDI-TOF of monomer 6 is shown. [Figure 16] 1H NMR of Monomer 7 is shown. [Figure 17] 13C NMR of monomer 7 is shown. [Figure 18] GC-MS of Monomer 7 is shown. [Figure 19] The MALDI-TOF of monomer 7 is shown. [Figure 20]1H NMR of monomer 8 is shown. [Figure 21] 13C NMR of monomer 8 is shown. [Figure 22] GC-MS of monomer 8 is shown. [Figure 23] The MALDI-TOF of monomer 8 is shown. [Figure 24] 1H NMR of monomer 9 is shown. [Figure 25] 13C NMR of monomer 9 is shown. [Figure 26] GC-MS of monomer 9 is shown. [Figure 27] The MALDI-TOF of monomer 9 is shown. [Figure 28] 1H NMR of monomer 10 is shown. [Figure 29] 1H NMR of monomer 11 is shown. [Figure 30] 1H NMR of monomer 12 is shown. [Figure 31] GC-MS of Monomer 12 is shown. [Figure 32] 1H NMR of monomer 13 is shown. [Figure 33] 1H NMR of monomer 14 is shown. [Figure 34] 1H NMR of monomer 15 is shown. [Figure 35] 1H NMR of monomer 16 is shown. [Figure 36] 1H NMR of monomer 17 is shown. [Figure 37] 1H NMR of monomer 18 is shown. [Figure 38] This shows the synthesis process of polymers with D1-A1 structure (19 to 28). [Figure 39] This shows the 1H NMR of the polymer 19.P(3CHO) with the D1-A1 structure. [Figure 40] This shows the 1H NMR of the polymer 20.P(3BA) with the D1-A1 structure. [Figure 41] This shows the 1H NMR of the polymer 21.P(3IN) with the D1-A1 structure. [Figure 42] This shows the 1H NMR of the polymer 22.P(3TC) with the D1-A1 structure. [Figure 43] This shows the 1H NMR of the polymer 23.P (3TC1Cl) with the D1-A1 structure. [Figure 44] This shows the 1H NMR of the polymer 24.P(3IN2Fl) with the D1-A1 structure. [Figure 45] This shows the 1H NMR of the polymer 27.P(Fu3IN) with the D1-A1 structure. [Figure 46] This shows the 1H NMR of the polymer 28.P(Fu3TC) with the D1-A1 structure. [Figure 47] This shows the synthesis process of polymers with D1-A1 structure (29 to 36). [Figure 48] This shows the 1H NMR of the polymer 29.P (F-3BA) with the D1-A1 structure. [Figure 49] This shows the 1H NMR of the polymer 30.P (F-3IN) with the D1-A1 structure. [Figure 50] This shows the 1H NMR of the polymer 31.P (Cl-3IN) with the D1-A1 structure. [Figure 51] This shows the 1H NMR of the polymer 32.P (C6C6-3IN) with the D1-A1 structure. [Figure 52] This shows the 1H NMR of the polymer 33.P (EDOT-3IN) with the D1-A1 structure. [Figure 53] This shows the 1H NMR of the polymer 36.P(3IN)-1D with the D1-A1 structure. [Figure 54] This shows the synthesis process of polymers with D1-A1 structure (37 to 39). [Figure 55]This shows the 1H NMR of the polymer 37.P (IFL-3IN) with the D1-A1 structure. [Figure 56] This shows the 1H NMR of the polymer 39.P (IDT-3IN) with the D1-A1 structure. [Figure 57] This shows the synthesis process of three-component polymers (40 to 45) with a D1-A1-D1-A2 structure. [Figure 58] This shows the 1H NMR of the ternary polymer 40.P(3IN) (3IN2F=0.5) with a D1-A1-D1-A2 structure. [Figure 59] This shows the 1H NMR of the ternary polymer 42.P(3TC) (3IN2F=0.5) with a D1-A1-D1-A2 structure. [Figure 60] This shows the 1H NMR of the ternary polymer 43.P(3TC) (3TC1Cl=0.5) with a D1-A1-D1-A2 structure. [Figure 61] This shows the 1H NMR of the ternary polymer 44.P(3TC) (3TC1Cl=0.4) with a D1-A1-D1-A2 structure. [Figure 62] The synthesis process of the three-component polymer (46, 47) with the D1-A1-D2-A1 structure is shown. [Figure 63] This shows the 1H NMR of the ternary polymer 47.P(3IN) (F-2DBDT=0.5) with a D1-A1-D2-A1 structure. [Figure 64] The synthesis process of a three-component polymer (48, 49) with a D1-A1-D1-A2 structure is shown. [Figure 65] This shows the 1H NMR of the ternary polymer 48.P(3IN2F) (BDD=0.5) with a D1-A1-D1-A2 structure. [Figure 66] This shows the 1H NMR of the ternary polymer 49.P(3IN2F) (FTT=0.2) with a D1-A1-D1-A2 structure. [Figure 67] The synthesis process of four-component polymers (50 to 53) with the D1-A1-D1-A2-D1-A3 structure is shown. [Figure 68]This shows the 1H NMR of the four-component polymer 50.P (3IN=0.3) (3IN2F=0.5) (BDD=0.2) with a D1-A1-D1-A2-D1-A3 structure. [Figure 69] This shows the 1H NMR of the four-component polymer 51.P (3TC=0.3) (3IN2F=0.5) (BDD=0.2) with a D1-A1-D1-A2-D1-A3 structure. [Figure 70] This shows the 1H NMR of the four-component polymer 52.P with the structure D1-A1-D1-A2-D1-A3 (3TC=0.3) (3IN2F=0.5) (D18=0.2). [Figure 71] This shows the 1H NMR of the four-component polymer 53.P (3TC=0.3) (3IN2F=0.5) (3ClTh=0.2) with the structure D1-A1-D1-A2-D1-A3. [Figure 72] This shows the synthesis process of single molecules (54 to 56) with the A1-D1-A1 structure. [Figure 73] This shows the 1H NMR of a single molecule 54.RR-2DBDT-3TC with the A1-D1-A1 structure. [Figure 74] This shows the 1H NMR of a single molecule 55.RR-2DBDT-3IN2F with the A1-D1-A1 structure. [Figure 75] This shows the 1H NMR of the single molecule 56.RR-2DBDT-3IN2F-2Br with the A1-D1-A1 structure. [Figure 76] This shows the synthesis process of the regioregular three-component polymer (57, 58) with the D1-(A1-D1-A1)-D1-A2 structure. [Figure 77] This shows the 1H NMR of the regioregular ternary polymer 57.RR-P(3IN2F) (BDD=0.5) with a D1-(A1-D1-A1)-D1-A2 structure. [Figure 78] This shows the 1H NMR of the regioregular ternary polymer 58.RR-P(3IN2F) (D18=0.5) with a D1-(A1-D1-A1)-D1-A2 structure. [Figure 79]The calculation results of the total synthesis number and overall yield of the highly efficient commercial polymer PM6 / PM7, the acceptor unit of D18, BDD and D18 (=E19) are shown. [Figure 80] 1 shows the calculation results of the total synthesis number and total yield of the monomer (acceptor unit) of the present invention. [Figure 81] 1 shows the results of Gaussian 16 computing simulations (structure optimization and DFT calculations) of model compounds in the repeating unit 1 of the P(F-3IN), P(3IN)-in / out, P(3IN2F), and P(3IN2Cl) polymers of the present invention. [Figure 82] 1 shows the results of computing simulation (structure optimization and DFT calculation) using Gaussian 16 for a model compound in repeating unit 1 of the P(3TC)-in / out and P(3TC1Cl) polymers of the present invention. [Figure 83] 1 shows the results of Gaussian 16 computing simulations (structure optimization and DFT calculations) of a model compound in repeating unit 2 of the P(3IN)-in, in, P(3IN)-in, out, and P(3IN)-out, out polymer of the present invention. [Figure 84] 1 shows TGA curves for analyzing the thermal stability characteristics of the polymers (two-component polymers, three-component polymers, and four-component polymers) of the present invention. [Figure 85] 1 shows UV-Vis curves for optical property analysis of the two-component polymer of the present invention. [Figure 86] 1 shows UV-Vis curves for optical property analysis of the ternary polymer of the present invention. [Figure 87] 1 shows UV-Vis curves for optical property analysis of the quaternary polymer of the present invention. [Figure 88] 1 shows UV-Vis curves for optical property analysis of the regioregular ternary polymer of the present invention. [Figure 89] 1 shows UV-Vis curves for analyzing the optical properties of the P(3CHO) polymer of the present invention in a CB solution as a function of temperature. [Figure 90] 1 shows UV-Vis curves for analyzing the optical properties of the P(3BA) polymer of the present invention in a CB solution as a function of temperature. [Figure 91] 1 shows UV-Vis curves for analyzing optical properties of the P(3IN) polymer of the present invention in CB solution as a function of temperature. [Figure 92] 1 shows UV-Vis curves for analyzing the optical properties of the P(3TC) polymer of the present invention in a CB solution as a function of temperature. [Figure 93] 1 shows UV-Vis curves for analyzing the optical properties of the P(3IN)-1D polymer of the present invention in CB solution as a function of temperature. [Figure 94] 1 shows UV-Vis curves for analyzing the optical properties of the P(3IN)(3IN2F=0.5) polymer of the present invention in a CB solution as a function of temperature. [Figure 95] 1 shows UV-Vis curves for analyzing the optical properties of the P(3IN)(3TC1Cl=0.4) polymer of the present invention in a CB solution as a function of temperature. [Figure 96] 1 shows UV-Vis curves for analyzing optical properties of the PM6 polymer of the present invention in a CB solution as a function of temperature. [Figure 97] 1 shows UV-Vis curves for analyzing the optical properties of the PTB7-Th polymer of the present invention in a CB solution as a function of temperature. [Figure 98] 1 shows UV-Vis curves for analyzing the optical properties of the P(3IN=0.3)(3IN2F=0.5)(BDD=0.2) polymer of the present invention in a CB solution as a function of temperature. [Figure 99] 1 shows UV-Vis curves for analyzing optical properties of the P(3IN=0.3)(3IN2F=0.5)(BDD=0.2) polymer of the present invention in an XY solution according to temperature. [Figure 100] 1 shows CV curves for electrochemical property analysis of the two-component polymer of the present invention. [Figure 101]1 shows the CV curves for electrochemical property analysis of the ternary polymer of the present invention. [Figure 102] 1 shows the CV curves for electrochemical property analysis of the quaternary polymer of the present invention. [Figure 103] 1 shows CV curves for electrochemical property analysis of the regioregular ternary polymer of the present invention. [Figure 104] 1 shows an optimized JV curve for analyzing the photovoltaic properties of a two-component polymer-based organic solar cell device of the present invention. [Figure 105] 1 shows an optimized EQE curve for analyzing the photovoltaic properties of a two-component polymer-based organic solar cell device of the present invention. [Figure 106] 1 shows an optimized JV curve for analyzing the photovoltaic properties of a three-component polymer-based organic solar cell device of the present invention. [Figure 107] 1 shows an optimized EQE curve for analyzing the photovoltaic properties of a three-component polymer-based organic solar cell device of the present invention. [Figure 108] 1 shows an optimized JV curve for analyzing the photovoltaic characteristics of a four-component polymer-based organic solar cell device according to the present invention. [Figure 109] 1 shows an optimized EQE curve for analyzing the photovoltaic properties of a four-component polymer-based organic solar cell device according to the present invention. [Figure 110] 1 shows an optimized JV curve for analyzing the photovoltaic properties of the regioregular ternary polymer-based organic solar cell device of the present invention. [Figure 111] 1 shows an optimized EQE curve for analyzing the photovoltaic properties of the regioregular ternary polymer-based organic solar cell device of the present invention. [Figure 112] 1 shows the results of GIWAXS measurements of two-component polymers of the present invention, clockwise from the left: P(3CHO), P(3BA), P(3IN), and P(3TC). [Figure 113]The GIWAXS measurement results for the blend films of the two-component polymer of the present invention and BTP-eC9 are shown. From the left, P(3CHO):BTP-eC9, P(3IN):BTP-eC9, and P(3TC):BTP-eC9. [Figure 114] 1 shows line-cut plots in the out-of-plane direction of GIWAXS measurement results for each blend film of the two-component polymer of the present invention and BTP-eC9. [Figure 115] GIWAXS measurement results of two-component and three-component polymers of the present invention are shown. Clockwise from left: P(3IN2F), P(3IN) (3IN2F = 0.5), P(3TC1Cl), P(3IN) (3TC1Cl = 0.4), and P(3IN2F) (BDD = 0.5). [Figure 116] 1 shows line-cut plots in the out-of-plane direction of the GIWAXS measurement results of the two-component polymer and the three-component polymer of the present invention. [Figure 117] GIWAXS measurement results for blend films of the ternary polymer of the present invention and BTP-eC9 are shown: (a) P(3IN)(3IN2F=0.5):BTP-eC9, P(3IN2F)(BDD=0.5):BTP-eC9) P(3IN):BTP-eC9. [Figure 118] FIG. 1 shows line-cut plots in the out-of-plane direction of the GIWAXS measurement results of the three-component polymer of the present invention. [Figure 119] The GIWAXS measurement results of the four-component polymer of the present invention and a commercial polymer (PM6) are shown. From the left, P(3IN=0.3)(3IN2F=0.5)(BDD=0.2) and PM6. [Figure 120] 1 shows line-cut plots in the out-of-plane direction of GIWAXS measurement results of the quaternary polymer of the present invention and a commercial polymer (PM6). [Figure 121]Figure 1 shows AFM results (2D-topography; 3D-topography; 2D phase) measured on a 10 × 10 μm scale for each blend film of the two-component polymer of the present invention and BTP-eC9: (a) P(3CHO):BTP-eC9, (b) P(3BA):BTP-eC9, (c) P(3IN):BTP-eC9, and (d) P(3TC):BTP-eC9. [Figure 122] Figure 1 shows AFM results (2D-topography; 3D-topography; 2D phase) measured on a 10 × 10 μm scale for blend films of the binary and ternary polymers of the present invention with BTP-eC9: (a) P(3IN2F):BTP-eC9, (b) P(3IN)(3IN2F=0.5):BTP-eC9, (c) P(3TC1Cl):BTP-eC9, and (d) P(3IN)(3TC1Cl=0.4):BTP-eC9. [Figure 123] The AFM results (2D-topography; 3D-topography; 2D phase) measured on a 10 × 10 μm2 scale for each blend film of the ternary polymer of the present invention and BTP-eC9 are shown. (a) P(3IN2F)(BDD=0.5):BTP-eC9. [Figure 124] The AFM results (2D-topography; 3D-topography; 2D phase) measured on a 10 × 10 μm2 scale for each blend film of the quaternary polymer of the present invention and BTP-eC9 are shown. (a) P(3IN=0.3)(3IN2F=0.5)(BDD=0.2):BTP-eC9. [Figure 125] Figure 1 shows the contact angle measurements in DIM and water for films of the two-component polymers of the present invention: (a) P(3CHO), (b) P(3BA), (c) P(3IN), and (d) P(3TC). [Figure 126]Figure 1 shows the contact angle measurements in DIM and water for films of the two-component and three-component polymers of the present invention: (a) P(3IN2F), (b) P(3IN) (3IN2F = 0.5), (c) P(3TC1Cl), and (d) P(3IN) (3TC1Cl = 0.4). [Figure 127] 1 shows the results of contact angle measurements in DIM and water for the three-component polymer film of the present invention. (a) P(3IN2F) (BDD=0.5). [Figure 128] 1 shows the results of contact angle measurements for the four-component polymer film of the present invention in DIM and water: (a) P(3IN=0.3)(3IN2F=0.5)(BDD=0.2). [Figure 129] The contact angle measurements in DIM and water for the commercial polymer and acceptor monomolecules used in this invention are shown. (a) PM6, (b) BTP-eC9. [Figure 130] 1 shows an optimized J-V curve for analyzing the photovoltaic properties of a three-component organic solar cell device based on the four-component polymer of the present invention, P(3IN=0.3)(3IN2F=0.5)(BDD=0.2):PM6:BTP-eC9. [Figure 131] 1 shows an optimized EQE curve for analyzing the photovoltaic properties of a three-component organic solar cell device based on the four-component polymer of the present invention, P(3IN=0.3)(3IN2F=0.5)(BDD=0.2):PM6:BTP-eC9. [Fig. 132a-132f] This is a Nano Convergence Practical Application Center (NCDPAC) certificate of the optimization results of an organic solar cell device based on the four-component polymer of the present invention, P(3IN=0.3)(3IN2F=0.5)(BDD=0.2):PM6:BTP-eC9=0.4:0.6:1.2. [Figure 133]The GIWAXS measurement results of a representative quaternary polymer of the present invention and a commercial polymer are shown below. (a) P(3IN=0.3)(3IN2F=0.5)(BDD=0.2), (b) PM6. [Figure 134] Figure 1 shows the GIWAXS measurement results for the ternary organic solar cell elements based on the quaternary polymer of the present invention, P(3IN=0.3)(3IN2F=0.5)(BDD=0.2):PM6:BTP-eC9, with the ratio combinations: (a) 1.0:0:1.2, (b) 0.8:0.2:1.2, (c) 0.6:0.4:1.2, (d) 0.4:0.6:1.2, (e) 0.2:0.8:1.2, and (f) 0:1.0:1.2. [Figure 135] The figures show the TEM (scale: 100 & 10 nm) measurement results of the ternary blend film based on P(3IN = 0.3)(3IN2F = 0.5)(BDD = 0.2):PM6:BTP-eC9 under the best conditions of the present invention and the PM6:BTP-eC9 blend film. (a) P(3IN = 0.3)(3IN2F = 0.5)(BDD = 0.2):PM6:BTP-eC9 = 0.4:0.6:1.2, (b) PM6:BTP-eC9 = 1.0:1.2 (CF). [Figure 136] 1 shows the elemental mapping results of TEM (scale: 500 nm) for the best condition ternary blend film of P(3IN = 0.3)(3IN2F = 0.5)(BDD = 0.2):PM6:BTP-eC9 and the PM6:BTP-eC9 blend film. (a) P(3IN = 0.3)(3IN2F = 0.5)(BDD = 0.2):PM6:BTP-eC9 = 0.4:0.6:1.2, (b) PM6:BTP-eC9 = 1.0:1.2 (CF). [Figure 137] 1 shows UV-Vis results of 10-5 M solutions of a representative quaternary polymer of the present invention, P(3IN=0.3)(3IN2F=0.5)(BDD=0.2), and PM6 at different concentrations, along with their photopic responses. [Figure 138]The UV-Vis results for films of a representative four-component polymer of the present invention, P(3IN=0.3)(3IN2F=0.5)(BDD=0.2), and PM6, are shown together with the photopic response, with the extinction coefficient calculated based on the Beer-Lambert equation. [Figure 139] The discrimination of words and colors is shown by actual photographs based on various films of the same thickness of the representative four-component polymers of the present invention, P(3IN=0.3)(3IN2F=0.5)(BDD=0.2) and PM6. [Figure 140] The optical simulation results of a representative quaternary polymer of the present invention and a commercial polymer are shown below: (a) P(3IN = 0.3)(3IN2F = 0.5)(BDD = 0.2), (b) P(3IN = 0.3)(3IN2F = 0.5)(BDD = 0.2):BTP-eC9 = 1.0:1.2, (c) ITO / PEDOT:PSS / P(3IN = 0.3)(3IN2F = 0.5)(BDD = 0.2):BTP-eC9 = 1.0:1.2 / P(NDIT-F3N) / Ag, (d) PM6, (e) PM6:BTP-eC9 = 1.0:1.2, and (f) ITO / PEDOT:PSS / PM6:BTP-eC9 = 1.0:1.2 / P(NDIT-F3N) / Ag. [Figure 141] 1 shows the UV-Vis results (absorbance) of the optimized ternary blend film based on P(3IN=0.3)(3IN2F=0.5)(BDD=0.2):PM6:BTP-eC9 of the present invention. [Figure 142] 1 shows the UV-Vis results (transmittance) of the optimized ternary blend film based on P(3IN=0.3)(3IN2F=0.5)(BDD=0.2):PM6:BTP-eC9 of the present invention. [Figure 143] 1 shows optimized J-V curves for analyzing the photovoltaic properties of a three-component semitransparent organic solar cell device based on the four-component polymer of the present invention, P(3IN=0.3)(3IN2F=0.5)(BDD=0.2):PM6:BTP-eC9. [Figure 144]1 shows an optimized EQE curve for analyzing the photovoltaic properties of a three-component semitransparent organic solar cell device based on the four-component polymer of the present invention, P(3IN=0.3)(3IN2F=0.5)(BDD=0.2):PM6:BTP-eC9. [Figure 145] 1 shows the UV-Vis measurement results (transmittance) of a three-component semi-transparent organic solar cell element based on the four-component polymer of the present invention, P(3IN=0.3)(3IN2F=0.5)(BDD=0.2):PM6:BTP-eC9. [Figure 146] Figure 1 shows actual photographs of ternary semitransparent organic solar cell devices based on the four-component polymer of the present invention, P(3IN=0.3)(3IN2F=0.5)(BDD=0.2):PM6:BTP-eC9: (a) 1.0:0:1.2, Ag(13 nm) / WO3(25 nm), (b) 0.4:0.6:1.2, Ag(13 nm) / WO3(25 nm), (c) 1.0:0:1.2, Ag(10 nm) / WO3(25 nm), and (d) 0.4:0.6:1.2, Ag(10 nm) / WO3(25 nm). [Figure 147] 1 shows actual photographs of three-component opaque / semitransparent inverted organic solar cell modules based on the four-component polymer of the present invention, P(3IN=0.3)(3IN2F=0.5)(BDD=0.2):PM6:BTP-eC9: (a) 1:0:1.2, Ag(100 nm), (b) 0.4:0.6:1.2, Ag(15 nm) / MoO3(30 nm). [Figure 148] The synthesis process of P(RR-3IN2F)(3TC=0.5) with the structure D1-(A1-D1-A1) or D1-(A1-D1-A1)-D1-A1 is shown. [Figure 149] 1H NMR of P(RR-3IN2F)(3TC=0.5) is shown. [Figure 150] The synthesis process of P(DPP-3TC) with the A1-A2 structure is shown. [Figure 151] 1H NMR of P(DPP-3TC) is shown. DETAILED DESCRIPTION OF THE INVENTION

[0014] Throughout this specification, the term "alkyl group" refers to a linear or branched C 1-20 , C 1-10 , or C 1-8 It may include alkyl groups such as, but not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, or any isomer thereof. Throughout this specification, the term "aromatic ring" means containing at least one aromatic ring, and 6-30 The term "aromatic hydrocarbon ring group" means an aromatic ring such as phenyl, naphthyl, biphenyl, terphenyl, fluorene, phenanthrenyl, triphenylenyl, perylenyl, chrysenyl, fluoranthenyl, benzofluorenyl, benzotriphenylenyl, benzochrysenyl, anthracenyl, stilbenyl, or pyrenyl. As used throughout this specification, the term "halogen" is meant to refer to elements in Group 17 of the periodic table, including fluorine (F), chlorine (Cl), bromine (Br), iodine (I), and the like. As used throughout this specification, the term "alkoxy" refers to an alkyl-oxygen radical with an alkyl group and is meant to include, for example, methoxy, ethoxy, propoxy, butoxy, pentoxy, and the like. Throughout this specification, the term "fused" refers to two or more rings and means that at least one pair of adjacent atoms is included in the two rings. Throughout this specification, the term "fused ring" means that one or more aromatic or unsaturated hydrocarbon rings having 6 to 20 carbon atoms are fused together.

[0015] The present invention relates to a compound represented by the following chemical formula (1): [ka] In the chemical formula (1), Ligands are reactive ligands, the same or different, each independently a halogen or pseudohalogen, the halogen being selected from the group consisting of Cl, Br, and I, and the pseudohalogen being selected from the group consisting of OTf, OPO(OR)2), and an acetoxy group; X and Y are the same or different and each independently represent a chalcogen, the chalcogen being selected from the group consisting of N, NR, C, O, S, and Se; EWG is a monomer structure containing a ketone group, a diketone group, a cyano group, or a monoketone group and a dicyano group, and is, for example, selected from the group consisting of the following structures: [ka] In the above chemical formula, R and R1 to R4 are the same or different and are each independently selected from the group consisting of hydrogen, a cyano group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted arylsulfoxy group, a substituted or unsubstituted boron group, a substituted or unsubstituted alkylamine group, a substituted or unsubstituted aralkylamine group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted heteroarylamine group, a substituted or unsubstituted aryl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted carbazole group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted thionyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted ester group, a substituted or unsubstituted aromatic group, and a substituted or unsubstituted heterocyclic group containing one or more elements selected from the group consisting of N, O, S, and Se, or two adjacent substituents may form a fused ring.

[0016] The compound represented by the chemical formula (1) may be selected from the following compounds, but is not limited thereto. [ka] In said compounds, EWG is as defined above.

[0017] The compound represented by the chemical formula (1) may be selected from the following compounds, but is not limited to these: [ka] In the above compounds, R and R1 to R4 are as defined above.

[0018] The compound represented by the chemical formula (1) may be selected from the following compounds, but is not limited to these: [ka]

[0019] The present invention also relates to an organic semiconductor compound represented by the following chemical formula (2-1): [ka] In the chemical formula (2-1), A is an electron acceptor unit which is a compound represented by the chemical formula (1) according to the present invention, n is an integer of 1 to 10,000, and D is an electron donor selected from compounds represented by the following structures: [ka] In the above structure, X and Y are the same or different and each independently represent a chalcogen, the chalcogen being selected from the group consisting of N, NR, C, O, S, and Se, and R are the same or different and each independently represent a hydrogen atom; a cyano group; a halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted arylsulfoxy group; a substituted or unsubstituted boron group; a substituted or unsubstituted alkylamine group; a substituted or unsubstituted aralkylamine group; a substituted or unsubstituted aryl substituted or unsubstituted alkoxy groups; substituted or unsubstituted thionyl groups; substituted or unsubstituted silyl groups; substituted or unsubstituted alkenyl groups; substituted or unsubstituted ester groups; substituted or unsubstituted aromatic groups; and substituted or unsubstituted heterocyclic groups containing one or more elements selected from the group consisting of N, O, S, and Se, or two adjacent substituents may form a fused ring.

[0020] The organic semiconductor compound represented by the chemical formula (2-1) may be selected from the compounds represented by the following chemical formulas (3-1) to (3-6), but is not limited thereto: [ka] In the chemical formulas (3-1) to (3-6), n is an integer of 1 to 10,000, and R, X, Y and EWG are as defined above.

[0021] The organic semiconductor compound represented by the chemical formula (2-1) may be selected from, but is not limited to, the following compounds: [ka]

[0022] The present invention also relates to an organic semiconductor compound represented by the following chemical formula (4-1): [ka] In the chemical formula (4-1), A is an electron acceptor unit which is a compound represented by the chemical formula (1) according to the present invention, n is an integer of 1 to 10,000, and A' is the following: an electron acceptor selected from compounds having the structure [ka] In the above structure, X and Y are the same or different and each independently represent a chalcogen, the chalcogen being selected from the group consisting of N, NR, C, O, S, and Se, and R are the same or different and each independently represent a hydrogen atom; a cyano group; a halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted arylsulfoxy group; a substituted or unsubstituted boron group; a substituted or unsubstituted alkylamine group; a substituted or unsubstituted aralkylamine group; a substituted or unsubstituted aryl substituted or unsubstituted alkoxy groups; substituted or unsubstituted thionyl groups; substituted or unsubstituted silyl groups; substituted or unsubstituted alkenyl groups; substituted or unsubstituted ester groups; substituted or unsubstituted aromatic groups; and substituted or unsubstituted heterocyclic groups containing one or more elements selected from the group consisting of N, O, S, and Se, or two adjacent substituents may form a fused ring.

[0023] The organic semiconductor compound represented by the chemical formula (4-1) may be selected from the compounds represented by the following chemical formulas (5-1) to (5-8), but is not limited thereto: [ka] TIFF2025530116000026.tif140125TIFF2025530116000027.tif105126In the chemical formulae (5-1) to (5-8), n is an integer of 1 to 10,000, and R, X, Y and EWG are as defined above.

[0024] The organic semiconductor compound represented by the chemical formula (4-1) may include, but is not limited to, the following compounds: [ka]

[0025] The present invention also relates to an organic semiconductor compound selected from the compounds represented by the following chemical formulas (6-1) to (6-5): [ka] In the chemical formulas (6-1) to (6-5), D1, D2, and D3 are the same or different and are electron donors selected from compounds represented by the following structures: [ka] A1, A2, and A3 are the same or different from one another, and at least one of them is an electron acceptor unit which is a compound represented by chemical formula (1) according to the present invention, and the rest are relative electron acceptors selected from compounds represented by the following structures: [ka] In the above structure, X and Y are the same as or different from each other, and each independently is a chalcogen, the chalcogen being selected from the group consisting of N, N-R, C, O, S, and Se, R being the same as or different from each other, and each independently being hydrogen; a cyano group; a halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted arylsulfoxy group; a substituted or unsubstituted boron group; a substituted or unsubstituted alkylamine group; a substituted or unsubstituted aralkylamine group; a substituted or unsubstituted arylamine group; a substituted or unsubstituted heteroarylamine group; a substituted or unsubstituted aryl group; a substituted or unsubstituted fluorenyl group; a substituted or unsubstituted carbazole group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted thionyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted ester group; a substituted or unsubstituted aromatic group; and a substituted or unsubstituted heterocyclic group containing one or more elements selected from the group consisting of N, O, S, and Se, or two adjacent substituents can form a condensed ring. k is a mole fraction and is a real number of 0 ≦ k < 1, l is a mole fraction and is a real number of 0 ≦ l < 1, m is a mole fraction and is a real number of 0 < m ≦ 1, k + l + m = 1, and n is an integer of 1 to 10,000.

[0026] The organic semiconductor compound represented by the above chemical formulas (6-1) to (6-5) may be selected from, but is not limited to, the compounds represented by the following chemical formulas (7-1) to (7-5):

Chemical formula

[0027] The organic semiconductor compound represented by the above chemical formulas (6-1) to (6-5) may be selected from, but is not limited to, the following compounds: [ka]

[0028] The present invention also provides an organic semiconductor compound selected from the compounds represented by the following chemical formulas (8-1) to (8-4): [ka] In the chemical formulas (8-1) to (8-4), A is an electron acceptor unit which is a compound represented by chemical formula (1) according to the present invention, n is an integer of 1 to 10,000, and A' is a relative electron acceptor selected from compounds represented by the following structures: [ka] D is an electron donor selected from compounds having the following structure: [ka] In the above structure, X and Y are the same or different and each independently represent a chalcogen, the chalcogen being selected from the group consisting of N, NR, C, O, S, and Se, and R are the same or different and each independently represent a hydrogen atom; a cyano group; a halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted arylsulfoxy group; a substituted or unsubstituted boron group; a substituted or unsubstituted alkylamine group; a substituted or unsubstituted aralkylamine group; a substituted or unsubstituted aryl substituted or unsubstituted alkoxy groups; substituted or unsubstituted thionyl groups; substituted or unsubstituted silyl groups; substituted or unsubstituted alkenyl groups; substituted or unsubstituted ester groups; substituted or unsubstituted aromatic groups; and substituted or unsubstituted heterocyclic groups containing one or more elements selected from the group consisting of N, O, S, and Se, or two adjacent substituents may form a fused ring.

[0029] The compound represented by the chemical formula (8-1) may be selected from, but is not limited to, compounds having the following structures: [ka]

[0030] The compound represented by the chemical formula (8-2) may be selected from, but is not limited to, compounds having the following structures: [ka] In the above structure, l, m, and n are as defined above, and X, Y, R1 to R3, and EWG are as defined above.

[0031] The organic semiconductor compounds represented by the chemical formulas (8-1) to (8-4) may be selected from the following compounds, but are not limited to these: [ka]

[0032] The present invention also provides an organic solar cell and an organic electronic device comprising the organic semiconductor compound according to the present invention. The organic solar cell may include a lower substrate through which electricity can flow; a hole transport layer including poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) stacked on the lower substrate; a photoactive layer stacked on the hole transport layer and including an electron donor and an electron acceptor, where the electron donor is the novel unit-based organic semiconductor compound according to the present invention; an organic electron transport layer stacked on the photoactive layer; and an electrode layer stacked on the organic electron transport layer. The organic solar cell may include a lower substrate through which electricity can flow; an inorganic electron transport layer stacked on the lower substrate; a photoactive layer stacked on the inorganic electron transport layer and including an electron donor and an electron acceptor, where the electron donor is the novel unit-based organic semiconductor compound according to the present invention; a hole transport layer stacked on the photoactive layer and including a metal oxide; and an electrode layer stacked on the hole transport layer. The lower substrate is an ITO substrate, and the organic electron transport layer is 2,9-Bis[3-[[3-(dimethylamino)propyl]amino]propyl]-anthra[2,1,9-def:6,5,10-d'e'f']diisoqu inoline-1,3,8,10(2H,9H)-tetrone (PDINN), Poly[[2,7-bis(2-ethylhexyl)-1,2,3,6,7,8-hexahydro-1,3,6,8-tetraoxobenzo[lmn][3,8]phenanthroline-4,9-diyl]-2,5-thiophenediyl[9,9-bis[3-(dimethylamino)propyl]-9H-fluorene-2,7-diyl]-2,5-thiophenediyl] Other Names:PF3N-2TNDI (=PNDIT-F3N), etc., and the electrode layer may contain at least one selected from the group consisting of silver (Ag) and aluminum (Al). The lower substrate is an ITO substrate, the inorganic electron transport layer includes zinc oxide (ZnO), the metal oxide includes molybdenum oxide (MoO), and the electrode layer includes at least one selected from the group consisting of silver (Ag) and aluminum (Al). [Example]

[0033] In order to facilitate understanding of the present invention, preferred examples, experimental examples and production examples are presented below. However, the following examples, experimental examples and production examples are provided to facilitate understanding of the present invention, and are not intended to limit the scope of the present invention.

[0034] Example 1: Synthesis of 4H-clopenta[b]thiophene-4,6(5H)-dione (1) [See Figure 1] Prepare a two-necked round-bottom flask and a condenser. Apply vacuum and flush with nitrogen. Add 11.37 g (85.27 mmol) of aluminum chloride, 100 ml of 1,2-dichloroethane, and 5.0 g (34.11 mmol) of 2-thiophenecarbonyl chloride in that order. Add 10.57 g (75.04 mmol) of malonyl chloride dropwise in an ice bath, then stir vigorously. Heat the reaction mixture to 80°C and stir for 12 hours. Pour the mixture into cold water and stir with chloroform for 12 hours. Extract the extracted organic layer with diluted hydrochloric acid (10%, 150 ml) and water (200 ml). After removing the water, perform column purification (chloroform:ethyl acetate = 9:1). Obtain a yellow powder (yield = 34.0%). 1 H NMR (500MHz, CDCl3): δ (ppm) = 8.0 (d, 1H), 7.39 (d, 1H), 3.48 (s, 2H) [see Figure 2] GC-MS (EI) m / z: Calcd. for C7H4O2S: 152.17; Found 152.19 [see Figure 3].

[0035] Example 2: Synthesis of 2-chloro-4H-clopenta[b]thiophene-4,6(5H)-dione (2) [See Figure 1] Under nitrogen purging, add 14.7 g (110 mmol) of aluminum chloride and 12.1 ml (74.5 mmol) of malonyl chloride to a 100 mL two-necked round-bottom flask, then add 50 ml of dichloromethane. Adjust the temperature to 0°C. Add 3.0 g (16.5 mmol) of 5-chlorothiophene-2-carbonyl chloride and 40 ml of dichloromethane, and stir at 39°C for 8 hours. After cooling to room temperature, add water until no more gas is released, then quench with an aqueous solution of oxalic acid. Then, adjust the pH to 7 with an aqueous solution of sodium bicarbonate. Extract with dichloromethane and water. Sodium chloride is used to remove salts. After removing the water, perform column purification (hexane:dichloromethane = 4:6). Obtain a yellow powder (yield = 28.0%). 1H NMR (500MHz, CDCl3): δ (ppm) = 7.28 (s, 1H), 3.36 (s, 2H) [see Figure 4] GC-MS (EI) m / z: Calcd. for C7H3ClO2S: 186.61; Found 186.06 [see Figure 5].

[0036] Example 3: Synthesis of 1H-cyclopenta[b]naphthalene-1,3(2H)-dione (3) [See Figure 1] A flame-dried 50 mL two-neck round-bottom flask equipped with a stir bar and reflux condenser was charged with 1 (2.5 g, 5.2 mmol), EtOAc (6.8 mL), and NaH (60% dispersion in mineral oil, 369 mg, 22.7 mmol) and flushed with nitrogen. The mixture was heated at reflux for 3 h. The suspension was cooled to room temperature and diluted with hexane (5 mL). The mixture was filtered through a Buchner funnel and washed with additional hexane (5 mL) to give a pale yellow powder. The yellow powder was resuspended in concentrated aqueous HCl (1 M, 25 mL) and heated at 80 °C for 1 h. The suspension was filtered through a Buchner funnel and washed with water to give an ivory powder. (Yield = 33.0%) 1 C 13 H8O2: 196.21; Found 196.18 [See Figure 7].

[0037] Example 4: Synthesis of 2,5-dibromo-3-formylthiophene (4) [See Figure 1] At 0°C, a solution of 5.0g (44.58mmol) thiophene-3-carboxaldehyde, 19.53ml hydrobromic acid (48%), and 19.53ml diethyl ether was mixed, to which a solution of 14.96g (93.62mmol) bromine and 14.65ml hydrobromic acid (48%) was added dropwise. After all the components were added, the mixture was heated to 50°C and left overnight. 50ml of aqueous sodium bisulfite solution was added to quench the mixture. The organic layer was extracted with ethyl acetate. The extract was dried over magnesium sulfate. The product was obtained by column chromatography (dichloromethane:hexane = 1:1). An ivory powder was obtained. (Yield = 90.0%) 1 H NMR (500MHz, CDCl3): δ (ppm) = 9.75 (s, 1H), 7.21 (s, 2H) [see Figure 8] GC-MS (EI) m / z: Calcd. for C5H2Br2OS: 269.94; Found 269.0 [see Figure 9].

[0038] Example 5: Synthesis of 5-((2,5-dibromothiophen-3-yl)methylene)-1,3-diethyl-2-thioxodihydropyridine-4,6(1H,5H)-dione (5) [See Figure 1] 0.54 g (2.0 mmol) of 2,5-dibromothiophene-3-carbaldehyde and 0.38 g (1.9 mmol) of 1,3-diethyl-2-thioxodihydropyridine-4,6(1H,5H)-dione were added to 20.0 ml of HPLC ethanol and vigorously stirred at 78°C for 10 hours. The mixture was washed with ethanol and filtered. An orange powder was obtained (yield = 83.0%). 1 H NMR (500MHz, CDCl3): δ(ppm)=8.42(s, 1H), 8.28(s, 1H), 4.58~4.52(m, 4H), 1.33~1.29(m, 6H) for C 13 H 12 Br2N2O2S2: 452.18; Found 371.97 (detected with one Br removed during measurement) [See Figure 11].

[0039] Example 6: Synthesis of 2-((2,5-dibromothiophen-3-yl)methylene)-1H-indene-1,3(2H)-dione (6) [See Figure 1] Add 1.59 g (5.89 mmol) of 2,5-dibromothiophene-3-carbaldehyde, 1.00 g (6.84 mmol) of 1H-indene-1,3(2H)-dione, and 79.5 ml of HPLC ethanol. Vacuum for 30 minutes, add 0.2 ml of piperidine dropwise, and then evacuate for 30 minutes. After purifying with nitrogen, reflux for 24 hours. Column purification (hexane:chloroform = 1:1) was performed. A yellow solid was obtained (yield = 92.9%). 1 H NMR (500MHz, CDCl3): δ(ppm)=8.76(s, 1H), 8.02~8.0(m, 2H), 7.85~7.83(m, 2H), 7.80(s, 1H) [See Figure 12] 13 C NMR(100 MHz, CDCl3): δ(ppm)=189.79, 189.11, 142.61, 140.39, 135.84, 135.64, 133.55, 133 .87, 133.25, 127.87, 126.90, 123.50, 123.46, 111.89 [See Figure 13] GC-MS(EI) m / z: Calcd. for C 14 H6Br2O2S: 398.07; Found 319.02 (detected with one Br removed during measurement) [See Figure 14] MS (MALDI-TOF) m / z: Calcd. for C 14 H6Br2O2S: 398.07; Found 319.71 (detected in a state where one Br was removed during measurement) [See Figure 15].

[0040] Example 7: Synthesis of (Z)-5-((2,5-dibromothiophen-3-yl)methylene)-4H-cyclopenta[b]thiophene-4,6(5H)-dione (7) [See Figure 1] Add 1.61 g (5.97 mmol) of 2,5-dibromothiophene-3-carbaldehyde, 1.00 g (6.57 mmol) of 4H-clopenta[b]thiophene-4,6(5H)-dione, and 80.5 ml of HPLC ethanol. Vacuum for 30 minutes, add 0.2 ml of piperidine dropwise, and then evacuate for 30 minutes. After purifying with nitrogen, reflux for 24 hours. Purify with a column (hexane:chloroform = 1:1). Obtain a yellow solid (yield = 96.0%). 1H NMR (500 MHz, CDCl): δ (ppm) = 8.58-8.57 (m, 1H), 7.96-7.94 (m, 1H), 7.62-7.60 (m, 1H), 7.47-7.46 (m, 1H) [see Figure 16] 13 C NMR (100MHz, CDCl3): δ(ppm)=189.77, 189.06, 142.46, 140.25, 135.70, 135.57, 135.49, 133.81, 133.12, 127.68, 126.90, 123.40, 123.36, 111.81 [See Figure 17] GC-MS(EI) m / z: Calcd. for C 12 H6Br2O2S2: 404.09; Found 324.97 (detected with one Br removed during measurement) [See Figure 18] MS (MALDI-TOF) m / z: Calcd. for C 12 H6Br2O2S2: 404.09; Found 324.92 (detected in a state where one Br was removed during measurement) [See Figure 19].

[0041] Example 8: Synthesis of (Z)-2-chloro-5-((2,5-dibromothiophen-3-yl)methylene)-4H-cyclopenta[b]thiophene-4,6(5H)-dione (8) [See Figure 1] Add 0.39 g (1.46 mmol) of 2,5-dibromothiophene-3-carbaldehyde, 0.30 g (1.61 mmol) of 2-chloro-4H-clopenta[b]thiophene-4,6(5H)-dione, and 14.6 ml of HPLC ethanol. Vacuum for 30 minutes. Add 0.06 ml of piperidine dropwise. Vacuum for 30 minutes. After purifying with nitrogen, reflux for 24 hours. Column purification (hexane:chloroform = 1:1) was performed. A pale yellow solid was obtained (yield = 82.9%). 1 H NMR (500 MHz, CDCl): δ (ppm) = 8.55 (s, 1H), 7.61 (s, 1H), 7.34 (s, 1H) [see Figure 20] 13C NMR (100MHz, CDCl3): δ(ppm)=182.68, 182.07, 181.28, 180.77, 155.62, 154.10, 153.34, 150.97, 146.78, 146 .46, 135.14, 133.08, 131.73, 129.40, 129.23, 125.82, 120.78, 120.72, 111.90 [See Figure 21] GC-MS(EI) m / z: Calcd. for C 12 H3Br2ClO2S2: 438.53; Found 358.86 (detected with one Br removed during measurement) [See Figure 22] MS (MALDI-TOF) m / z: Calcd. for C 12 H3Br2ClO2S2: 438.53; Found 358.46 (detected in a state where one Br was removed during measurement) [See Figure 23].

[0042] Example 9: Synthesis of 2-((2,5-dibromothiophen-3-yl)methylene)-5,6-difluoro-1H-indene-1,3(2H)-dione (9) [See Figure 1] Add 1.62 g (6.0 mmol) of 2,5-dibromothiophene-3-carbaldehyde, 1.20 g (6.6 mmol) of 5,6-difluoro-1H-indene-1,3(2H)-dione, and 60.0 ml of HPLC ethanol, then vacuum for 3.5 minutes. Add 0.2 ml of piperidine dropwise, vacuum for 30 minutes, then flush with nitrogen. Reflux for 24 hours. Column purification (hexane:dichloromethane = 1:1) was performed (yield = 73.0%). 1 H NMR (500MHz, CDCl3): δ(ppm)=8.67(s, 1H), 7.81~7.77(m, 2H), 7.75(s, 1H) [See Figure 24] 13 C NMR (100MHz, CDCl3): δ(ppm)=187.74, 186.61, 156.59, 156.47, 154.48, 139.71, 135.42, 134.36, 132.88, 127.84, 126.50, 112.47, 112.40, 112.32, 112.25, 112.06 [See Figure 25] GC-MS(EI) m / z: Calcd. for C 14H4Br2F2O2S: 434.05; Found 354.96 (detected with one Br removed during measurement) [See Figure 26] MS (MALDI-TOF) m / z: Calcd. for C 14 H4Br2F2O2S: 438.53; Found 354.85 (detected in a state where one Br was removed during measurement) [See Figure 27].

[0043] Example 10: Synthesis of 2-((2,5-dibromothiophen-3-yl)methylene)-5,6-dichloro-1H-indene-1,3(2H)-dione (10) [See Figure 1] Add 1.62 g (6.0 mmol) of 2,5-dibromothiophene-3-carbaldehyde, 1.42 g (6.6 mmol) of 5,6-dichloro-1H-indene-1,3(2H)-dione, and 60.0 ml of HPLC ethanol. Vacuum for 30 minutes. Add 0.2 ml of piperidine dropwise. Vacuum for 30 minutes. After purifying with nitrogen, reflux for 24 hours. Column purification (hexane:dichloromethane = 1:1) was performed (yield = 86.1%). 1 H NMR (500MHz, CDCl3): δ (ppm) = 8.70 (s, 1H), 8.09-8.06 (ss, 2H), 7.81 (1H) [see Figure 28].

[0044] Example 11: Synthesis of 2-((2,5-dibromothiophen-3-yl)methylene)-1H-cyclopenta[b]naphthalene-1,3(2H)-dione (11) [See Figure 1] Add 0.54 g (2.0 mmol) of 2,5-dibromothiophene-3-carbaldehyde, 0.43 g (2.2 mmol) of 1H-cyclopenta[b]naphthalene-1,3(2H)-dione, and 20.0 ml of HPLC ethanol. Vacuum for 30 minutes. Add 0.1 ml of piperidine dropwise. Vacuum for 30 minutes. After purifying with nitrogen, reflux for 24 hours. Column purification (hexane:dichloromethane = 1:1) was performed (yield = 56.8%). 1H NMR (500MHz, CDCl3): δ(ppm) = 8.86 (s, 1H), 8.55~8.52 (ss, 2H), 8.13~8.12 (m, 2H), 7.88 (s, 1H), 7.74~7.72 (m, 2H) [see Figure 29].

[0045] Example 12: Synthesis of 2,5-dibromofuran-3-carbaldehyde (12) [See Figure 1] To a solution of 3.0 g (31.0 mmol) of furan-3-carbaldehyde and 60.0 ml of anhydrous chloroform at 0°C, add 11.12 g (62.5 mmol) of N-bromosuccinimide in small portions. After adding all the components, heat to 50°C and leave overnight. Quench by adding 50 ml of aqueous sodium bisulfite solution. Extract the organic layer with ethyl acetate. Dry the extract with magnesium sulfate. Pour through a column (dichloromethane:hexane = 2:8) to obtain the product. An ivory powder is obtained. (Yield = 16.0%) 1 H NMR (500MHz, CDCl3): δ (ppm) = 9.80 (s, 1H), 6.74 (s, 2H) [see Figure 30] GC-MS (EI) m / z: Calcd. for C5H2Br2O2: 253.88; Found 253.96 [see Figure 31].

[0046] Example 13: Synthesis of 2-((2,5-dibromofuran-3-yl)methylene)-1H-indene-1,3(2H)-dione (13) [See Figure 1] Add 0.51 g (2.0 mmol) of 2,5-dibromofuran-3-carbaldehyde, 0.32 g (2.2 mmol) of 1H-indene-1,3(2H)-dione, and 20.0 ml of HPLC ethanol. Vacuum for 30 minutes. Add 0.1 ml of piperidine dropwise. Vacuum for 30 minutes. After purifying with nitrogen, reflux for 24 hours. Column purification (hexane:dichloromethane = 1:1) was performed (yield = 66.8%). 1 H NMR (500MHz, CDCl3): δ(ppm)=8.04(s, 1H), 8.03~7.99(m, 2H), 7.84~7.83(m, 2H), 7.55(s, 1H) [see Figure 32].

[0047] Example 14: Synthesis of 2-((2,5-dibromothiophen-3-yl)methylene)-1H-cyclopenta[b]naphthalene-1,3(2H)-dione (14) [See Figure 1] Add 0.51 g (2.0 mmol) of 2,5-dibromofuran-3-carbaldehyde, 0.33 g (2.2 mmol) of 4H-clopenta[b]thiophene-4,6(5H)-dione, and 20.0 ml of HPLC ethanol. Vacuum for 30 minutes. Add 0.1 ml of piperidine dropwise. Vacuum for 30 minutes. After purifying with nitrogen, reflux for 24 hours. Column purification (hexane:dichloromethane = 1:1) was performed (yield = 59.9%). 1 H NMR (500MHz, CDCl3): δ (ppm) = 7.97~7.89 (m, 2H), 7.47~7.45 (s, 1H), 7.36~7.34 (m, 1H) [see Figure 33].

[0048] Example 15: Synthesis of 2-((2,5-dibromothiophen-3-yl)methylene)-1H-cyclopenta[b]naphthalene-1,3(2H)-dione (15) [See Figure 1] Add 0.38 g (2.0 mmol) of 2-bromothiophene-3-carbaldehyde, 0.33 g (2.2 mmol) of 4H-clopenta[b]thiophene-4,6(5H)-dione, and 20.0 ml of HPLC ethanol. Vacuum for 30 minutes. Add 0.1 ml of piperidine dropwise. Vacuum for 30 minutes. After purifying with nitrogen, reflux for 24 hours. Column purification (hexane:dichloromethane = 1:1) was performed (yield = 87.8%). 1 H NMR (500 MHz, CDCl): δ (ppm) = 8.52–8.50 (d, 1H), 7.95–7.92 (d, 1H), 7.75–7.73 (d, 1H), 7.47–7.46 (s, 1H), 7.35–7.34 (d, 1H) [see Figure 34].

[0049] Example 16: Synthesis of 5-bromothiophene-3-carbaldehyde (16) [See Figure 1] To a solution of 3.5 g (31.0 mmol) of thiophene-3-carbaldehyde and 60.0 ml of anhydrous dimethylformamide, add 5.56 g (31.25 mmol) of N-bromosuccinimide in small portions. After adding all the components, leave the mixture at room temperature overnight. Quench the mixture by adding 50 ml of aqueous sodium bisulfite solution. Extract the organic layer with ethyl acetate. Dry the extract with magnesium sulfate. Pour on a column (dichloromethane:hexane = 2:8) to obtain the product. A pale yellow oil is obtained. (Yield = 77.5%) 1 H NMR (500 MHz, CDCl): δ (ppm) = 9.78 (s, 1H), 8.01 (s, 1H), 7.50 (s, 1H) [see Figure 35].

[0050] Example 17: Synthesis of 5-bromo-2-iodothiophene-3-carbaldehyde (17) [See Figure 1] To a solution of 3.81 g (19.94 mmol) of 5-bromothiophene-3-carbaldehyde and 44.0 ml of anhydrous dimethyl chloride at 0°C, add 3.47 g (10.77 mmol) of PhI(OAc) and 2.53 g (9.97 mmol) of iodine in small portions. After all the components have been added, the mixture is stirred at room temperature for 3 hours in the dark. Quench the mixture by adding 50 ml of aqueous sodium thiosulfate solution. Extract the organic layer with ethyl acetate. Dry the extract with magnesium sulfate. Pour through a column (dichloromethane:hexane = 4:6) to obtain the product. A pale yellow solid is obtained. (Yield = 80.3%) 1 H NMR (500 MHz, CDCl3): δ (ppm) = 9.54 (s, 1H), 7.26 (s, 1H) [see Figure 36].

[0051] Example 18: Synthesis of 2-((5-bromo-2-iodothiophen-3-yl)methylene)-5,6-difluoro-1H-indene-1,3(2H)-dione (18) [See Figure 1] Add 0.38 g (2.0 mmol) of 5-bromo-2-iodothiophene-3-carbaldehyde, 0.4 g (2.2 mmol) of 5,6-difluoro-1H-indene-1,3(2H)-dione, and 20.0 ml of HPLC ethanol. Vacuum for 30 minutes. Add 0.1 ml of piperidine dropwise. Vacuum for 30 minutes. After purifying with nitrogen, reflux for 24 hours. Column purification (hexane:dichloromethane = 1:1) was performed (yield = 77.8%). 1 H NMR (500MHz, CDCl3): δ (ppm) = 8.65 (s, 1H), 7.82-7.76 (m, 2H), 7.62 (s, 1H) [see Figure 37].

[0052] Example 19: Synthesis of DA polymer P(3CHO) [see Figure 38] 2,5-Dibromo-3-formylthiophene (4) (54.0 mg, 0.20 mmol), 2DBDT (180.9 mg, 0.20 mmol), and Pd(PPh3)4 (7.0 mg) were added to a 10-20 mL microwave-assisted vial and capped. After applying a vacuum for 30 minutes, the mixture was replaced with N2 and vigorously sparged for 15 minutes. Dry toluene (5.0 mL) was added to completely dissolve the mixture. The reaction mixture was then heated to 110 °C and stirred for 24 hours. After end-capping with 2-3 drops of 2-bromothiophene, the mixture was stirred for an additional hour. The reaction mixture was precipitated in methanol and stirred for approximately 30 minutes. The precipitate was then filtered through a thimble. Subsequently, the oligomers and residual catalyst were removed by Soxhlet purification using methanol (24 hours), acetone (24 hours), hexane (24 hours), and dichloromethane (24 hours) in that order. Finally, the product was dissolved in chloroform (24 hours), and after removing all the solvent, it was reprecipitated in methanol to obtain 120.5 mg of a red substance (87.4% yield). 1 H NMR (500 MHz, CDCl): δ (ppm) [see Figure 39].

[0053] Example 20: Synthesis of DA-structured polymer P(3BA) [See Figure 38] 5-((2,5-dibromothiophen-3-yl)methylene)-1,3-diethyl-2-thioxodihydropyrimidine-4,6(1H,5H)-dione (5) (90.4 mg, 0.20 mmol), 2DBDT (180.9 mg, 0.20 mmol), and Pd(PPh3)4 (7.0 mg) were added to a 10-20 mL microwave-assisted vial and capped. After applying vacuum for 30 minutes or more, the vial was replaced with N2 and vigorously sparged for 15 minutes. Dry toluene (5.0 mL) was added to completely dissolve the residue. The reaction mixture was then heated to 110 °C and stirred for 24 hours. After end-capping with 2-bromothiophene (2-3 drops), the mixture was stirred for an additional hour. The reaction mixture was precipitated in methanol and stirred for approximately 30 minutes. The precipitate was then filtered through a thimble. Subsequently, the oligomers and residual catalyst were removed by Soxhlet purification using methanol (24 hours), acetone (24 hours), and hexane (24 hours) in that order. Finally, the product was dissolved in chloroform (24 hours), and after removing all the solvent, it was reprecipitated in methanol to obtain 118.1 mg (67.8% yield) of a brown substance. 1 H NMR (500 MHz, CDCl): δ (ppm) [see Figure 40].

[0054] Example 21: Synthesis of DA polymer P(3IN) [See Figure 38] 2-((2,5-dibromothiophen-3-yl)methylene)-1H-indene-1,3(2H)-dione (6) (79.6 mg, 0.20 mmol), 2DBDT (180.9 mg, 0.20 mmol), and Pd(PPh3)4 (7.0 mg) were added to a 10-20 mL microwave-assisted vial and capped. After applying a vacuum for 30 minutes, the vial was replaced with N2 and vigorously sparged for 15 minutes. Dry toluene (5.0 mL) was added to completely dissolve the residue. The reaction mixture was then heated to 110 °C and stirred for 24 hours. After end-capping with 2-bromothiophene (2-3 drops), the mixture was stirred for another hour. The reaction mixture was precipitated in methanol and stirred for approximately 30 minutes. The precipitate was then filtered through a thimble. Subsequently, the oligomers and residual catalyst were removed by Soxhlet purification using methanol (24 hours), acetone (24 hours), hexane (24 hours), and dichloromethane (24 hours), and finally the product was dissolved in chloroform (24 hours). After removing all the solvent, the product was reprecipitated in methanol to obtain 151.0 mg (92.4% yield) of a dark green substance. 1 H NMR (500 MHz, CDCl): δ (ppm) [see Figure 41].

[0055] Example 22: Synthesis of DA polymer P(3TC) [see Figure 38] (Z)-5-((2,5-dibromothiophen-3-yl)methylene)-4H-cyclopenta[b]thiophene-4,6(5H)-dione (7) (80.8 mg, 0.20 mmol), 2DBDT (180.9 mg, 0.20 mmol), and Pd(PPh3)4 (7.0 mg) were added to a 10-20 mL microwave-assisted vial and capped. After applying a vacuum for 30 minutes, the mixture was replaced with N2 and vigorously sparged for 15 minutes. Dry toluene (5.0 mL) was added to completely dissolve the residue. The reaction mixture was then heated to 110 °C and stirred for 24 hours. After end-capping with 2-bromothiophene (2-3 drops), the mixture was stirred for another hour. The reaction mixture was precipitated in methanol and stirred for approximately 30 minutes. The precipitate was then filtered through a thimble. Subsequently, the oligomers and residual catalyst were removed by Soxhlet purification using methanol (24 hours), acetone (24 hours), hexane (24 hours), and dichloromethane (24 hours), and finally the product was dissolved in chloroform (24 hours). After removing all the solvent, the product was reprecipitated in methanol to obtain 147.9 mg (89.8% yield) of a dark brown substance. 1 H NMR (500 MHz, CDCl): δ (ppm) [see Figure 42].

[0056] Example 23: Synthesis of DA polymer P(3TC1Cl) [See Figure 38] (Z)-2-chloro-5-((2,5-dibromothiophen-3-yl)methylene)-4H-cyclopenta[b]thiophene-4,6(5H)-dione (8) (87.7 mg, 0.20 mmol), 2DBDT (180.9 mg, 0.20 mmol), and Pd(PPh3)4 (7.0 mg) were added to a 10-20 mL microwave-assisted vial and capped. After applying a vacuum for 30 minutes, the mixture was replaced with N2 and vigorously sparged for 15 minutes. Dry toluene (5.0 mL) was added to completely dissolve the residue. The reaction mixture was then heated to 110 °C and stirred for 12 hours. After end-capping with 2-bromothiophene (2-3 drops), the mixture was stirred for another hour. The reaction mixture was precipitated in methanol and stirred for approximately 30 minutes. The precipitate was then filtered through a thimble. Subsequently, the oligomers and residual catalyst were removed by Soxhlet purification using methanol (24 hours), acetone (24 hours), hexane (24 hours), and dichloromethane (24 hours) in that order. Finally, the product was dissolved in chloroform (24 hours), and after removing all the solvent, it was reprecipitated in methanol to obtain 112.5 mg (65.6% yield) of a dark brown substance. 1 H NMR (500 MHz, CDCl): δ (ppm) [see Figure 43].

[0057] Example 24: Synthesis of DA polymer P(3IN2F) [See Figure 38] 2-((2,5-dibromothiophen-3-yl)methylene)-5,6-difluoro-1H-indene-1,3(2H)-dione (9) (86.8 mg, 0.20 mmol), 2DBDT (180.9 mg, 0.20 mmol), and Pd(PPh3)4 (7.0 mg) were added to a 10-20 mL microwave-assisted vial and capped. After applying vacuum for 30 minutes or more, the mixture was replaced with N2 and vigorously sparged for 15 minutes. Dry toluene (5.0 mL) was added to completely dissolve the residue. The reaction mixture was then heated to 110 °C and stirred for 18 hours. After end-capping with 2-bromothiophene (2-3 drops), the mixture was further stirred for approximately 1 hour. The reaction mixture was precipitated in methanol and stirred for approximately 30 minutes. The precipitate was then filtered through a thimble. Subsequently, the oligomers and residual catalyst were removed by Soxhlet purification using methanol (24 hours), acetone (24 hours), hexane (24 hours), and dichloromethane (24 hours), and finally the product was dissolved in chloroform (24 hours). After removing all the solvent, the product was reprecipitated in methanol to obtain 138.8 mg (81.3% yield) of a dark green substance. 1 H NMR (500 MHz, CDCl): δ (ppm) [see Figure 44].

[0058] Example 25: Synthesis of DA polymer P(3IN2Cl) [See Figure 38] 2-((2,5-dibromothiophen-3-yl)methylene)-5,6-dichloro-1H-indene-1,3(2H)-dione (10) (93.4 mg, 0.20 mmol), 2DBDT (180.9 mg, 0.20 mmol), and Pd(PPh3)4 (7.0 mg) were added to a 10-20 mL microwave-assisted vial and capped. After applying a vacuum for 30 minutes, the mixture was replaced with N2 and vigorously sparged for 15 minutes. Dry toluene (5.0 mL) was added to completely dissolve the residue. The reaction mixture was then heated to 110 °C and stirred for 12 hours. After end-capping with 2-bromothiophene (2-3 drops), the mixture was stirred for another hour. The reaction mixture was precipitated in methanol and stirred for approximately 30 minutes. The precipitate was then filtered through a thimble. Subsequently, the oligomers and residual catalyst were removed by Soxhlet purification using methanol (24 hours), acetone (24 hours), hexane (24 hours), and dichloromethane (24 hours) in that order. Finally, the product was dissolved in chloroform (24 hours), and after removing all the solvent, it was reprecipitated in methanol to obtain 136.3 mg (76.9% yield) of a dark green substance. 1 H NMR (500 MHz, CDCl3): δ (ppm) [none; insoluble after reprecipitation].

[0059] Example 26: Synthesis of DA polymer P(3NT) [See Figure 38] 2-((2,5-dibromothiophen-3-yl)methylene)-1H-cyclopenta[b]naphthalene-1,3(2H)-dione (11) (89.6 mg, 0.20 mmol), 2DBDT (180.9 mg, 0.20 mmol), and Pd(PPh3)4 (7.0 mg) were added to a 10-20 mL microwave-assisted vial and capped. After applying a vacuum for 30 minutes, the vial was replaced with N2 and vigorously sparged for 15 minutes. Dry toluene (5.0 mL) was added to completely dissolve the residue. The reaction mixture was then heated to 110 °C and stirred for 12 hours. After end-capping with 2-bromothiophene (2-3 drops), the mixture was stirred for another hour. The reaction mixture was precipitated in methanol and stirred for approximately 30 minutes. The precipitate was then filtered through a thimble. Subsequently, the oligomers and residual catalyst were removed by Soxhlet purification using methanol (24 hours), acetone (24 hours), hexane (24 hours), and dichloromethane (24 hours) in that order. Finally, the product was dissolved in chloroform (24 hours), and after removing all the solvent, it was reprecipitated in methanol to obtain 97.3 mg (56.1% yield) of a dark green substance. 1 H NMR (500 MHz, CDCl3): δ (ppm) [none; insoluble after reprecipitation].

[0060] Example 27: Synthesis of DA polymer P(Fu3IN) [See Figure 38] 2-((2,5-dibromofuran-3-yl)methylene)-1H-indene-1,3(2H)-dione (13) (57.3 mg, 0.15 mmol), 2DBDT (135.6 mg, 0.15 mmol), and Pd(PPh3)4 (5.3 mg) were added to a 10-20 mL microwave-assisted vial and capped. After applying a vacuum for 30 minutes, the vial was replaced with N2 and vigorously sparged for 15 minutes. Dry toluene (3.8 mL) was added to completely dissolve the residue. The reaction mixture was then heated to 110 °C and stirred for 24 hours. After end-capping with 2-bromothiophene (2-3 drops), the mixture was stirred for an additional hour. The reaction mixture was precipitated in methanol and stirred for approximately 30 minutes. The precipitate was then filtered through a thimble. Subsequently, the oligomers and residual catalyst were removed by Soxhlet purification using methanol (24 hours), acetone (24 hours), hexane (24 hours), and dichloromethane (24 hours) in that order. Finally, the product was dissolved in chloroform (24 hours), and after removing all the solvent, it was reprecipitated in methanol to obtain 64.1 mg (53.3% yield) of a green substance. 1 H NMR (500 MHz, CDCl): δ (ppm) [see Figure 45].

[0061] Example 28: Synthesis of DA polymer P(Fu3TC) [See Figure 38] (Z)-5-((2,5-dibromofuran-3-yl)methylene)-4H-cyclopenta[b]thiophene-4,6(5H)-dione (14) (58.2 mg, 0.15 mmol), 2DBDT (135.6 mg, 0.15 mmol), and Pd(PPh3)4 (5.3 mg) were added to a 10-20 mL microwave-assisted vial and capped. After applying a vacuum for 30 minutes, the mixture was replaced with N2 and vigorously sparged for 15 minutes. Dry toluene (3.8 mL) was added to completely dissolve the residue. The reaction mixture was then heated to 110 °C and stirred for 24 hours. After end-capping with 2-bromothiophene (2-3 drops), the mixture was stirred for another hour. The reaction mixture was precipitated in methanol and stirred for approximately 30 minutes. The precipitate was then filtered through a thimble. Subsequently, the product was purified by Soxhlet purification using methanol (24 hours), acetone (24 hours), hexane (24 hours), and dichloromethane (24 hours) in that order to remove oligomers and residual catalyst. Finally, the product was dissolved in chloroform (24 hours), and after removing all the solvent, it was reprecipitated in methanol to obtain 67.5 mg of a light brown substance (53.9% yield). 1 H NMR (500 MHz, CDCl): δ (ppm) [see Figure 46].

[0062] Example 29: Synthesis of DA polymer P(F-3BA) [See Figure 47] 5-((2,5-dibromothiophen-3-yl)methylene)-1,3-diethyl-2-thioxodihydropyrimidine-4,6(1H,5H)-dione (4) (90.5 mg, 0.20 mmol), F-2DBDT (188.0 mg, 0.20 mmol), and Pd(PPh3)4 (6.6 mg) were placed in a 10-20 mL microwave-assisted vial and capped. After applying vacuum for 30 minutes, the vial was replaced with N2 and vigorously sparged for 15 minutes. Dry toluene (5.5 mL) was added to completely dissolve the residue. The reaction mixture was then heated to 110 °C and stirred for 16 hours. After end-capping with 2-bromothiophene (2-3 drops), the mixture was further stirred for approximately 1 hour. The reaction mixture was precipitated in methanol and stirred for approximately 30 minutes. The precipitate was then filtered through a thimble. Subsequently, the oligomers and residual catalyst were removed by Soxhlet purification using methanol (24 hours), acetone (24 hours), hexane (24 hours), and dichloromethane (24 hours), and finally the product was dissolved in chloroform (24 hours). After removing all the solvent, the product was reprecipitated in methanol to obtain 109.9 mg (60.6% yield) of a brown substance. 1 H NMR (500 MHz, CDCl): δ (ppm) [see Figure 48].

[0063] Example 30: Synthesis of DA polymer P(F-3IN) [See Figure 47] 2-((2,5-dibromothiophen-3-yl)methylene)-1H-indene-1,3(2H)-dione (6) (79.6 mg, 0.20 mmol), F-2DBDT (188.0 mg, 0.20 mmol), and Pd(PPh3)4 (7.0 mg) were added to a 10-20 mL microwave-assisted vial and capped. After applying vacuum for 30 minutes or more, the vial was replaced with N2 and vigorously sparged for 15 minutes. Dry toluene (5.0 mL) was added to completely dissolve the residue. The reaction mixture was then heated to 110 °C and stirred for 16 hours. After end-capping with 2-bromothiophene (2-3 drops), the mixture was further stirred for approximately 1 hour. The reaction mixture was precipitated in methanol and stirred for approximately 30 minutes. The precipitate was then filtered through a thimble. Subsequently, the oligomers and residual catalyst were removed by Soxhlet purification using methanol (24 hours), acetone (24 hours), hexane (24 hours), and dichloromethane (24 hours) in that order. Finally, the product was dissolved in chloroform (24 hours), and after removing all the solvent, it was reprecipitated in methanol to obtain 92.4 mg (54.1% yield) of a dark green substance. 1 H NMR (500 MHz, CDCl): δ (ppm) [see Figure 49].

[0064] Example 31: Synthesis of DA polymer P(Cl-3IN) [See Figure 47] 2-((2,5-dibromothiophen-3-yl)methylene)-1H-indene-1,3(2H)-dione (6) (79.6 mg, 0.20 mmol), Cl-2DBDT (194.6 mg, 0.20 mmol), and Pd(PPh3)4 (7.0 mg) were added to a 10-20 mL microwave-assisted vial and capped. After applying vacuum for 30 minutes, the mixture was replaced with N2 and vigorously sparged for 15 minutes. Dry toluene (5.0 mL) was added to completely dissolve the residue. The reaction mixture was then heated to 110 °C and stirred for 20 hours. After end-capping with 2-bromothiophene (2-3 drops), the mixture was stirred for an additional hour. The reaction mixture was precipitated in methanol and stirred for approximately 30 minutes. The precipitate was then filtered through a thimble. Subsequently, the oligomers and residual catalyst were removed by Soxhlet purification using methanol (24 hours), acetone (24 hours), hexane (24 hours), and dichloromethane (24 hours) in that order. Finally, the product was dissolved in chloroform (24 hours), and after removing all the solvent, it was reprecipitated in methanol to obtain 79.6 mg (44.9% yield) of a dark green substance. 1 H NMR (500 MHz, CDCl): δ (ppm) [see Figure 50].

[0065] Example 32: Synthesis of DA polymer P(C6C6-3IN) [See Figure 47] 2-((2,5-dibromothiophen-3-yl)methylene)-1H-indene-1,3(2H)-dione (6) (79.6 mg, 0.20 mmol), CC-2DBDT (203.4 mg, 0.20 mmol), and Pd(PPh) (7.0 mg) were added to a 10-20 mL microwave-assisted vial and capped. After applying vacuum for 30 minutes, the mixture was replaced with N and vigorously sparged for 15 minutes. Dry toluene (5.0 mL) was added to completely dissolve the residue. The reaction mixture was then heated to 110 °C and stirred for 24 hours. Endcapping was performed with 2-3 drops of 2-bromothiophene, followed by stirring for an additional hour. The reaction mixture was precipitated in methanol and stirred for approximately 30 minutes. The precipitate was then filtered through a thimble. Subsequently, the oligomers and residual catalyst were removed by Soxhlet purification using methanol (24 hours), acetone (24 hours), hexane (24 hours), and dichloromethane (24 hours), and finally the product was dissolved in chloroform (24 hours). After removing all the solvent, the product was reprecipitated in methanol to obtain 88.8 mg (46.4% yield) of a dark green substance. 1 H NMR (500 MHz, CDCl): δ (ppm) [see Figure 51].

[0066] Example 33: Synthesis of DA polymer P(EDOT-3IN) [See Figure 47] 2-((2,5-dibromothiophen-3-yl)methylene)-1H-indene-1,3(2H)-dione (6) (79.6 mg, 0.20 mmol), EDOT-2DBDT (204.0 mg, 0.20 mmol), and Pd(PPh3)4 (7.0 mg) were added to a 10-20 mL microwave-assisted vial and capped. After applying a vacuum for 30 minutes, the mixture was replaced with N2 and vigorously sparged for 15 minutes. Dry toluene (5.0 mL) was added to completely dissolve the residue. The reaction mixture was then heated to 110 °C and stirred for 24 hours. After end-capping with 2-bromothiophene (2-3 drops), the mixture was stirred for another hour. The reaction mixture was precipitated in methanol and stirred for approximately 30 minutes. The precipitate was then filtered through a thimble. Subsequently, the oligomers and residual catalyst were removed by Soxhlet purification using methanol (24 hours), acetone (24 hours), hexane (24 hours), and dichloromethane (24 hours) in that order. Finally, the product was dissolved in chloroform (24 hours), and after removing all the solvent, it was reprecipitated in methanol to obtain 68.2 mg (37.7% yield) of a dark green substance. 1 H NMR (500 MHz, CDCl): δ (ppm) [see Figure 52].

[0067] Example 34: Synthesis of DA polymer P(SEH-3IN) [See Figure 47] 2-((2,5-dibromothiophen-3-yl)methylene)-1H-indene-1,3(2H)-dione (6) (38.8 mg, 0.10 mmol), SEH-2DBDT (96.9 mg, 0.10 mmol), and Pd(PPh3)4 (3.5 mg) were added to a 10-20 mL microwave-assisted vial and capped. After applying vacuum for 30 minutes or more, the mixture was replaced with N2 and vigorously sparged for 15 minutes. Dry toluene (3.0 mL) was added to completely dissolve the residue. The reaction mixture was then heated to 110 °C and stirred for 24 hours. After end-capping with 2-bromothiophene (2-3 drops), the mixture was further stirred for approximately 1 hour. The reaction mixture was precipitated in methanol and stirred for approximately 30 minutes. The precipitate was then filtered through a thimble. Subsequently, the oligomers and residual catalyst were removed by Soxhlet purification using methanol (24 hours), acetone (24 hours), hexane (24 hours), and dichloromethane (24 hours) in that order. Finally, the product was dissolved in chloroform (24 hours), and after removing all the solvent, it was reprecipitated in methanol to obtain 71.1 mg (80.7% yield) of a dark green substance. 1 H NMR (500 MHz, CDCl3): δ (ppm) [none; insoluble after reprecipitation].

[0068] Example 35: Synthesis of DA polymer P(SC8-3IN) [See Figure 47] 2-((2,5-dibromothiophen-3-yl)methylene)-1H-indene-1,3(2H)-dione (6) (38.8 mg, 0.10 mmol), SC8-2DBDT (96.9 mg, 0.10 mmol), and Pd(PPh3)4 (3.5 mg) were added to a 10-20 mL microwave-assisted vial and capped. After applying vacuum for 30 minutes or more, the vial was replaced with N2 and vigorously sparged for 15 minutes. Dry toluene (3.0 mL) was added to completely dissolve the residue. The reaction mixture was then heated to 110 °C and stirred for 24 hours. After end-capping with 2-bromothiophene (2-3 drops), the mixture was further stirred for approximately 1 hour. The reaction mixture was precipitated in methanol and stirred for approximately 30 minutes. The precipitate was then filtered through a thimble. Subsequently, the oligomers and residual catalyst were removed by Soxhlet purification using methanol (24 hours), acetone (24 hours), hexane (24 hours), and dichloromethane (24 hours) in that order. Finally, the product was dissolved in chloroform (24 hours), and after removing all the solvent, it was reprecipitated in methanol to obtain 58.0 mg (65.8% yield) of a dark green substance. 1 H NMR (500 MHz, CDCl3): δ (ppm) [none; insoluble after reprecipitation].

[0069] Example 36: Synthesis of DA polymer P(3IN)-1D [see Figure 47] 2-((2,5-dibromothiophen-3-yl)methylene)-1H-indene-1,3(2H)-dione (6) (39.8 mg, 0.10 mmol), 1DBDT (77.2 mg, 0.10 mmol), and Pd(PPh3)4 (3.5 mg) were added to a 10-20 mL microwave-assisted vial and capped. After applying vacuum for 30 minutes or more, the vial was replaced with N2 and vigorously sparged for 15 minutes. Dry toluene (3.0 mL) was added to completely dissolve the residue. The reaction mixture was then heated to 110 °C and stirred for 24 hours. After end-capping with 2-bromothiophene (2-3 drops), the mixture was stirred for an additional hour. The reaction mixture was precipitated in methanol and stirred for approximately 30 minutes. The precipitate was then filtered through a thimble. Subsequently, the oligomers and residual catalyst were removed by Soxhlet purification using methanol (24 hours), acetone (24 hours), hexane (24 hours), and dichloromethane (24 hours), respectively. Finally, the product was dissolved in chloroform (24 hours), and after removing all the solvent, it was reprecipitated in methanol to obtain 52.0 mg (75.9% yield) of a light green substance. 1 H NMR (500 MHz, CDCl): δ (ppm) [see Figure 53].

[0070] Example 37: Synthesis of DA polymer P(IFL-3IN) [See Figure 54] 2-((2,5-dibromothiophen-3-yl)methylene)-1H-indene-1,3(2H)-dione (6) (79.6 mg, 0.20 mmol), IFL (191.0 mg, 0.20 mmol), and Pd(PPh3)4 (7.0 mg) were placed in a 10-20 mL microwave-assisted vial and capped. After applying vacuum for 30 minutes, the vial was replaced with N2 and vigorously sparged for 15 minutes. Dry toluene (3.0 mL), dry hydrofuran (0.5 mL), and 2 M K2CO3 (1.5 mL) were added to completely dissolve the residue. The reaction mixture was then heated to 110 °C and stirred for 24 hours. After end-capping with 2-bromothiophene (2-3 drops), the mixture was stirred for an additional hour. The reaction mixture was precipitated in methanol and stirred for approximately 30 minutes. The precipitate was then filtered through a thimble. Subsequently, the oligomers and residual catalyst were removed by Soxhlet purification using methanol (24 hours), acetone (24 hours), hexane (24 hours), and dichloromethane (24 hours) in that order. Finally, the product was dissolved in chloroform (24 hours), and after removing all the solvent, it was reprecipitated in methanol to obtain 122.0 mg (64.8% yield) of a reddish-brown substance. 1 H NMR (500 MHz, CDCl): δ (ppm) [see Figure 55].

[0071] Example 38: Synthesis of DA polymer P(NDT-3IN) [See Figure 54] 2-((2,5-dibromothiophen-3-yl)methylene)-1H-indene-1,3(2H)-dione (6) (39.8 mg, 0.10 mmol), NDT (82.2 mg, 0.10 mmol), and Pd(PPh3)4 (3.5 mg) were added to a 10-20 mL microwave-assisted vial and capped. After applying vacuum for 30 minutes or more, the vial was replaced with N2 and vigorously sparged for 15 minutes. Dry toluene (2.5 mL) was added to completely dissolve the residue. The reaction mixture was then heated to 110 °C and stirred for 24 hours. After end-capping with 2-3 drops of 2-bromothiophene, the mixture was stirred for an additional hour. The reaction mixture was precipitated in methanol and stirred for approximately 30 minutes. The precipitate was then filtered through a thimble. Subsequently, the oligomers and residual catalyst were removed by Soxhlet purification using methanol (24 hours), acetone (24 hours), hexane (24 hours), and dichloromethane (24 hours) in that order. Finally, the product was dissolved in chloroform (24 hours), and after removing all the solvent, it was reprecipitated in methanol to obtain 63.8 mg of a brown substance (86.8% yield). 1 H NMR (500 MHz, CDCl3): δ (ppm) [none; insoluble after reprecipitation].

[0072] Example 39: Synthesis of DA polymer P(IDT-3IN) [See Figure 54] 2-((2,5-dibromothiophen-3-yl)methylene)-1H-indene-1,3(2H)-dione (6) (79.6 mg, 0.20 mmol), IDT (246.6 mg, 0.20 mmol), and Pd(PPh3)4 (7.0 mg) were added to a 10-20 mL microwave-assisted vial and capped. After applying vacuum for 30 minutes or more, the vial was replaced with N2 and vigorously sparged for 15 minutes. Dry toluene (5.0 mL) was added to completely dissolve the residue. The reaction mixture was then heated to 110 °C and stirred for 24 hours. After end-capping with 2-bromothiophene (2-3 drops), the mixture was further stirred for approximately 1 hour. The reaction mixture was precipitated in methanol and stirred for approximately 30 minutes. The precipitate was then filtered through a thimble. Subsequently, the oligomers and residual catalyst were removed by Soxhlet purification using methanol (24 hours), acetone (24 hours), hexane (24 hours), and dichloromethane (24 hours) in that order. Finally, the product was dissolved in chloroform (24 hours), and after removing all the solvent, it was reprecipitated in methanol to obtain 179.7 mg (78.4% yield) of a brown substance. 1 H NMR (500 MHz, CDCl): δ (ppm) [see Figure 56].

[0073] Example 40: Synthesis of three-component polymer P(3IN) (3IN2F=0.5) with D1-A1-D1-A2 structure [see Figure 57] 2-((2,5-dibromothiophen-3-yl)methylene)-1H-indene-1,3(2H)-dione (6) (39.8 mg, 0.10 mmol), 2-((2,5-dibromothiophen-3-yl)methylene)-5,6-difluoro-1H-indene-1,3(2H)-dione (9) (43.4 mg, 0.10 mol), 2DBDT (180.9 mg, 0.20 mmol), and Pd(PPh3)4 (7.0 mg) were placed in a 10-20 mL microwave-assisted vial and capped. After applying vacuum for 30 min, the mixture was replaced with N2 and vigorously sparged for 15 min. Dry toluene (5.0 mL) was added to completely dissolve the mixture. The reaction mixture was then heated to 110 °C and stirred for 18 h. After end-capping with 2-3 drops of 2-bromothiophene, the mixture was stirred for another hour. The reaction mixture was precipitated in methanol and stirred for approximately 30 minutes. The precipitate was then filtered through a thimble. The product was then purified by Soxhlet purification using methanol (24 hours), acetone (24 hours), hexane (24 hours), and dichloromethane (24 hours) to remove oligomers and residual catalyst. Finally, the product was dissolved in chloroform (12 hours) to obtain 153.1 mg of a dark green product (91.7% yield). 1 H NMR (400 MHz, CDCl): δ (ppm) [see Figure 58].

[0074] Example 41: Synthesis of three-component polymer P(3IN) (3IN2Cl=0.5) with D1-A1-D1-A2 structure [see Figure 57] 2-((2,5-dibromothiophen-3-yl)methylene)-1H-indene-1,3(2H)-dione (6) (39.8 mg, 0.10 mmol), 2-((2,5-dibromothiophen-3-yl)methylene)-5,6-dichloro-1H-indene-1,3(2H)-dione (10) (46.7 mg, 0.10 mol), 2DBDT (180.9 mg, 0.20 mmol), and Pd(PPh3)4 (7.0 mg) were placed in a 10-20 mL microwave-assisted vial and capped. After applying vacuum for 30 min, the mixture was replaced with N2 and vigorously sparged for 15 min. Dry toluene (5.0 mL) was added to completely dissolve the components. The reaction mixture was then heated to 110 °C and stirred for 18 h. After end-capping with 2-3 drops of 2-bromothiophene, the mixture was stirred for another hour. The reaction mixture was precipitated in methanol and stirred for approximately 30 minutes. The precipitate was then filtered through a thimble. The product was then purified by Soxhlet purification using methanol (24 hours), acetone (24 hours), hexane (24 hours), and dichloromethane (24 hours) to remove oligomers and residual catalyst. Finally, the product was dissolved in chloroform (12 hours) to obtain 148.5 mg of a dark green product (87.2% yield). 1 H NMR (400 MHz, CDCl3): δ (ppm) [none; insoluble after reprecipitation].

[0075] Example 42: Synthesis of three-component polymer P(3TC) (3IN2F=0.5) with D1-A1-D1-A2 structure [see Figure 57] (Z)-5-((2,5-dibromothiophen-3-yl)methylene)-4H-cyclopenta[b]thiophene-4,6(5H)-dione (7) (40.4 mg, 0.10 mmol), 2-((2,5-dibromothiophen-3-yl)methylene)-5,6-difluoro-1H-indene-1,3(2H)-dione (9) (43.4 mg, 0.10 mol), 2DBDT (180.9 mg, 0.20 mmol), and Pd(PPh) (7.0 mg) were placed in a 10-20 mL microwave-assisted vial and capped. After applying vacuum for 30 min, the mixture was replaced with N and vigorously sparged for 15 min. Dry toluene (5.0 mL) was added to completely dissolve the mixture. The reaction mixture was then heated to 110 °C and stirred for 18 h. After end-capping with 2-3 drops of 2-bromothiophene, the mixture was stirred for another hour. The reaction mixture was precipitated in methanol and stirred for approximately 30 minutes. The precipitate was then filtered through a thimble. The product was then purified by Soxhlet purification using methanol (24 hours), acetone (24 hours), hexane (24 hours), and dichloromethane (24 hours) to remove oligomers and residual catalyst. Finally, the product was dissolved in chloroform (12 hours) to obtain 149.0 mg of a light brown substance (88.9% yield). 1 H NMR (400 MHz, CDCl): δ (ppm) [see Figure 59].

[0076] Example 43: Synthesis of three-component polymer P(3TC) (3TC1Cl=0.5) with D1-A1-D1-A2 structure [see Figure 57] (Z)-5-((2,5-dibromothiophen-3-yl)methylene)-4H-cyclopenta[b]thiophene-4,6(5H)-dione (7) (40.4 mg, 0.10 mmol), (Z)-2-chloro-5-((2,5-dibromothiophen-3-yl)methylene)-4H-cyclopenta[b]thiophene-4,6(5H)-dione (8) (43.9 mg, 0.10 mol), 2DBDT (180.9 mg, 0.20 mmol), and Pd(PPh3)4 (7.0 mg) were placed in a 10-20 mL microwave-assisted vial and capped. After applying vacuum for 30 min, the mixture was replaced with N2 and vigorously sparged for 15 min. Dry toluene (5.0 mL) was added to completely dissolve the components. The reaction mixture was then heated to 110 °C and stirred for 18 h. After end-capping with 2-3 drops of 2-bromothiophene, the mixture was stirred for another hour. The reaction mixture was precipitated in methanol and stirred for approximately 30 minutes. The precipitate was then filtered through a thimble. The product was then purified by Soxhlet purification using methanol (24 hours), acetone (24 hours), hexane (24 hours), and dichloromethane (24 hours) to remove oligomers and residual catalyst. Finally, the product was dissolved in chloroform (12 hours) to obtain 120.1 mg of a brown substance (71.4% yield). 1 H NMR (400 MHz, CDCl): δ (ppm) [see Figure 60].

[0077] Example 44: Synthesis of three-component polymer P(3IN) (3TC1Cl=0.4) with D1-A1-D1-A2 structure [see Figure 57] 2-((2,5-dibromothiophen-3-yl)methylene)-1H-indene-1,3(2H)-dione (6) (47.8 mg, 0.12 mmol), (Z)-2-chloro-5-((2,5-dibromothiophen-3-yl)methylene)-4H-cyclopenta[b]thiophene-4,6(5H)-dione (8) (35.1 mg, 0.08 mol), 2DBDT (180.9 mg, 0.20 mmol), and Pd(PPh3)4 (7.0 mg) were placed in a 10-20 mL microwave-assisted vial and capped. After applying vacuum for 30 min, the mixture was replaced with N2 and vigorously sparged for 15 min. Dry toluene (5.0 mL) was added to completely dissolve the components. The reaction mixture was then heated to 110 °C and stirred for 18 h. After end-capping with 2-3 drops of 2-bromothiophene, the mixture was stirred for another hour. The reaction mixture was precipitated in methanol and stirred for approximately 30 minutes. The precipitate was then filtered through a thimble. The product was then purified by Soxhlet purification using methanol (24 hours), acetone (24 hours), hexane (24 hours), and dichloromethane (24 hours) to remove oligomers and residual catalyst. Finally, the product was dissolved in chloroform (12 hours) to obtain 139.7 mg of a dark brown substance (83.4% yield). 1 H NMR (400 MHz, CDCl): δ (ppm) [see Figure 61].

[0078] Example 45: Synthesis of three-component polymer P(3IN) (3TC1Cl=0.2) with D1-A1-D1-A2 structure [see Figure 57] 2-((2,5-dibromothiophen-3-yl)methylene)-1H-indene-1,3(2H)-dione (6) (63.7 mg, 0.16 mmol), (Z)-2-chloro-5-((2,5-dibromothiophen-3-yl)methylene)-4H-cyclopenta[b]thiophene-4,6(5H)-dione (8) (17.5 mg, 0.04 mol), 2DBDT (180.9 mg, 0.20 mmol), and Pd(PPh3)4 (7.0 mg) were placed in a 10-20 mL microwave-assisted vial and capped. After applying vacuum for 30 min, the mixture was replaced with N2 and vigorously sparged for 15 min. Dry toluene (5.0 mL) was added to completely dissolve the components. The reaction mixture was then heated to 110 °C and stirred for 24 h. After end-capping with 2-3 drops of 2-bromothiophene, the mixture was stirred for another hour. The reaction mixture was precipitated in methanol and stirred for approximately 30 minutes. The precipitate was then filtered through a thimble. The product was then purified by Soxhlet purification using methanol (24 hours), acetone (24 hours), hexane (24 hours), and dichloromethane (24 hours) to remove oligomers and residual catalyst. Finally, the product was dissolved in chloroform (12 hours) to obtain 143.3 mg of a brown substance (86.8% yield). 1 H NMR (400 MHz, CDCl3): δ (ppm) [none; insoluble after reprecipitation].

[0079] Example 46: Synthesis of three-component polymer P(3IN) (SEH-2DBDT=0.5) with D1-A1-D2-A1 structure [see Figure 62] 2-((2,5-dibromothiophen-3-yl)methylene)-1H-indene-1,3(2H)-dione (6) (79.6 mg, 0.20 mmol), 2DBDT (90.4 mg, 0.10 mmol), SEH-2DBDT (96.8 mg, 0.10 mmol), and Pd(PPh3)4 (7.0 mg) were added to a 10-20 mL microwave-assisted vial and capped. After applying vacuum for 30 minutes or more, the vial was replaced with N2 and vigorously sparged for 15 minutes. Dry toluene (5.0 mL) was added to completely dissolve the residue. The reaction mixture was then heated to 110 °C and stirred for 24 hours. After end-capping with 2-bromothiophene (2-3 drops), the mixture was further stirred for approximately 1 hour. The reaction mixture was precipitated in methanol and stirred for approximately 30 minutes. The precipitate was then filtered through a thimble. Subsequently, Soxhlet purification was performed in the order of methanol (24 hours), acetone (24 hours), hexane (24 hours), and dichloromethane (24 hours) to remove oligomers and residual catalyst, and finally the product was dissolved in chloroform (12 hours) to obtain 153.2 mg (90.2% yield) of a dark green material. 1 H NMR (400 MHz, CDCl3): δ (ppm) [none; insoluble after reprecipitation].

[0080] Example 47: Synthesis of three-component polymer P(3IN) (F-2DBDT=0.5) with D1-A1-D2-A1 structure [see Figure 62] 2-((2,5-dibromothiophen-3-yl)methylene)-1H-indene-1,3(2H)-dione (6) (79.6 mg, 0.20 mmol), 2DBDT (90.4 mg, 0.10 mmol), F-2DBDT (94.0 mg, 0.10 mmol), and Pd(PPh3)4 (7.0 mg) were added to a 10-20 mL microwave-assisted vial and capped. After applying a vacuum for 30 minutes, the mixture was replaced with N2 and vigorously sparged for 15 minutes. Dry toluene (5.0 mL) was added to completely dissolve the residue. The reaction mixture was then heated to 110 °C and stirred for 24 hours. After end-capping with 2-bromothiophene (2-3 drops), the mixture was stirred for another hour. The reaction mixture was precipitated in methanol and stirred for approximately 30 minutes. The precipitate was then filtered through a thimble. Subsequently, Soxhlet purification was performed in the order of methanol (24 hours), acetone (24 hours), hexane (24 hours), and dichloromethane (24 hours) to remove oligomers and residual catalyst, and finally the product was dissolved in chloroform (12 hours) to give 128.8 mg (77.1% yield) of a dark green material. 1 H NMR (400 MHz, CDCl): δ (ppm) [see Figure 63].

[0081] Example 48: Synthesis of three-component polymer P(3IN2F) (BDD=0.5) with D1-A1-D1-A2 structure [see Figure 64] 2-((2,5-dibromothiophen-3-yl)methylene)-5,6-difluoro-1H-indene-1,3(2H)-dione (9) (43.4 mg, 0.10 mmol), BDD (76.7 mg, 0.10 mmol), 2DBDT (180.9 mg, 0.20 mmol), and Pd(PPh3)4 (7.0 mg) were added to a 10-20 mL microwave-assisted vial and capped. After applying vacuum for 30 minutes, the mixture was replaced with N2 and vigorously sparged for 15 minutes. Dry toluene (5.0 mL) was added to completely dissolve the residue. The reaction mixture was then heated to 110 °C and stirred for 24 hours. After end-capping with 2-bromothiophene (2-3 drops), the mixture was stirred for an additional hour. The reaction mixture was precipitated in methanol and stirred for approximately 30 minutes. The precipitate was then filtered through a thimble. Subsequently, the oligomers and residual catalyst were removed by Soxhlet purification using methanol (24 hours), acetone (24 hours), hexane (24 hours), and dichloromethane (24 hours), and finally the product was dissolved in chloroform (12 hours) to obtain 177.5 mg (87.0% yield) of a black-purple substance. 1 H NMR (400 MHz, CDCl): δ (ppm) [see Figure 65].

[0082] Example 49: Synthesis of three-component polymer P(3IN2F) (FTT=0.2) with D1-A1-D1-A2 structure [see Figure 64] 2-((2,5-dibromothiophen-3-yl)methylene)-5,6-difluoro-1H-indene-1,3(2H)-dione (9) (69.4 mg, 0.16 mmol), FTT (18.9 mg, 0.04 mmol), 2DBDT (180.9 mg, 0.20 mmol), and Pd(PPh3)4 (7.0 mg) were added to a 10-20 mL microwave-assisted vial and capped. After applying vacuum for 30 minutes or more, the vial was replaced with N2 and vigorously sparged for 15 minutes. Dry toluene (5.0 mL) was added to completely dissolve the residue. The reaction mixture was then heated to 110 °C and stirred for 24 hours. After end-capping with 2-bromothiophene (2-3 drops), the mixture was stirred for another hour. The reaction mixture was precipitated in methanol and stirred for approximately 30 minutes. The precipitate was then filtered through a thimble. Subsequent Soxhlet purification using methanol (24 hours), acetone (24 hours), hexane (24 hours), and dichloromethane (24 hours) in that order removed oligomers and residual catalyst, and finally dissolution in chloroform (12 hours) yielded 139.3 mg (80.9% yield) of a dark blue material. 1 H NMR (400 MHz, CDCl): δ (ppm) [see Figure 66].

[0083] Example 50: Synthesis of a quaternary polymer P (3IN = 0.3) (3IN2F = 0.5) (BDD = 0.2) with a D1-A1-D1-A2-D1-A3 structure [see Figure 67] 2-((2,5-dibromothiophen-3-yl)methylene)-1H-indene-1,3(2H)-dione (6) (23.9 mg, 0.06 mmol), 2-((2,5-dibromothiophen-3-yl)methylene)-5,6-difluoro-1H-indene-1,3(2H)-dione (9) (43.4 mg, 0.10 mmol), BDD (30.67 mg, 0.04 mmol), 2DBDT (180.9 mg, 0.20 mmol), and Pd(PPh3)4 (7.0 mg) were placed in a 10-20 mL microwave-assisted vial and capped. After applying vacuum for 30 min, the mixture was replaced with N2 and vigorously sparged for 15 min. Dry toluene (5.0 mL) was added to completely dissolve the components. The reaction mixture was then heated to 110 °C and stirred for 20 h. After end-capping with 2-3 drops of 2-bromothiophene, the mixture was stirred for another hour. The reaction mixture was precipitated in methanol and stirred for approximately 30 minutes. The precipitate was then filtered through a thimble. The product was then purified by Soxhlet purification using methanol (24 hours), acetone (24 hours), hexane (24 hours), and dichloromethane (24 hours) to remove oligomers and residual catalyst. Finally, the product was dissolved in chloroform (12 hours) to obtain 167.2 mg of a pale-green black material (92.0% yield). 1 H NMR (400 MHz, CDCl): δ (ppm) [see Figure 68].

[0084] Example 51: Synthesis of a quaternary polymer P (3TC=0.3) (3IN2F=0.5) (BDD=0.2) with a D1-A1-D1-A2-D1-A3 structure [see Figure 67] (Z)-5-((2,5-dibromothiophen-3-yl)methylene)-4H-cyclopenta[b]thiophene-4,6(5H)-dione (7) (24.2 mg, 0.06 mmol), 2-((2,5-dibromothiophen-3-yl)methylene)-5,6-difluoro-1H-indene-1,3(2H)-dione (9) (43.4 mg, 0.10 mmol), BDD (30.67 mg, 0.04 mmol), 2DBDT (180.9 mg, 0.20 mmol), and Pd(PPh) (7.0 mg) were placed in a 10-20 mL microwave-assisted vial and capped. After applying vacuum for over 30 min, the mixture was replaced with N and vigorously sparged for 15 min. Dry toluene (5.0 mL) was added to completely dissolve the mixture. The reaction mixture was then heated to 110°C and stirred for 18 hours. Endcapping was performed using 2-3 drops of 2-bromothiophene, followed by stirring for an additional hour. The reaction mixture was precipitated in methanol and stirred for approximately 30 minutes. The precipitate was then filtered through a thimble. Subsequently, the product was purified by Soxhlet purification using methanol (24 hours), acetone (24 hours), hexane (24 hours), and dichloromethane (24 hours) to remove oligomers and residual catalyst. Finally, the product was dissolved in chloroform (12 hours) to obtain 169.9 mg of a dark brown substance (93.3% yield). 1 H NMR (400 MHz, CDCl): δ (ppm) [see Figure 69].

[0085] Example 52: Synthesis of a quaternary polymer P (3TC=0.3) (3IN2F=0.5) (D18=0.2) with a D1-A1-D1-A2-D1-A3 structure [see Figure 67] (Z)-5-((2,5-dibromothiophen-3-yl)methylene)-4H-cyclopenta[b]thiophene-4,6(5H)-dione (7) (24.2 mg, 0.06 mmol), 2-((2,5-dibromothiophen-3-yl)methylene)-5,6-difluoro-1H-indene-1,3(2H)-dione (9) (43.4 mg, 0.10 mmol), D18 (36.3 mg, 0.04 mmol), 2DBDT (180.9 mg, 0.20 mmol), and Pd(PPh) (7.0 mg) were placed in a 10-20 mL microwave-assisted vial and capped. After applying vacuum for over 30 min, the mixture was replaced with N and vigorously sparged for 15 min. Dry toluene (5.0 mL) was added to completely dissolve the mixture. The reaction mixture was then heated to 110°C and stirred for 18 hours. Endcapping was performed using 2-3 drops of 2-bromothiophene, followed by stirring for an additional hour. The reaction mixture was precipitated in methanol and stirred for approximately 30 minutes. The precipitate was then filtered through a thimble. The product was then purified by Soxhlet purification using methanol (24 hours), acetone (24 hours), hexane (24 hours), and dichloromethane (24 hours) to remove oligomers and residual catalyst. Finally, the product was dissolved in chloroform (12 hours) to obtain 166.2 mg of a pale purple-black substance (88.5% yield). 1 H NMR (400 MHz, CDCl): δ (ppm) [see Figure 70].

[0086] Example 53: Synthesis of quaternary polymer P (3TC=0.3) (3IN2F=0.5) (3ClTh=0.2) with D1-A1-D1-A2-D1-A3 structure [see Figure 67] (Z)-5-((2,5-dibromothiophen-3-yl)methylene)-4H-cyclopenta[b]thiophene-4,6(5H)-dione (7) (24.2 mg, 0.06 mmol), 2-((2,5-dibromothiophen-3-yl)methylene)-5,6-difluoro-1H-indene-1,3(2H)-dione (9) (43.4 mg, 0.10 mmol), 3ClTh (11.1 mg, 0.04 mmol), 2DBDT (180.9 mg, 0.20 mmol), and Pd(PPh) (7.0 mg) were placed in a 10-20 mL microwave-assisted vial and capped. After applying vacuum for over 30 min, the mixture was replaced with N and vigorously sparged for 15 min. Dry toluene (5.0 mL) was added to completely dissolve the mixture. The reaction mixture was then heated to 110°C and stirred for 18 hours. Endcapping was performed using 2-3 drops of 2-bromothiophene, followed by stirring for an additional hour. The reaction mixture was precipitated in methanol and stirred for approximately 30 minutes. The precipitate was then filtered through a thimble. The product was then purified by Soxhlet purification using methanol (24 hours), acetone (24 hours), hexane (24 hours), and dichloromethane (24 hours) to remove oligomers and residual catalyst. Finally, the product was dissolved in chloroform (12 hours) to obtain 148.7 mg of a dark brown substance (91.5% yield). 1 H NMR (400MHz, CDCl3): δ(ppm) [Figure 71].

[0087] Example 54: Synthesis of ADA-structured single molecule RR-2DBDT-3TC [see Figure 72] (Z)-5-((2-bromothiophen-3-yl)methylene)-4H-cyclopenta[b]thiophene-4,6(5H)-dione (15) (541.4 mg, 1.665 mmol), 2DBDT (502.0 mg, 0.555 mmol), Pd(dba) (23.0 mg), and P(o-toly) (15.0 mg) were added to a 10-20 mL microwave-assisted vial and capped. After applying vacuum for 30 min, the mixture was replaced with N and vigorously sparged for 15 min. Dry toluene (15.0 mL) was added to completely dissolve the residue. The reaction mixture was then heated to 110 °C and stirred for 18 h. After monitoring the progress of the reaction by TLC, a short column was run using a silica pad with dichloromethane. The solvent was removed, and the mixture was then purified by column chromatography (dichloromethane:hexane = 1:1). 518.5 mg (87.5% yield) of a reddish-brown material was obtained. 1 H NMR (400MHz, CDCl3): δ(ppm)=8.44~8.42(d, 2H), 8.05~8.03(d, 2H), 7.94~7.92(d, 2H), 7.75~7.74(s, 2H), 7.49~7.48(d, 2H), 7.46 (s, 2H), 7.40~7.39(d, 2H), 6.88~6.87(s, 2H), 2.81~2.79(m, 4H), 1.58~1.56(m, 2H), 1.34~1.25(m, 16H), 0.86~0.83(m, 12H) [Figure 73].

[0088] Example 55: Synthesis of ADA-structured single molecule RR-2DBDT-3IN2F [see Figure 72] In a 10-20 mL microwave-assist vial, add 2-((2-bromothiophen-3-yl)methylene)-5,6-difluoro-1H-indene-1,3(2H)-dione (15') (591.3 mg, 1.665 mmol), 2DBDT (502.0 mg, 0 The reaction mixture was heated to 110°C and stirred for 18 hours. After monitoring the progress of the reaction by TLC, a short column was run using dichloromethane on a silica pad. The solvent was removed and the mixture was purified by column chromatography (dichloromethane:hexane = 1:1). 533.0 mg of a dark brown substance (85.2% yield) was obtained. 1 H NMR (400MHz, CDCl3): δ(ppm)=8.60~8.59(d, 2H), 8.23(s, 2H), 7.86~7.82(m, 4H), 7.81~7.79(s,2H), 7.48~7.47(d, 2H), 7.46~7. 45(d, 2H), 7.46(s, 2H), 6.89~6.88(d, 2H), 2.83~2.81(m, 4H), 1.60~1.58(m, 2H), 1.30~1.25(m, 16H), 0.88~0.85(m, 12H) [Figure 74].

[0089] Example 56: Synthesis of ADA-structured single molecule RR-2DBDT-3IN2F-2Br [see Figure 72] 2-((5-bromo-2-iodothiophen-3-yl)methylene)-5,6-difluoro-1H-indene-1,3(2H)-dione (18) (601.3 mg, 1.25 mmol), 2DBDT (452.3 mg, 0.50 mmol), and Pd(pph3)4 (30.0 mg) were added to a 10-20 mL microwave-assisted vial and capped. After applying vacuum for 30 min, the mixture was replaced with N2 and vigorously sparged for 15 min. Dry toluene (10.0 mL) and dimethylformamide (1.0 mL) were added to completely dissolve the residue. The reaction mixture was then heated to 110 °C and stirred for 18 h. After monitoring the progress of the reaction by TLC, a short column was run using a silica pad with dichloromethane. The solvent was removed, and the mixture was then purified by column chromatography (dichloromethane:hexane = 1:1). 485.0 mg (75.5% yield) of a dark brown substance was obtained. 1H NMR (400MHz, CDCl3): δ(ppm)=8.60(s, 2H), 8.09(s, 2H), 7.79~7.77(m, 4H), 7.76(s, 2H), 7.44~7.43(s, 2H), 7 .46(s, 2H), 6.88(s, 2H), 2.82~2.80(m, 4H), 1.60~1.58(m, 2H), 1.34~1.25(m, 16H), 0.86~0.85(m, 12H) [Figure 75].

[0090] Example 57: Regioregular ternary polymer RR- with D-(ADA)-D-A' structure Synthesis of P(3IN2F) (BDD=0.5) [See Figure 76] RR-2DBDT-3IN2F-2Br (128.5 mg, 0.10 mmol), BDD (76.7 mg, 0.10 mmol), 2DBDT (180.9 mg, 0.20 mmol), and Pd(PPh3)4 (7.0 mg) were added to a 10-20 mL microwave-assisted vial and capped. After applying vacuum for 30 minutes, the mixture was replaced with N2 and vigorously bubbled for 15 minutes. Dry toluene (5.0 mL) was added to completely dissolve the residue. The reaction mixture was then heated to 110 °C and stirred for 12 hours. After end-capping with 2-3 drops of 2-bromothiophene, the mixture was stirred for an additional hour. The reaction mixture was precipitated in methanol and stirred for approximately 30 minutes. The precipitate was then filtered through a thimble. Subsequently, the oligomers and residual catalyst were removed by Soxhlet purification using methanol (24 hours), acetone (24 hours), hexane (24 hours), and dichloromethane (24 hours), and finally the product was dissolved in chloroform (12 hours) to obtain 178.8 mg (77.4% yield) of a black-purple substance. 1 H NMR (400MHz, CDCl3): δ (ppm) [Figure 77].

[0091] Example 58: Regioregular ternary polymer RR- with D-(ADA)-D-A' structure Synthesis of P(3IN2F) (D18=0.5) [See Figure 76] RR-2DBDT-3IN2F-2Br (128.5 mg, 0.10 mmol), D18 (76.7 mg, 0.10 mmol), 2DBDT (180.9 mg, 0.20 mmol), and Pd(PPh3)4 (7.0 mg) were added to a 10-20 mL microwave-assisted vial and capped. After applying vacuum for 30 minutes, the mixture was replaced with N2 and vigorously sparged for 15 minutes. Dry toluene (5.0 mL) was added to completely dissolve the residue. The reaction mixture was then heated to 110 °C and stirred for 12 hours. After end-capping with 2-3 drops of 2-bromothiophene, the mixture was stirred for an additional hour. The reaction mixture was precipitated in methanol and stirred for approximately 30 minutes. The precipitate was then filtered through a thimble. Subsequently, the oligomers and residual catalyst were removed by Soxhlet purification using methanol (24 hours), acetone (24 hours), hexane (24 hours), and dichloromethane (24 hours), and finally the product was dissolved in chloroform (12 hours) to obtain 196.5 mg (80.0% yield) of a black-purple substance. 1 H NMR (400MHz, CDCl3): δ (ppm) [Figure 78].

[0092] Example 59: Synthesis of polymer P(DPP-3TC) with A'-A structure [see Figure 150] (Z)-5-((2,5-dibromothiophen-3-yl)methylene)-4H-cyclopenta[b]thiophene-4,6(5H)-dione (7) (40.4 mg, 0.10 mmol), 2,5-bis(2-octyldodecyl)-3,6-bis(5-(trimethylstannyl)thiophen-2-yl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione (DPP) (118.7 mg, 0.10 mmol), and Pd(PPh) (3.5 mg) were placed in a 10-20 mL microwave-assisted vial and capped. After applying vacuum for over 30 min, the mixture was replaced with N and vigorously sparged for 15 min. Dry toluene (5.0 mL) was added to completely dissolve the mixture. The reaction mixture was then heated to 110 °C and stirred for 20 h. After end-capping with 2-3 drops of 2-bromothiophene, the mixture was stirred for another hour. The reaction mixture was precipitated in methanol and stirred for approximately 30 minutes. The precipitate was then filtered through a thimble. The product was then purified by Soxhlet purification using methanol (24 hours), acetone (24 hours), hexane (24 hours), and dichloromethane (24 hours) to remove oligomers and residual catalyst. Finally, the product was dissolved in chloroform (12 hours) to obtain 79.0 mg of a pale-green-black substance (71.4% yield). 1 H NMR (400 MHz, CDCl3): δ (ppm) [see Figure 151].

[0093] Example 60: Synthesis of three-component polymer P(RR-3IN2F) (3TC=0.5) having D-(ADA) or D-(ADA)-DA structure [see Figure 148] (Z)-5-((2,5-dibromothiophen-3-yl)methylene)-4H-cyclopenta[b]thiophene-4,6(5H)-dione (7) (40.4 mg, 0.10 mmol), RR-2DBDT-3INF-2Br (128.5 mg, 0.10 mmol), 2DBDT (180.9 mg, 0.20 mmol), and Pd(PPh3)4 (7.0 mg) were placed in a 10-20 mL microwave-assisted vial and capped. After applying vacuum for 30 min, the mixture was replaced with N2 and vigorously sparged for 15 min. Dry toluene (5.0 mL) was added to completely dissolve the mixture. The reaction mixture was then heated to 110 °C and stirred for 15 h. The mixture was end-capped with 2-bromothiophene (2-3 drops) and stirred for an additional 1 h. The reactant was precipitated in methanol, stirred for approximately 30 minutes, and then filtered through a thimble. Subsequently, the precipitate was purified by Soxhlet filtration using methanol (24 hours), acetone (24 hours), hexane (24 hours), and dichloromethane (24 hours) to remove oligomers and residual catalyst. Finally, the product was dissolved in chloroform (12 hours) to obtain 168.9 mg (86.7% yield) of a dark brown substance. 1 H NMR (400 MHz, CDCl3): δ (ppm) [see Figure 149].

[0094] <Example 61> Design, synthesis, and application of efficient organic semiconductors for electron donors based on 3-vinylene heterocyclics incorporating highly planar electron-withdrawing units: Development of new acceptor units with low synthetic complexity and high scalability and new polymers incorporating the same, computational simulation calculations, and theoretical analysis [See Figures 79, 80, 81, 82, and 83] Comparison of the synthetic complexity of acceptor units of previously developed high-performance polymers (e.g., PM6 / 7, D18, PTB7-Th, etc.) with newly developed 3-vinylene heterocyclic units incorporating highly planar electron-withdrawing units: Synthetic complexity (SC; Macromolecules 2015, 48, 3, 453-461) is a mathematical formula used by Ricardo Po and his team in 2015 to evaluate the commercialization index of organic solar cell materials. It is calculated by adding up five parameters in a normalized database, including the number of synthetic steps (NSS), reciprocal yield (RY), number of operation units for the isolation / purification (NUO), number of column chromatographies for the isolation / purification (NCC), and number of hazardous chemicals (NHC), with weights of 35%, 25%, 15%, 15%, and 10%, respectively. Therefore, the closer the SC is to zero, the higher the commercial viability and the more cost-competitive the product. However, estimating a material's SC can be somewhat challenging due to various interpretations and assumptions regarding the factors involved in the separation and purification process, as well as inconsistencies in the number and characteristics of hazardous materials labeled for the same chemical by different chemical suppliers. Therefore, in 2021, Iain McCulloch and his team took these factors into account and proposed a new formula for evaluating the commercial viability index of organic solar cell materials. This formula, which takes only the NSS and RY of the synthetic route into account, provides a simpler and more reliable method for calculating the scalability factor (SF) of a specific organic solar cell device. Starting materials were defined as in the literature, i.e., "chemicals that can be found on the market in sufficient quantities to produce hundreds of kilograms of polymer." Therefore, we always traced synthetic routes until we found such starting materials and, if possible, defined them in the literature. Based on this reliability, we compared and analyzed the scalability coefficients of the BDD and D18 units that constitute the well-known highly efficient polymers, such as PM6 / 7 and D18, with those of the newly developed 3-vinylene heterocyclic unit incorporating a highly planar electron-withdrawing moiety. As shown in Figure 79, the BDD and D18 units showed NSS of 5 and 10, respectively, and RY of 4.97 and 4.76. On the other hand, as shown in Figure 80, the newly developed 3CHO, 3BA, 3IN, 3TC, 3TC1Cl, 3IN2F, 3IN2Cl, etc. showed NSS of 1 to 4 and RY of 1.11 to 3.93, all of which were lower than the acceptor units of highly efficient polymers already available commercially. Therefore, polymers composed of 3-vinylene heterocyclic units incorporating the newly developed highly planar electron-withdrawing moiety can have a high scalability factor with much lower synthetic complexity. In other words, if only efficiency is ensured, they can be evaluated as being sufficiently price competitive (a detailed comparison of the efficiency and scalability factors of the newly developed polymers will be discussed in detail later). Computational simulation and analysis of polymers based on 3-vinylene heterocyclic units incorporating newly developed highly planar electron-withdrawing units: Next, to understand the change in frontier energy levels when new units are introduced into the polymer backbone, density functional theory (DFT) calculations were performed using Gaussian 16, a computational simulation software. The functions used were b3lyp and 6-31G(d). The aforementioned BDD and D18 units are highly planar derivatives with moderate electron-withdrawing properties, and contain two long branched chains of 2-ethylhexyl and 2-butyloctyl, which induce a thermal-dependent aggregation (TDA) effect in the polymer backbone, thereby providing the advantage of simultaneously achieving high solubility and degree of polymerization in common organic solvents. Meanwhile, the new unit, a group with relatively strong electron-withdrawing properties linked to the 3-vinylene, can more effectively reduce the band gap of the polymer. Unlike conventional side chains, it has a single linked plate-like structure, which generates a large regiorandom (RA) tilting angle between adjacent 2DBDT donor derivatives, resulting in a TDA effect similar to BDD and D18. Furthermore, due to the large tilting angle, the 2DBDT on the opposite side has a relatively restored planar angle, which allows for the formation of a face-on structure on the substrate. Furthermore, the high aromaticity resulting from the sharing and hybridization of the electron clouds linked to the 3-vinylene allows for the polymer to be designed to simultaneously possess a deep HOMO energy level. More importantly, the asymmetric structure of the new unit can impart a larger dipole moment to the polymer than BDD and D18, thereby enabling high solubility in common organic solvents and high polymerization degree despite the relatively low side chain substitution. As shown in Figure 81, the effects of halogenation on the dihedral angle, dipole moment (D), HOMO and LUMO energy levels, and band gap were investigated using the Gaussian function of the repeating unit (n) (n = 1) of a model compound containing 2DBDT and 3IN derivatives as the main backbone. First, as mentioned above, the new acceptor unit forms an asymmetric RA backbone. Therefore, the P(3IN)-in / out structure showed different results in all DFT calculation parameters. Notably, the dihedral angle was significantly tilted at 41.0° for the in structure, while the out structure restored planarity to 12.9°, suggesting that the actual structure possesses a flexible backbone as expected. On the other hand, when halogenation, especially fluorination, was introduced into 2DBDT and 3IN, there was no significant change in the dihedral angle, but there was a significant difference in the frontier energy levels. Finally, the introduction of chlorine into the polymer resulted in a deeper HOMO energy level and a lower band gap than fluorination. Figure 82 shows the Gaussian calculation results for model compounds with 2DBDT and 3TC derivatives as the main skeleton (n = 1). Similar to P(3IN)-in / out, P(3TC)-in / out also exhibited different dihedral angles and frontier energy levels. However, the dipole moments were similar, which could be resolved through more detailed structural analysis and simulation of the expected structures. In particular, because the S on the TC side can be oriented in two directions toward RA, the total number of possible structures for 3TC is four, twice that of 3IN. 3TC can also be halogenated, and, like the results for the chlorinated 3TC1Cl, all DFT calculation parameters except the dihedral angle increase. In other words, the dipole moment increases, the LUMO and HOMO energy levels become deeper, and the band gap becomes smaller. Finally, in Figure 83, we compared the DFT calculation results for P(3IN)-in, in / in, out / out, and out structures at n = 2 to more accurately predict the energy levels of actual polymers. As the repeating unit was extended to a dimer, the molecular hybridization energy levels stabilized, and all three structures exhibited similar LUMO, HOMO, and band gaps. Meanwhile, for dihedral angles, the planarity of the polymer backbone was found to change significantly depending on the orientation of the 3IN units to the 2DBDT. Notably, the dihedral angles between the 2DBDT and 3IN units alternated between shifting and recovering, suggesting that the formation of the in and out structures would result in a more planar polymer backbone. This suggests that the polymers inherently possess high π-π stacking, resulting in a predominantly face-on structure.

[0095] Example 62: Design, synthesis, and application of efficient organic semiconductors for 3-vinylene heterocyclic-based electron donors incorporating highly planar electron-withdrawing groups: Analysis of physical, thermal, optical, and electrochemical properties [see Figures 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, and 103] Physical and thermal properties of the polymers: All newly synthesized polymers / monomers were successfully synthesized by Stille CC coupling reactions. The synthesis yields of each are listed in the synthesis methods in the Examples. After reprecipitation, all polymers showed excellent solubility in common organic solvents, except for a few polymers that were insoluble. As shown in Table 1, the relative molecular weight was measured through gel permeation chromatography (GPC) using polystyrene as a standard substance, and most of the polymers had a weight average molecular weight (M) of more than 30,000. w) and a polydispersity index (PDI) in the 2-point range, confirming the formation of an appropriate molecular weight. Therefore, it was sufficient to investigate the relationship between the polymer structure and properties. As the structure expands from binary to ternary and quaternary polymers, the molecular weight gradually increases. This is due to the increased stereo-irregularity in the molecular chains and the increased structural complexity resulting from the increased number of possible structures, which in turn reduces the relative rigidity of the polymer. As shown in Figure 84, thermogravimetric analysis (TGA) showed that all four polymers had a decomposition temperature T d The thermal stability (temperature at which a 5% sample weight loss occurs) was above 300°C. This indicates that all four structures have sufficient thermal stability for organic electronic applications such as organic solar cells. Furthermore, increasing the halogenation within the structure or introducing 3TC instead of 3IN tended to further increase the thermal stability, with the two-component, three-component, and finally four-component structures showing the highest thermal stability. Detailed measurement results are summarized in Table 1.

[0096] The crystalline properties of the molecular structure were examined by differential scanning calorimeter (DSC) measurements, and all polymers showed no obvious thermal transition between 25 and 300°C.

[0097] [Table 1]

[0098] Optical and electrochemical properties of polymers: The optical and electrochemical properties of the primary polymers were studied by UV-Vis spectroscopy and cyclic voltammetry (CV). As shown in Figures 85, 86, 87, and 88, when the absorption wavelengths of all polymers in the normalized film state were confirmed, it was confirmed that the strong 0-0 peak around 550-600 nm that was clearly present in the P(3CHO) polymer disappeared, while the polymer had a narrower band gap. P(3CHO) showed UV behavior with the typical push-pull structure of a general donor-acceptor, while all other polymers showed unique π-π behavior around 300-400 nm and 450-550 nm. * The transition characteristic was observed, and no clear peak indicating intramolecular charge transfer (ICT) was observed, but the peak shifted to the long wavelength region. This means that the electron flow along the main chain changes, unlike the structural morphology between a general donor and acceptor. Therefore, it is expected that the Y6 derivative, which has a strong absorption band in the 700-950 nm range, and especially the BTP-eC9 acceptor, will have complementary properties. In the thin film state, the optical band gap (E g opt ) were calculated and are summarized in Table 2. Among the new acceptor units excluding 3CHO, the band gaps tended to become narrower in the order 3BA, 3TC1Cl, 3TC, 3IN, 3IN2F, and 3IN2Cl. This trend also appeared when the structure was expanded from binary to ternary and quaternary polymers. Figures 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, and 99 compare the TDA properties of representative polymers developed using this technology, including the commercial polymers PM6 and PTB7-Th. All polymers, except for P(3BA) and P(3IN)-1D, exhibited strong aggregation behavior at room temperature, and the aggregation behavior was observed to resolve as the temperature gradually increased. Polymers with such properties can align and aggregate in a regular manner, which has the advantage of enabling more efficient charge transport when used in organic solar cell devices and for orientation depending on the substrate. As shown in Figures 100, 101, 102, and 103, the frontier energy levels of a polymer can be calculated from the oxidation-reduction curves obtained by CV curves. More specifically, the HOMO (E HOMO ) and LUMO energy level (E LUMO ) are the onset oxidation potentials (E ox onset ) and reduction potential (E red onset ) can be obtained by the following electrochemical equation: E HOMO or E LUMO =-4.8-(E ox Mataha red onset -E 1 / 2 , ferrocene ), where E 1 / 2. ferrocene = 0.44-0.48 eV (ferrocene data obtained for each measurement). In this study, we used a method that allows for a more rational and accurate understanding of trends by determining only the HOMO energy levels of all polymers by CV and then calculating the LUMO energy levels from the difference with the optical band gap. All polymers are expected to have properly aligned frontier energy levels when mixed with Y6 derivatives, especially the BTP-eC9 acceptor, which enables efficient charge transport. Furthermore, considering that the HOMO and LUMO energy levels of the near-infrared (NIR) acceptor BTP-eC9 are -5.68 eV and -4.05 eV, all polymers are expected to have minimized energy offsets of 0.23 to 0, resulting in little energy loss. In particular, among the new acceptor units, the order of 3BA, 3IN, 3TC, 3IN2F, 3CHO, and 3IN2Cl is such that the HOMO energy level is deep enough to be introduced into the polymer, and the open-circuit voltage (V oc ) was expected to increase. Detailed values ​​showing the optical and electrochemical properties are summarized in Table 2.

[0099] [Table 2]

[0100] Example 63: Design, synthesis, and application of efficient organic semiconductors for electron donors based on 3-vinylene heterocyclics incorporating highly planar electron-withdrawing moieties: organic solar cell fabrication, crystal / orientation, morphology analysis, and contact angle analysis [see Figures 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, and 129] Optimization of polymer organic solar cells with conventional structures: The newly developed representative polymer has optical and electrochemical properties very complementary to BTP-eC9 with a band gap of 1.34 eV, making it very reasonable to fabricate devices based on it. The organic solar cell structure used in this invention was a conventional structure, ITO / PEDOT:PSS (30 nm) / Polymer:BTP-eC9 / PDINN (10 nm or less) or PNDIT-F3N (10 nm or less) / Ag (100 nm) stacked, and the performance of the photovoltaic cell was observed. Each device was optimized by adjusting the donor-to-acceptor ratio, heat treatment temperature, and solvent / additive. All blend films had a polymer to BTP-eC9 ratio of 1:1.2 and were optimized for thicknesses between 90 and 100 nm. The effective photoactive measurement area covered by the mask was measured using an optical microscope to determine the area of ​​0.04 cm. 2 It was confirmed that... Figures 104, 105, 106, 107, 108, 109, 110, and 111 show the JV and external quantum efficiency (EQE) waveforms of optimized organic solar cells using representative binary, ternary, quaternary, and stereoregular polymers. First, due to limited solubility, binary polymers were optimized using all-halogen solvents as the base solvent (chloroform, CF with 0.5% 1,8-diiodooctane, DIO for P(3CHO), P(3BA); chlorobenzene, CB with 0.5% DIO for P(3IN), P(3TC1Cl), P(3IN2F); CB with 3.5% 1-chloronaphthalene, CN for P(3TC)). It is noteworthy here that the open circuit voltage (V) as well as the change in the HOMO energy level due to the introduction of the new acceptor units into the polymer backbone as mentioned above are notable. oc ) was formed, and all polymers except P(3BA) showed high efficiencies of over 10%. In particular, in the case of P(3TC), the efficiencies were 24 mA / cm 2 Excellent current density (short circuit current density, J sc ) and achieved an efficiency of 11.7%, the highest among two-component polymers. This is due to a photoreaction rate of over 70% across the entire range of 400-850 nm, the main photon energy band of sunlight. As the morphology of donor-acceptor building blocks expanded from binary to ternary polymers, the stereoirregularity and structural complexity of the moieties within the polymer backbone further increased. Therefore, the processability of the polymers could be improved by utilizing relatively environmentally friendly solvents, toluene and xylene, as the parent solvents. The optimized solvent conditions were as follows: o-xylene, XY with 0.8% 1-phenylnaphthalene, PN for P(3IN) (3IN2F = 0.5), P(3IN) (3TC1Cl = 0.5); toluene with 0.8% PN for P(3IN2F) (BDD = 0.5). Despite optimizing the device under environmentally friendly solvent conditions, improved efficiency was achieved compared to binary polymers. In particular, the P(3IN) (BDD = 0.5) structure achieved a photoelectric conversion efficiency of up to 13.0% due to the increased ICT effect resulting from the introduction of 50% BDD units as the acceptor. However, the introduction of 50% BDD resulted in cost losses and also reduced transmittance in the visible light range, making structural changes necessary. As mentioned above, the effectiveness of the ternary building blocks was confirmed, so the results of organic solar cells using quaternary polymers were promising. Similarly, the quaternary polymers also showed excellent solubility in environmentally friendly solvents and were optimized under the following conditions: XY with 0.8% PN for P(3IN = 0.3)(3IN2F = 0.5)(BDD = 0.2), P(3TC = 0.3)(3IN2F = 0.5)(BDD = 0.2), and P(3TC = 0.3)(3IN2F = 0.5)(3ClTh = 0.2). All three quaternary polymers exhibited high photoelectric conversion efficiencies of over 13.7%, with photoresponses approaching 80% across the entire wavelength range from 450 to 850 nm, as evidenced by the EQE graphs. More importantly, the cost, efficiency, and transparency were all increased simultaneously by reducing the BDD content from approximately 50% in the ternary polymer to 20%. Furthermore, by introducing the 3ClTh acceptor unit, which has a simpler structure than BDD, lower costs were achieved while maintaining efficiency. Among the quaternary polymers, P(3IN=0.3)(3IN2F=0.5)(BDD=0.2) exhibited the most balanced solar cell parameter values, demonstrating the highest efficiency of 14.0%.

[0101] [Table 3]

[0102] To analyze the photovoltaic properties of polymers in detail, the crystalline and orientation characteristics of the polymers in their raw or blended film state were investigated using Grazing-Incidence Wide-Angle X-ray Scattering (GIWAXS). As shown in Figure 112, among the two-component polymers, P(3CHO) exhibited the tightest stacking distance in the out-of-plane direction. This indicates that it possesses an orientation that allows for high charge transport and crystallinity when mixed with BTP-eC9. On the other hand, the crystallinity and orientation properties weakened and then strengthened again in the order of P(3BA), P(3IN), and P(3TC). In particular, the amorphous phase predominates in the untreated polymer film for P(3BA), which explains the low device efficiency. Although not as pronounced as P(3CHO), the face-on structure was restored in the P(3IN) and P(3TC) structures, suggesting high charge transport. As shown in Figures 113 and 114, the P(3CHO), P(3IN), and P(3TC) polymers, which have excellent crystal and orientation properties, were analyzed for their respective BTP-eC9 and blend films. As a result, it was confirmed that (a) P(3CHO) lost its original strong face-on structure, while (b) P(3IN) strongly formed an edge-on crystal structure, and finally (c) P(3TC) showed the most dominant face-on crystal structure. This is because, for each solar cell parameter, P(3CHO) lost its crystal structure but maintained a high V oc P(3IN) has the weakest face-on structure, but achieves 10.6% with high FF due to the strong (100) character. P(3CHO) achieves high J due to the strong π-π stacking. sc It is analyzed to have an efficiency of 11.7%. In Figure 115, we observed the changes in the crystallization and orientation properties of P(3TC1Cl) and P(3IN2F) due to halogenation in P(3TC) and P(3IN) polymers. Although parallel comparisons with previous data are difficult due to differences in the X-ray analysis equipment used, we were able to confirm the trend and effect of this halogenated ternary polymer developed using these novel halogenated units. As shown in Figure 116, the P(3IN) (3IN2F = 0.5) ternary polymer exhibited a weaker face-on structure than P(3IN2F) with 100% 3IN2F, and the fluorination of 3IN had a positive effect on the orientation of the polymer. Similarly, chlorination of P(3TC1Cl) showed a similar trend. However, while P(3IN2F) and P(3TC1Cl) possessed excellent properties in terms of crystallization and orientation, they also exhibited several issues, such as relatively low molecular weights, strong molecular aggregation behavior, and limited solubility. On the other hand, ternary polymers such as P(3IN)(3IN2F=0.5) and P(3IN)(3TC1Cl=0.4) showed significant improvements in device efficiency, despite the use of environmentally friendly solvents. This is due to the strong face-on structure of the polymers, which enabled smooth charge transfer when blended with BTP-eC9. Finally, the P(3IN2F)(BDD=0.5) polymer, which incorporates 50% 3IN2F and 50% BDD as acceptor units into the polymer backbone, exhibited the strongest face-on structure and resulted in the highest efficiency of 13%. More specifically, as shown in Figures 117 and 118, both P(3IN)(3IN2F=0.5) and P(3IN2F)(BDD=0.5) polymers exhibited increased crystallinity and relatively high J when blended with BTP-eC9 compared to their respective untreated films. sc The characteristics allowed high efficiencies of 12.6% and 13.0% to be achieved. Finally, as shown in Figures 119 and 120, the P(3IN = 0.3)(3IN2F = 0.5)(BDD = 0.2) polymer, further expanded into a quaternary morphology, exhibited a stronger face-on structure in the unprocessed film despite a 30% relative reduction in BDD in the backbone compared to the P(3IN2F)(BDD = 0.5) polymer. This confirms the opposite crystalline and orientational properties of the commercial polymer PM6, which has a predominantly edge-on structure. The quaternary structure exhibited reduced rigidity compared to the ternary polymer, resulting in increased miscibility. When blended with BTP-eC9, the polymer achieved the highest efficiency of 14.0% among the polymers synthesized with a high FF of 66.8%. Since the morphology of the active layer is closely related to charge transport and collection in photovoltaic performance, the surface of the optimized mixed film was observed in detail using atomic force microscopy (AFM). As shown in Figures 121, 122, 123, and 124, most polymers exhibited smooth and favorable morphologies similar to BTP-eC9 at the microscale. Notably, as we progressed from binary to ternary and quaternary polymers, the relative reduction in aggregates led to a gradual decrease in root-mean-square (RMS) roughness from approximately 3.0 nm to 0.7–0.8 nm, which is an appropriate value for efficient charge transport. In addition, the FF and J of the element can be observed in the respective 2D / 3D topography and phase images. sc# In particular, the three polymers P(3IN)(3IN2F=0.5), P(3IN2F)(BDD=0.5), and P(3IN=0.3)(3IN2F=0.5)(BDD=0.2), which showed high efficiencies of 12.6%, 13.0%, and 14.0%, respectively, all formed interpenetrating networks between donor and acceptor groups, exhibiting clean phase images and demonstrating the feasibility of nanoscale phase separation. Finally, as shown in Figures 125, 126, 127, 128, and 129, we measured the surface contact angles of each material in diiodomethane (DIM) and water using the DSA100 instrument. This allowed us to understand and calculate the correlation between the miscibility of the newly synthesized donor polymers and BTP-eC9. Briefly, we used the Owens, Wendt, Rabel, and Kaelble (OWRK) model to examine the surface energy of each material based on the contact angle measurements. We found that for highly efficient polymers, including the commercial polymer PM6, the difference in surface energy between them and BTP-eC9 was relatively large, leading to the formation of purer domains within the mixed film. This resulted in the donor-acceptor mixture being properly mixed while maintaining high crystallinity, resulting in excellent photovoltaic performance. The detailed values ​​are summarized in Table 4.

[0103] [Table 4]

[0104] Example 64: Design, synthesis, and application of efficient organic semiconductors for electron donors based on 3-vinylene heterocyclic compounds incorporating highly planar electron-withdrawing groups: Optimization of organic solar cells by adjusting the donor ratio of a P(3IN=0.3)(3IN2F=0.5)(BDD=0.2) polymer ternary system, external authentication, and fabrication of semi-transparent, highly efficient organic solar cell elements / modules [see Figures 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144, 145, 146, and 147] Based on the excellent structure-property relationship, crystalline / orientation, and morphological properties of the P(3IN = 0.3)(3IN2F = 0.5)(BDD = 0.2) polymer, we first attempted to fabricate ternary organic solar cells for higher efficiency. To improve FF by increasing edge-on orientation in the conventional P(3IN = 0.3)(3IN2F = 0.5)(BDD = 0.2):BTP-eC9 blend film, we employed and introduced PM6 polymer as the ternary donor. Devices with conventional structures were fabricated and evaluated under the same environmentally friendly solvent conditions. In particular, TL was selected instead of XY solvent to induce highly crystalline film formation during coating and annealing. The results of the optimized ternary organic solar cell devices are summarized in Table 5, and the JV and EQE waveforms of the optimized ternary organic solar cell devices are shown in Figures 130 and 131. The JV and EQE curves of the optimized ternary organic solar cell devices were significantly improved by gradually increasing the ratio of PM6 instead of P(3IN = 0.3)(3IN2F = 0.5)(BDD = 0.2). sc The FF improved, and especially the dramatic increase in FF led to the highest PCE of 16.5% at the ratio of P(3IN=0.3)(3IN2F=0.5)(BDD=0.2):PM6=0.4:0.6. However, the more PM6 was introduced in place of P(3IN=0.3)(3IN2F=0.5)(BDD=0.2) by 0.6 or more, the lower the PCE. sc Due to the significant reduction in efficiency, a relatively low efficiency of 13.9% was achieved at PM6:BTP-eC9=1:1.2. To verify the highest cell efficiency, an external evaluation was conducted at the Nano Convergence Practical Application Center (NCPAC) in Daegu, South Korea, and a high PCE of 16.564% was confirmed, just as in the laboratory. Furthermore, the efficiency deviation within a single cell was less than 0.1%, and the average value of all four points within the element confirmed a high uniformity of 16.469% (see Figure 132).

[0105] [Table 5]

[0106] With the device structure designed as described above, GIWAXS measurements were performed to understand the crystallinity and orientation trends of the ternary organic solar cell devices. First, as shown in Figure 133, untreated thin films of P(3IN = 0.3)(3IN2F = 0.5)(BDD = 0.2) and PM6 were examined. P(3IN = 0.3)(3IN2F = 0.5)(BDD = 0.2) exhibited a predominantly face-on structure, while PM6 exhibited a predominantly edge-on structure, demonstrating contrasting crystallinity and orientation characteristics. As shown in Figure 134, the crystallinity and orientation of the blended films were observed depending on the ratio between the two donors, allowing us to understand the results of the optimized ternary organic solar cell devices. Gradually increasing the ratio of PM6 instead of P(3IN = 0.3)(3IN2F = 0.5)(BDD = 0.2) improved the edge-on crystallinity, and a balance between the face-on and edge-on structures was achieved at a ratio of 0.4:0.6. On the other hand, as with the device results, increasing the PM6 ratio above 0.6 resulted in excessive edge-on orientation, leading to the breakdown of the face-on structure. Using transmission electron microscopy (TEM), surface and elemental analysis was performed at the nanoscale for the ternary organic solar cell that showed the highest efficiency and compared it with PM6:BTP-eC9 (PCE = 16.9%) fabricated with CF. As shown in Figure 135, at the 100 nm scale, the ternary organic solar cell film exhibited more uniform and continuous thin-film properties than PM6:BTP-eC9. Expanding the analysis to the 10 nm scale revealed that PM6:BTP-eC9 formed very small, uniform domains that could overcome the exciton diffusion length of less than 10 nm. This indicates that the ternary organic solar cell also formed high-quality domains and had excellent thin-film properties. As shown in Figure 136, elemental analysis (F signal: P(3IN = 0.3) (3IN2F = 0.5) (BDD = 0.2) and PM6; N, Cl signal: BTP-eC9) was used to compare the donor-acceptor mixture distribution in more detail, and it was found that both films were dense and uniform, forming bi-continuous DA networks with smooth charge transfer. Based on the optimized device results, semitransparent organic solar cells based on P(3IN=0.3)(3IN2F=0.5)(BDD=0.2) and P(3IN=0.3)(3IN2F=0.5)(BDD=0.2):PM6 were designed. First, as shown in Figure 137, -5 UV-Vis measurements of each polymer at M concentration confirmed that P(3IN = 0.3)(3IN2F = 0.5)(BDD = 0.2) had higher transmittance than PM6 across the entire average visible light range (AVT; Joule 2019, 3, 1803-1809) from 380 to 780 nm. This is due to the significant difference in transmittance in the photopic response region, which is the most important region for eye color discrimination. In other words, when the absorbance coefficient of the solution was calculated as the average value according to the Beer-Lambert equation at 555 nm, PM6 had an absorbance of approximately 50,000, while P(3IN = 0.3)(3IN2F = 0.5)(BDD = 0.2) showed a relatively smaller absorbance of approximately 30,000. The lower absorbance in this region suggests greater application in transparent solar cells and increases the ability and probability of human identification through windows fabricated based on this material. As shown in Figure 138, a comparative analysis of the absorption coefficients of thin films applied to actual solar cells confirmed that they showed the same results as those of solutions. In fact, as shown in Figure 139, two polymer thin films were formed with the same thicknesses of 30, 50, 85, and 135 nm, and then a comparative analysis of their ability to distinguish rainbow-colored words was conducted. It was found that P(3IN=0.3)(3IN2F=0.5)(BDD=0.2) had better properties than PM6. In particular, at the same thickness of 135 nm, PM6 had difficulty distinguishing both words and colors, while P(3IN=0.3)(3IN2F=0.5)(BDD=0.2) was still able to distinguish both words and colors. Next, we used an ellipsometer to confirm the change in the optical polarization properties of the two polymers and measured their complex refractive indexes as a function of light wavelength. Based on this, we analyzed the optical electric field using optical simulation (Figure 140). From 300 to 500 nm, PM6 exhibited a slightly lower electric field than P(3IN = 0.3) (3IN2F = 0.5) (BDD = 0.2), demonstrating high transmittance in this region. However, from 500 to 700 nm, which includes the photopic response (maximum at 555 nm), it exhibited relatively high transmittance at the lowest electric field near 0.4, a trend consistent with the UV results. We confirmed that this trend persisted even when mixed with BTP-eC9. Simulations using the same stacked thicknesses as the optimized device structures for each polymer substrate also showed that P(3IN=0.3)(3IN2F=0.5)(BDD=0.2):BTP-eC9 had a lower electric field than PM6:BTP-eC9 in the 555 nm region, suggesting that it is indeed possible to fabricate transparent solar cell elements with high translucency. As shown in Figures 141 and 142, the absorbance and transmittance of the optimized ternary blend films based on P(3IN=0.3)(3IN2F=0.5)(BDD=0.2) were measured using UV-Vis. A clear trade-off relationship between absorbance and transmittance was confirmed. Based on this, the AVT was calculated based on the ratio of the two donors. The results for the P(3IN=0.3)(3IN2F=0.5)(BDD=0.2):PM6:BTP-eC9 blends were 62.0%, 60.9%, 59.4%, 56.6%, 53.7%, and 50.7% in increasing order of PM6 ratio. This confirmed that the PM6:BTP-eC9 blend phase had a relatively superior transmittance compared to its 47.6% transmittance. Based on the remarkable results of the ternary-based opaque organic solar cells and the advantages of their transparency, semitransparent organic solar cells were fabricated using the following conventional structure: ITO / PEDOT:PSS (30 nm) / P(3IN = 0.3) (3IN2F = 0.5) (BDD = 0.2):PM6:BTP-eC9 / PDINN (10 nm) / Ag (10 or 13 nm) / WO3 (25 nm). As a result, high-performance semitransparent organic solar cells with both high efficiency and high transmittance were obtained, as shown in Table 6. The JV and EQE waveforms of the optimized semitransparent organic solar cell devices are shown in Figures 143 and 144, and AVT calculations for these devices were performed using UV-Vis measurements, as shown in Figure 145. In summary, among the devices incorporating Ag (13 nm) / WO3 (25 nm) as the top transparent electrode, the P(3IN = 0.3)(3IN2F = 0.5)(BDD = 0.2):BTP-eC9 = 1:1.2 mixture showed the highest transmittance (AVT) of 35.1%, as previously mentioned. The P(3IN = 0.3)(3IN2F = 0.5)(BDD = 0.2):PM6:BTP-eC9 = 0.4:0.6:1.2 mixture showed the highest PCE (PCE) of 12.7%. The semi-transparent PM6:BTP-eC9 = 1:1.2 mixture showed a higher efficiency of 13.2%, but the AVT (AVT) was the lowest at 17.0%, due to the use of CF, a toxic solvent. The best light transmittance and efficiency were achieved by slightly thinning the Ag electrode and introducing Ag(10nm) / WO3(25nm). The PCE and AVT of P(3IN=0.3)(3IN2F=0.5)(BDD=0.2):BTP-eC9=1:1.2 were 9.8% and 40.7%, respectively, and the highest light utilization efficiency (LUE = PCE x AVT) was 3.99%. The PCE and AVT of P(3IN=0.3)(3IN2F=0.5)(BDD=0.2):PM6:BTP-eC9=0.4:0.6:1.2 were 11.6% and 32.4%, respectively, with an LUE of 3.76%, a significant increase of 0.61% over the device with Ag(13nm) / WO3(25nm).This suggests that if advanced transparent electrode technology is introduced instead of a metal / metal oxide combination, the highest LUE with a higher PCE and AVT can be achieved under the conditions of P(3IN = 0.3)(3IN2F = 0.5)(BDD = 0.2):PM6:BTP-eC9 = 0.4:0.6:1.2. Figure 146 shows an actual photo of the best semi-transparent device incorporating Ag (10 or 13 nm) / WO3 (25 nm). The photovoltaic performance and transmittance of this transparent organic solar cell are remarkable achievements worthy of being recognized as top research, even when compared with recent literature.

[0107] [Table 6]

[0108] Finally, to confirm the potential of building-integrated photovoltaics (BIPVs), an important application area for the future transparent solar cell market, as windows on building exteriors, a 15x15cm substrate with a P(3IN=0.3)(3IN2F=0.5)(BDD=0.2) was used. 2 A large-area opaque / semitransparent organic solar cell module of 1000nm was fabricated as a prototype and evaluated. Figure 147 shows an actual photograph of the fabricated opaque / semitransparent organic solar cell module. The opaque / semitransparent organic solar cell adopted an inverted structure due to the relative instability of the organic ETL when scaling up, which is the same as ITO / ZnO (20nm) / P (3IN = 0.3) (3IN2F = 0.5) (BDD = 0.2): BTP-eC9 = 1:1.2 / MoO3 (10nm) / Ag (15nm) / MoO3 (30nm). The fabricated opaque / semitransparent module showed an efficiency of less than 1% due to insufficient scaling up technology and equipment, but V ocIn the case of (1), it was confirmed that the propellers were formed relatively stably at 5-7V or above, and that they could rotate at high speed at 3-5V or above when irradiated with light. Figure 144 shows an actual photo of an opaque / semitransparent organic solar cell module. Looking at the technologies up to now, if advanced large-area technology is realized along with future top transparent electrode technology, it is expected that they will dominate not only the BIPV market, but also automotive-integrated photovoltaics (AIPV), Internet of Things (IoT) sensors, etc. As described above, in the present invention, the design, synthesis, and application methods of an efficient organic semiconductor for a 3-vinylene heterocyclic-based electron donor into which a highly planar electron withdrawer is introduced have been described in the above examples. However, there is no need to be limited thereto, and any manufacturing method that satisfies the above reaction scheme may be used. Furthermore, the organic solar cell element of the present invention may be manufactured in the order of anode / hole transport layer / photoelectric conversion layer / electron transport layer / cathode as described above, or may be manufactured in the reverse order, i.e., cathode / electron transport layer / photoelectric conversion layer / hole transport layer / anode. The present invention has been discussed above with a focus on preferred embodiments thereof. Those skilled in the art will recognize that the present invention can be embodied in various modified forms without departing from the essential characteristics of the present invention. Therefore, the disclosed embodiments should be considered from an illustrative rather than a restrictive perspective. The scope of the present invention is defined by the appended claims, rather than the foregoing description, and all variations within the scope of the claims should be construed as encompassed within the scope of the present invention.

Claims

1. A compound represented by the following chemical formula (1): 【Chemical 1】 In the chemical formula (1), Ligand is a reactive ligand, which may be the same or different, and each independently represents H, a halogen, or a pseudohalogen, wherein the halogen is selected from the group consisting of Cl, Br, and I, and the pseudohalogen is selected from the group consisting of OTf, OPO(OR) 2 ) and an acetoxy group; X and Y are the same or different and each independently represent a chalcogen, the chalcogen being selected from the group consisting of N, N—R, C, O, S, and Se; EWG is selected from the group consisting of the following structures: 【Chemistry 2】 In the above chemical formula, R and R 1 ~R 4 are the same or different and are each independently selected from the group consisting of hydrogen, a cyano group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted arylsulfoxy group, a substituted or unsubstituted boron group, a substituted or unsubstituted alkylamine group, a substituted or unsubstituted aralkylamine group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted heteroarylamine group, a substituted or unsubstituted aryl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted carbazole group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted thionyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted ester group, a substituted or unsubstituted aromatic group, and a substituted or unsubstituted μ-heterocyclic group containing one or more elements selected from the group consisting of N, O, S, and Se, or two adjacent substituents can form a fused ring.

2. The compound of claim 1, wherein the compound is selected from the following compounds: 【Chemistry 3】 In said compound, EWG is as defined in claim 1.

3. An organic semiconductor compound represented by the following chemical formula (2-1): 【Chemistry 4】 In the chemical formula (2-1), A is an electron acceptor unit which is a compound according to claim 1; n is an integer from 1 to 10,000; D is an electron donor selected from compounds having the following structure: 【Chemistry 5】 In the above structure, X and Y are the same or different and each independently represent a chalcogen, the chalcogen being selected from the group consisting of N, N—R, C, O, S, and Se; R's may be the same or different and are each independently selected from the group consisting of hydrogen, a cyano group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted arylsulfoxy group, a substituted or unsubstituted boron group, a substituted or unsubstituted alkylamine group, a substituted or unsubstituted aralkylamine group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted heteroarylamine group, a substituted or unsubstituted aryl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted carbazole group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted thionyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted ester group, a substituted or unsubstituted aromatic group, and a substituted or unsubstituted heterocyclic group containing one or more elements selected from the group consisting of N, O, S, and Se, or two adjacent substituents may form a fused ring.

4. The organic semiconductor compound according to claim 3, wherein the organic semiconductor compound is selected from compounds represented by the following chemical formulas (3-1) to (3-6): 【Chemistry 6】 In the chemical formulas (3-1) to (3-6), n is an integer from 1 to 10,000; R, X, Y and EWG are as defined in claim 1.

5. An organic semiconductor compound represented by the following chemical formula (4-1): 【Chemistry 7】 In the chemical formula (4-1), A is an electron acceptor unit which is a compound according to claim 1; n is an integer from 1 to 10,000; A' is an electron acceptor selected from compounds having the following structure: 【Chemistry 8】 In the above structure, X and Y are the same or different and each independently represent a chalcogen, the chalcogen being selected from the group consisting of N, N—R, C, O, S, and Se; R's may be the same or different and are each independently selected from the group consisting of hydrogen, a cyano group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted arylsulfoxy group, a substituted or unsubstituted boron group, a substituted or unsubstituted alkylamine group, a substituted or unsubstituted aralkylamine group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted heteroarylamine group, a substituted or unsubstituted aryl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted carbazole group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted thionyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted ester group, a substituted or unsubstituted aromatic group, and a substituted or unsubstituted heterocyclic group containing one or more elements selected from the group consisting of N, O, S, and Se, or two adjacent substituents may form a fused ring.

6. The organic semiconductor compound according to claim 5, wherein the organic semiconductor compound is selected from compounds represented by the following chemical formulas (5-1) to (5-8): 【Chemistry 9】 【change】 In the chemical formulas (5-1) to (5-8), n is an integer from 1 to 10,000; R, X, Y and EWG are as defined in claim 1.

7. An organic semiconductor compound selected from compounds represented by the following chemical formulas (6-1) to (6-5). 【Chemistry 10】 In the chemical formulas (6-1) to (6-5), D 1 , D 2 and D 3 are the same or different electron donors selected from compounds represented by the following structures: 【Chemistry 11】 A 1 , A 2 , and A 3 are the same or different, at least one of which is an electron acceptor unit that is the compound of claim 1, and the rest are relative electron acceptors selected from compounds represented by the following structures: 【Chemistry 12】 In the above structure, X and Y are the same or different and each independently represent a chalcogen, the chalcogen being selected from the group consisting of N, N—R, C, O, S, and Se; R are the same or different and are each independently selected from the group consisting of hydrogen, a cyano group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted arylsulfoxy group, a substituted or unsubstituted boron group, a substituted or unsubstituted alkylamine group, a substituted or unsubstituted aralkylamine group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted heteroarylamine group, a substituted or unsubstituted aryl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted carbazole group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted thionyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted ester group, a substituted or unsubstituted aromatic group, and a substituted or unsubstituted heterocyclic group containing one or more elements selected from the group consisting of N, O, S, and Se, or two adjacent substituents can form a fused ring; k is a mole fraction and is a real number in the range of 0≦k<1; l is a mole fraction and is a real number in the range 0≦l<1; m is a mole fraction and is a real number in the range of 0<m≦1; k+l+m=1, n is an integer from 1 to 10,000.

8. The organic semiconductor compound according to claim 7, wherein the organic semiconductor compound is selected from compounds represented by the following chemical formulas (7-1) to (7-5): 【Chemistry 13】 In the chemical formulas (7-1) to (7-5), k, l, m and n are as defined in claim 7; R, X, Y and EWG are as defined in claim 1.

9. An organic semiconductor compound selected from compounds represented by the following chemical formulas (8-1) to (8-4). 【Chemistry 14】 In the chemical formulas (8-1) to (8-4), A is an electron acceptor unit which is a compound according to claim 1; n is an integer from 1 to 10,000; A' is a relative electron acceptor selected from compounds having the following structure: 【Chemistry 15】 D is an electron donor selected from compounds having the following structure: 【Chemistry 16】 In the above structure, X and Y are the same or different and each independently represent a chalcogen, the chalcogen being selected from the group consisting of N, N—R, C, O, S, and Se; R's may be the same or different and are each independently selected from the group consisting of hydrogen, a cyano group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted arylsulfoxy group, a substituted or unsubstituted boron group, a substituted or unsubstituted alkylamine group, a substituted or unsubstituted aralkylamine group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted heteroarylamine group, a substituted or unsubstituted aryl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted carbazole group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted thionyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted ester group, a substituted or unsubstituted aromatic group, and a substituted or unsubstituted heterocyclic group containing one or more elements selected from the group consisting of N, O, S, and Se, or two adjacent substituents may form a fused ring.

10. The compound represented by the chemical formula (8-1) is selected from compounds having the following structure: 【Chemistry 17】 In the above structure, R 1 , R 2 , X, Y and EWG are as defined in claim 1.

11. The compound represented by the chemical formula (8-2) is selected from compounds having the following structure: 【Chemistry 18】 In the structure, l, m, and n are as defined in claim 7, and R 1 , R 2 , R 3 , X, Y and EWG are as defined in claim 1.

12. An organic solar cell comprising the organic semiconductor compound according to any one of claims 3 to 11.

13. An organic electronic device comprising the organic semiconductor compound according to any one of claims 3 to 11.

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