Organic semiconductor compound and organic solar cell comprising same

Abstract

The present invention relates to an electron-acceptor organic semiconductor compound having low synthesis complexity, and an organic solar cell comprising same. The organic semiconductor compound significantly reduces synthesis complexity through simple structural modification of a Y6 derivative, which is well known as an excellent conventional electron-acceptor material, and thus can be mass-produced at low cost and maintains high planarity and an energy level similar to that of the Y6 derivative, and a ternary organic solar cell device to which same is applied has been identified to have high efficiency, thereby enabling effective use in related industries.

Description

Organic semiconductor compound and organic solar cell containing the same

[0001] The present invention relates to an electron acceptor organic semiconductor compound having low synthesis complexity and an organic solar cell comprising the same.

[0002] With the emergence of high oil prices and environmental pollution caused by the use of fossil fuels worldwide, the demand for sustainable, eco-friendly energy sources is rapidly increasing. Representative eco-friendly energy sources include solar, wind, hydroelectric, wave, and geothermal power; among these, solar cells, which generate electricity using sunlight, are attracting attention as an infinite source of electrical energy that is least constrained by location.

[0003] It is estimated that the amount of solar energy that can be practically extracted from the 1.7 × 10 TW of solar energy reaching the Earth's surface is 600 TW. If a photovoltaic power plant with 10% efficiency is utilized, approximately 60 TW of power can be supplied. Compared to the Earth's projected energy demand of 28 TW in 2050, this is a massive amount that is more than enough to satisfy future demands for sustainable energy sources.

[0004] Currently, first-generation crystalline silicon solar cells using inorganic materials account for 90% of the solar power generation market. However, because the cost of generating electricity is 5 to 20 times higher than that of fossil fuels, they are mainly used for long-term medium-to-large scale power generation, and their utility value is limited due to the problem of the finiteness of the materials.

[0005] As a result, second-generation film-type solar cell technologies (such as CdTe and CIGS) replacing silicon have rapidly emerged and occupy more than half of the remaining 10% market. However, second-generation solar cell technologies also require expensive equipment because some materials are classified as precious metals and semiconductor films are formed through vacuum and high-temperature processes during device fabrication.

[0006] Organic solar cells are a solar cell technology that can solve these problems. Because they utilize organic materials, mass production is possible through solution processes, which can lower the unit cost of solar cells. Furthermore, they are attracting attention as next-generation solar cells due to their mechanical flexibility, ease of design, and versatility, which offer limitless application possibilities in areas such as clothing and portable electrical and electronic products.

[0007] For the practical application of organic solar cells, the development of printable photoactive layer materials capable of realizing high efficiency, high stability, large area, and modularization is a critical prerequisite. Among these, achieving high efficiency in organic solar cells is by far the absolute necessity.

[0008] The development of highly soluble, high-performance (high-efficiency and high-stability) materials capable of low-temperature solution processing alone can drastically lower production costs and sequentially resolve technical problems.

[0009] Recently, organic solar cells are 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 world's highest efficiency for fullerene-based organic solar cells is 11.5%, certified by HKUST based on NREL (National Renewable Energy Laboratory) certification standards, while for non-fullerene-based organic solar cells, the world's highest efficiency is 19.2%, certified by SJTU, which is higher than that of fullerene-based cells.

[0010] While it took more than 15 years for fullerene-based organic solar cells to develop to their current level, it took less than 5 years for non-fullerene-based organic solar cells. In addition, non-fullerene types have been reported to be superior to fullerene types in terms of stability, leading to the rapid development of high-performance non-fullerene organic solar cells (Nature Communication, 2016, 7, 11585; Nature Materials, 2017, 16, 363-369).

[0011] For example, in the case of PCE11, a derivative that exhibits the world's highest efficiency in fullerene-based organic solar cells, burn-in occurs after 5 days of aging in the atmosphere, and efficiency decreases rapidly by about 39%. On the other hand, in the case of non-fullerene-based cells, efficiency did not decrease by even 15% after 5 days of aging.

[0012] Most recently, an efficiency of 20.2% was reported for a tandem organic solar cell device (https: / doi.org / 10.1016 / j.joule.2021.12.017), and an efficiency of nearly 21% is being reported for a single organic solar cell device (https: / doi.org / 10.1038 / s41563-025-02305-8). Despite having surpassed the efficiency of currently commercialized silicon solar cells, the field of organic solar cells has not yet been commercialized. This suggests that the standard for commercialization of organic solar cells cannot be based solely on the pursuit of higher efficiency. Therefore, it is now important to develop target-oriented materials from the perspective of maximizing the advantages of organic solar cells and focusing on end products and industries unique to organic solar cells (preferably for applications such as indoor power generation or transparent solar cells, rather than outdoor power generation where silicon and perovskite solar cells are strong in various aspects).

[0013] Accordingly, the inventors have completed the present invention by developing an organic semiconductor compound that can be mass-produced at low cost by significantly reducing synthesis complexity through a simple structural modification of a Y6 derivative, which is well known as an excellent electron acceptor material, while maintaining high planarity and similar energy levels and possessing high efficiency for ternary organic solar cell devices.

[0014] In order to achieve the above objective,

[0015] The present invention provides an organic semiconductor compound represented by the following chemical formula 1.

[0016] [Chemical Formula 1]

[0017]

[0018] In the above chemical formula 1,

[0019] A' is or And,

[0020] X are identical or different from each other, and each independently is O, S, Se, N, NR, CR, C-(R)2 or C=R, and

[0021] D is based on vinylene linkage, is identical or different from one another, and each independently or And,

[0022] The above D' is , , , , , or And,

[0023] Y are identical or different from each other, and each independently is O, S, Se, NR, C-(R)2 or C=R, and

[0024] A are identical or different from one another and are each independently electron withdrawing groups (EWG), said electron withdrawing groups are monomers substituted with one or more functional groups selected from nitro (-NO2), cyano (-CN), trifluoromethyl (-CF3), carboxyl (-COOH), carbonyl (-COR), ester (-COOR), sulfonic acid (-SO3H), amide (-CONH2), halogen (F, Cl, Br, I, etc.), or dicyano (-(CN)2) groups.

[0025] The above unit , , , , or And,

[0026] Z are identical or different from each other, and each independently O, S, NR, C-(R)2, C=R, OR, SR, N-(R)2, C-(R)3, CR=R, C=RR, or C≡R, and

[0027] The above A', D, and A are bonded to each other at arbitrary bonding sites, and

[0028] The above X, Y, and Z are arbitrarily selected from among elements satisfying the number of combinations, and

[0029] R is identical or different from one another, and each is independently absent, or H; O; S; Se; N; P; halogen group; alkyl group having 1 to 30 carbon atoms; aryl group having 6 to 60 carbon atoms; cycloalkyl group having 3 to 15 carbon atoms; alkenyl group having 2 to 30 carbon atoms; alkynyl group having 2 to 24 carbon atoms; alcohol having 1 to 30 carbon atoms; alkoxy group having 1 to 30 carbon atoms; alkylamino group having 1 to 30 carbon atoms; alkylthio group having 1 to 30 carbon atoms; alkylcyano group having 1 to 30 carbon atoms; alkylidenemalononitrile group having 1 to 30 carbon atoms; A heterocyclic ring having 5 to 60 carbon atoms containing one or more elements selected from the group consisting of N, O, S and Se, or two or more adjacent substituents may form a condensation ring.

[0030] In addition, the present invention provides an organic solar cell comprising the organic semiconductor compound.

[0031] In addition, the present invention provides an organic electronic device comprising the above organic semiconductor compound.

[0032] The organic semiconductor compound of the present invention enables low-cost mass production by significantly reducing synthesis complexity through a simple structural modification of the Y6 derivative, which is well known as an excellent electron acceptor material. It maintains high planarity and an energy level similar to that of the Y6 derivative, and high efficiency has been confirmed in ternary organic solar cell devices to which it is applied, making it useful for related industries.

[0033] Figure 1 shows the structural formula of the organic semiconductor compound of the present invention.

[0034] Figure 2 shows the potential energy according to the dihedral angle (θ) of the organic semiconductor compound of the present invention.

[0035] Figure 3 shows the LUMO and HOMO energy levels of the organic semiconductor compound of the present invention.

[0036] Figure 4 shows the ESP surface of the organic semiconductor compound of the present invention.

[0037] Figure 5 shows the ESP area distribution of the organic semiconductor compound of the present invention.

[0038] Figure 6 shows the DFT calculation of the organic semiconductor compound of the present invention.

[0039] Figure 7 shows the structural formula of the active material of the organic semiconductor compound of the present invention.

[0040] Figure 8 shows the absorption coefficient of the organic semiconductor compound of the present invention in a film state.

[0041] Figure 9 shows the absorption spectrum of the organic semiconductor compound of the present invention.

[0042] Figure 10 shows the energy band diagram of the active material in the film state of the organic semiconductor compound of the present invention.

[0043] Figure 11 shows the JV curve and EQE curve of the binary organic solar cell of the present invention.

[0044] Figure 12 shows the JV curve of the ternary organic solar cell PM6:L8-BO:M-Y6 of the present invention.

[0045] Figure 13 shows the EQE curve of the ternary organic solar cell PM6:L8-BO:M-Y6 of the present invention.

[0046] Figure 14 shows the absorption spectrum of the organic semiconductor compound of the present invention according to the solvent.

[0047] Figure 15 shows the JV curve of the ternary organic solar cell D18 / L8-BO:M-Y6 of the present invention.

[0048] Figure 16 shows the EQE curve of the ternary organic solar cell D18 / L8-BO:M-Y6 of the present invention.

[0049] Figure 17 shows the JV curve and EQE curve of the ternary organic solar cells D18 / L8-BO:4F and D18 / L8-BO:4Cl of the present invention.

[0050] Figure 18 shows the absorption spectra in a eutectic solvent of the ternary organic solar cells D18 / L8-BO:4F and D18 / L8-BO:4Cl of the present invention.

[0051] Figure 19 shows the absorption spectrum of the active layer of the present invention in a eutectic solvent.

[0052] FIG. 20 shows the JV curve and EQE curve of D18 / L8-BO:BT(BO)-vT(C12)-4F(CF + CS2) having the double layer HTL (PEDOT:PSS / Cl-2PACz) of the present invention.

[0053] FIG. 21 shows the certificate (TP-NC-25S-0199; Daegu Technopark Nanotechnology Process Center, Korea) of the optimal air-treated ternary organic solar cell (LBL) based on D18 / L8-BO:BT(BO)-vT(C12)-4F(CF + CS2) having a double-layer HTL (PEDOT:PSS / Cl-2PACz) of the present invention.

[0054] FIG. 22 shows the certificate (TP-NC-25S-0199; Daegu Technopark Nanotechnology Process Center, Korea) of the optimal air-treated ternary organic solar cell (LBL) based on D18 / L8-BO:BT(BO)-vT(C12)-4F(CF + CS2) having a double-layer HTL (PEDOT:PSS / Cl-2PACz) of the present invention.

[0055] FIG. 23 shows the 2D-GIWAXS pattern of a single / binary / ternary blend film based on the BHJ / LBL structure of the present invention.

[0056] FIG. 24 shows line-cut profiles extracted in the vertical (out-of-plane) and horizontal (in-plane) directions of the 2D-GIWAXS film of the present invention.

[0057] Figure 25 shows an AFM image of the binary blend film of the present invention.

[0058] Figure 26 shows an AFM image of the ternary blend film of the present invention.

[0059] Figure 27 shows an AFM 3D topography image of the ternary blend film of the present invention.

[0060] Figure 28 shows the phase image and HR-TEM image of the ternary blend film of the present invention.

[0061] Figure 29 shows the contact angle of the blend film of the present invention.

[0062] Figure 30 shows the DSC curve of the blend film of the present invention.

[0063] Figure 31 shows the output characteristics of the BT(BO)-vT(C12)-4F-based organic field-effect transistor (OFET) of the present invention.

[0064] FIG. 32 shows the transfer characteristics of the BT(BO)-vT(C12)-4F-based organic field-effect transistor (OFET) of the present invention.

[0065] Figure 33 shows the output characteristics of the BT(BO)-vT(C12)-4Cl-based organic field-effect transistor (OFET) of the present invention.

[0066] Figure 34 shows the transfer characteristics of the BT(BO)-vT(C12)-4Cl-based organic field-effect transistor (OFET) of the present invention.

[0067] Hereinafter, the present invention will be described in detail with reference to the attached drawings and embodiments thereof. However, the following embodiments are presented as examples of the present invention, and if it is determined that a detailed description of a technology or configuration well known to those skilled in the art may unnecessarily obscure the essence of the present invention, such detailed description may be omitted, and the present invention is not limited by this. The present invention is capable of various modifications and applications within the scope of the claims set forth below and the equivalent scope interpreted therefrom.

[0068] Furthermore, the terminology used in this specification is used to appropriately describe preferred embodiments of the present invention, and may vary depending on the intent of the user or operator, or the conventions of the field to which the present invention belongs. Accordingly, the definitions of these terms should be based on the content throughout this specification. Throughout the specification, when a part is described as "comprising" a certain component, unless specifically stated otherwise, this means that it may include additional components rather than excluding other components.

[0069] The terms used in the present invention are explained below.

[0070] Throughout the entire specification, the term “alkyl group” may each include a linear or branched C1-20, C1-10, or C1-8 alkyl group. For example, 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, ethylhexyl, butyloctyl, hexyldecyl, octyldodecyl, decyltetradecyl, etc. may be included, and all possible isomers thereof may be included, but are not limited thereto.

[0071] Throughout this specification, the term “aromatic ring” means comprising at least one aromatic ring and may include a C6-30 aromatic hydrocarbon ring group. For example, aromatic rings such as phenyl, naphthyl, biphenyl, terphenyl, fluorenyl, phenanthrenyl, triphenylenyl, perylenyl, chrysenyl, fluoranthenyl, benzofluorenyl, benzotriphenylenyl, benzochrysenyl, anthracenyl, stilbenyl, and pyrenyl may be included.

[0072] Throughout the entire specification, the term “halogen” means an element of Group 17 of the periodic table, including fluorine (F), chlorine (Cl), bromine (Br), iodine (I), etc.

[0073] Throughout the entire specification, the term “alkoxy” means an alkyl-oxygen radical having an alkyl group, and may include, for example, methoxy, ethoxy, propoxy, butoxy, pentoxy, etc.

[0074] Throughout this specification, the term "fusion" means that with respect to two or more rings, at least one pair of adjacent atoms are included in common in both rings.

[0075] Throughout this specification, the term “bonded ring” means a structure in which one or more aromatic rings or unsaturated hydrocarbon rings having 6 to 20 carbon atoms are fused.

[0076] The present invention provides an organic semiconductor compound represented by the following chemical formula 1.

[0077]

[0078] In the above chemical formula 1,

[0079] A' is or And,

[0080] X are identical or different from each other, and each independently is O, S, Se, N, NR, CR, C-(R)2 or C=R, and

[0081] D is based on vinylene linkage, is identical or different from one another, and each independently or And,

[0082] The above D' is , , , , , or And,

[0083] Y are identical or different from each other, and each independently is O, S, Se, NR, C-(R)2 or C=R, and

[0084] A are identical or different from one another and are each independently electron withdrawing groups (EWG), said electron withdrawing groups are monomers substituted with one or more functional groups selected from nitro (-NO2), cyano (-CN), trifluoromethyl (-CF3), carboxyl (-COOH), carbonyl (-COR), ester (-COOR), sulfonic acid (-SO3H), amide (-CONH2), halogen (-F, -Cl, -Br, -I), or dicyano (-(CN)2) groups.

[0085] The above unit , , , , or And,

[0086] Z are identical or different from each other, and each independently O, S, NR, C-(R)2, C=R, OR, SR, N-(R)2, C-(R)3, CR=R, C=RR, or C≡R, and

[0087] The above A', D, and A are bonded to each other at arbitrary bonding sites, and

[0088] The above X, Y, and Z are arbitrarily selected from among elements satisfying the number of combinations, and

[0089] R is identical or different from one another, and each is independently absent, or H; O; S; Se; N; P; halogen group; alkyl group having 1 to 30 carbon atoms; aryl group having 6 to 60 carbon atoms; cycloalkyl group having 3 to 15 carbon atoms; alkenyl group having 2 to 30 carbon atoms; alkynyl group having 2 to 24 carbon atoms; alcohol having 1 to 30 carbon atoms; alkoxy group having 1 to 30 carbon atoms; alkylamino group having 1 to 30 carbon atoms; alkylthio group having 1 to 30 carbon atoms; alkylcyano group having 1 to 30 carbon atoms; alkylidenemalononitrile group having 1 to 30 carbon atoms; A heterocyclic ring having 5 to 60 carbon atoms containing one or more elements selected from the group consisting of N, O, S and Se, or two or more adjacent substituents may form a condensation ring.

[0090] According to one embodiment of the present invention, A' may be selected from the group of compounds below, but is not limited thereto.

[0091]

[0092] In the structure of the above group of compounds,

[0093] R is identical or different from one another, and each is independently absent, or H; O; S; Se; N; P; halogen group; alkyl group having 1 to 30 carbon atoms; aryl group having 6 to 60 carbon atoms; cycloalkyl group having 3 to 15 carbon atoms; alkenyl group having 2 to 30 carbon atoms; alkynyl group having 2 to 24 carbon atoms; alcohol having 1 to 30 carbon atoms; alkoxy group having 1 to 30 carbon atoms; alkylamino group having 1 to 30 carbon atoms; alkylthio group having 1 to 30 carbon atoms; alkylcyano group having 1 to 30 carbon atoms; alkylidenemalononitrile group having 1 to 30 carbon atoms; A heterocyclic ring having 5 to 60 carbon atoms containing one or more elements selected from the group consisting of N, O, S and Se, or two or more adjacent substituents may form a condensation ring.

[0094] According to one embodiment of the present invention, D may be selected from the group of compounds below, but is not limited thereto.

[0095]

[0096] In the structure of the above group of compounds,

[0097] R, R1, and R2 are identical or different from each other, and each is independently absent, H; O; S; Se; N; P; halogen group; alkyl group having 1 to 30 carbon atoms; aryl group having 6 to 60 carbon atoms; cycloalkyl group having 3 to 15 carbon atoms; alkenyl group having 2 to 30 carbon atoms; alkynyl group having 2 to 24 carbon atoms; alcohol having 1 to 30 carbon atoms; alkoxy group having 1 to 30 carbon atoms; alkylamino group having 1 to 30 carbon atoms; alkylthio group having 1 to 30 carbon atoms; alkylcyano group having 1 to 30 carbon atoms; alkylidenemalononitrile group having 1 to 30 carbon atoms; A heterocyclic ring having 5 to 60 carbon atoms containing one or more elements selected from the group consisting of N, O, S and Se, or two or more adjacent substituents may form a condensation ring.

[0098] According to one embodiment of the present invention, A may be selected from the group of compounds below, but is not limited thereto.

[0099]

[0100] In the structure of the above group of compounds,

[0101] Y3 are identical or different from each other, and each is independently O, S, Se, NR, C-(R)2 or C=R, and

[0102] R, R1, and R2 are identical or different from each other, and each is independently absent, H; O; S; Se; N; P; halogen group; alkyl group having 1 to 30 carbon atoms; aryl group having 6 to 60 carbon atoms; cycloalkyl group having 3 to 15 carbon atoms; alkenyl group having 2 to 30 carbon atoms; alkynyl group having 2 to 24 carbon atoms; alcohol having 1 to 30 carbon atoms; alkoxy group having 1 to 30 carbon atoms; alkylamino group having 1 to 30 carbon atoms; alkylthio group having 1 to 30 carbon atoms; alkylcyano group having 1 to 30 carbon atoms; alkylidenemalononitrile group having 1 to 30 carbon atoms; A heterocyclic ring having 5 to 60 carbon atoms containing one or more elements selected from the group consisting of N, O, S and Se, or two or more adjacent substituents may form a condensation ring.

[0103] According to one embodiment of the present invention, the organic semiconductor compound may include one or more compounds selected from those represented by the following chemical formulas 2 and 3, but is not limited thereto.

[0104]

[0105]

[0106] In addition, the present invention provides an organic solar cell or an organic electronic device comprising the above organic semiconductor compound.

[0107] The above organic solar cell may comprise: a lower substrate capable of conducting electricity; an organic hole transport layer stacked on the lower substrate; a photoactive layer stacked on the hole transport layer and comprising an electron donor and an electron acceptor, wherein the electron acceptor is an organic semiconductor compound based on the novel unit 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.

[0108] The lower substrate is an ITO substrate, the hole transport layer comprises poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), etc., the photoactive layer comprises one selected from the group consisting of compounds represented by Chemical Formulas 1 to 3 and any combination thereof, the organic electron transport layer comprises 2,9-Bis[3-[[3- (dimethylamino)propyl]amino]propyl]-anthra[2,1,9-def:6,5,10-d'e'f']diisoquinoline-1,3,8,10(2H,9H)-tetrone (PDINN), N,N'-bis[3-(dimethylamino)propyl]perylene-3,4,9,10-tetracarboxylic diimide (PDIN), etc., and the electrode layer may comprise one or more selected from the group consisting of silver (Ag) and aluminum (Al).

[0109] Hereinafter, embodiments of the present invention will be described in more detail with reference to the attached drawings. However, the following embodiments are intended only to embody the content of the present invention and are not to limit the present invention.

[0110] <Example 1> Preparation of Organic Semiconductor Compound

[0111] The M-Y6 (Modified-Y6) series organic semiconductor compound of the AD-A'-DA structure of the present invention was prepared using the following reaction scheme 1.

[0112] [Reaction Equation 1]

[0113]

[0114] 1-1. Synthesis of Compound M1

[0115] A solution of 3-dodecylthiophene (4.65 g, 18.42 mmol) and anhydrous THF (63 mL) mixed under an inert gas was cooled to -78 °C, and n-BuLi (8.11 mL, 20.27 mmol) was added dropwise. After stirring for 30 minutes, 1-formylpiperidine (2.26 mL, 20.27 mmol) was added all at once and stirred at room temperature for 2 hours. The reaction mixture was poured into water (200 mL), and the organic layer was extracted three times with ethyl acetate (EA). The bound organic layer was washed with saline solution and dried with anhydrous MgSO4. The solvent was removed, and the remaining residue was purified by silica gel column chromatography (EA:Hxn=1:6) to obtain 4-dodecylthiophene-2-carbaldehyde (compound M1; 4.01 g, yield 77.6%, yellow oil).

[0116] 1 H NMR (CDCl3, 300 MHz): δ 9.88 (s, 1H), 7.61 (s, 1H), 7.38 (s, 1H), 2.66-2.62 (t, 2H), 1.63-1.61 (m, 2H), 1.31-1.26 (m, 18H), 0.98-0.86 (m, 3H).

[0117] 1-2. Synthesis of Compound M2

[0118] A solution of butylpotassium (t-BuOK, 4.34 g, 38.6 mmol), methyltriphenylphosphonium bromide (9.2 g, 25.8 mmol), and anhydrous THF (200 mL) was mixed under an inert gas, cooled to 0 °C, and stirred for 30 minutes. Then, compound M1 (3.59 g, 12.8 mmol) was added all at once and stirred for 24 hours. The reaction mixture was poured into water (200 mL), and the organic layer was extracted three times with ethyl acetate (EA). The combined organic layer was washed with saline solution and dried with anhydrous MgSO4. The solvent was removed, and the remaining residue was purified by silica gel column chromatography (EA:Hxn=1:6) to obtain 4-dodecyl-2-vinylthiophene (compound M2; 3.38 g, yield 94.8%, yellowish oil).

[0119] 1 H NMR (CDCl3, 300 MHz): δ 6.81-6.72 (m, 3H), 5.54-5.51 (d, 1H), 5.11-5.08 (d, 1H), 2.59-2.53 (t, 2H), 1.58 (m, 2H), 1.30-1.20 (m, 18H), 0.88 (m, 3H).

[0120] 1-3. Synthesis of Compound M3

[0121] 4,7-dibromo-5,6-bis((2-butyloctyl)oxy)benzo[c][1,2,5]thiadiazole (0.663 g, 1.0 mmol), compound M2 (0.668 g, 2.4 mmol), Pd(OAc)2 (0.014 g, 0.06 mmol), Pd(o-tolyl)3 (0.08 g, 0.133 mmol), anhydrous DMF (2.0 mL), and triethylamine (1.0 mL) were mixed in a microwave reaction vial and, after injecting argon gas several times under vacuum and sealing, reacted sequentially at 100 °C for 10 minutes, at 120 °C for 10 minutes, and at 140 °C for 5 hours. After cooling to room temperature and filtering, the mixture was washed three times with chloroform (CF). The solvent was removed and the remaining residue was purified by silica gel column chromatography (Hxn:DCM=4:1) to obtain 5,6-bis((2-butyloctyl)oxy)-4,7-bis((E)-2-(4-dodecylthiophen-2-yl)vinyl)benzo[c][1,2,5]thiadiazole (compound M3; 0.90 g, yield 85.1%, pale red solid).

[0122] 1 H NMR (CDCl3, 300 MHz): δ 8.60-8.56 (d, 2H), 7.51-7.47 (d, 2H), 7.07 (s, 2H), 6.85 (s, 2H), 3.94-3.93 (m, 4H), 2.61-2.57 (m, 4H), 1.93 (m, 2H), 1.56-1.21 (m, 64H), 0.94-0.80 (m, 18H).

[0123] 1-4. Synthesis of Compound M4

[0124] Compound M3 (0.22 g, 0.208 mmol), anhydrous dichloroethane (13.2 mL), anhydrous DMF (0.164 mL), and POCl3 (0.16 mL) were mixed in a microwave reaction vial at room temperature, sealed, and stirred at 80 °C for 6 hours under an inert gas. The mixture was cooled to room temperature and the reaction was stopped with a saturated aqueous solution of NaHCO3. The reaction mixture was poured into water (200 mL), and the organic layer was washed three times with chloroform (CF). The solvent was removed and the remaining residue was purified by silica gel column chromatography (Hxn:DCM=1:1) to obtain 5,5'-((1E,1'E)-(5,6-bis((2-butyloctyl)oxy)benzo[c][1,2,5]thiadiazole-4,7-diyl)bis(ethene-2,1-diyl))bis(3-dodecylthiophene-2-carbaldehyde) (compound M4; 0.20 g, yield 86.3%, red solid).

[0125] 1 H NMR (CDCl3, 300 MHz): δ 10.02 (s, 2H), 8.63-8.59 (d, 2H), 7.74-7.70 (d, 2H), 7.13 (s, 2H), 3.98-3.97 (m, 4H), 2.96-2.94 (m, 4H), 1.93 (m, 2H), 1.72-1.70 (m, 4H), 1.68-1.66 (m, 4H), 1.63-1.57 (m, 4H), 1.52-1.21 (m, 52H), 0.94-0.82 (m, 18H).

[0126] 1-5. Synthesis of BT(BO)-vT(C12)-4F

[0127] Materials with high scalability can be synthesized from the smallest divisible monomers or / and readily available starting materials (raw materials) as shown in Reaction Scheme 1-1 below. Compound M4 (106 mg, 0.095 mmol), 2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-1-ylidene)malononitrile (66 mg, 0.286 mmol), anhydrous chloroform (5.0 mL), anhydrous ethanol (0.5 mL), and L-proline (3.28 mg, 0.0594 mmol) were mixed in a microwave reaction vial and stirred vigorously at 25 °C for 12 hours under a sealed and inert gas atmosphere. The reaction mixture was filtered through a short silica filter and washed several times with a large amount of chloroform. The filtrate was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (Hxn:CF=1:9) to obtain 2,2'-((2Z,2'Z)-((((1E,1'E)-(5,6-bis((2-butyloctyl)oxy)benzo[c][1,2,5]thiadiazole-4,7-diyl)bis(ethene-2,1-diyl))bis(3-dodecylthiophene-5,2-diyl))bis(methanylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile (compound BT(BO)-vT(C12)-4F, hereinafter "4F"; 139 mg, yield 95.1%, dark blue solid).

[0128] [Reaction Equation 1-1]

[0129]

[0130] 1H NMR (CDCl3, 300 MHz): δ 8.95 (s, 2H), 8.64-8.59 (d, 2H), 8.54-8.50 (m, 2H), 7.87-7.83 (d, 2H), 7.67-7.64 (m, 2H), 4.08-4.07 (m, 4H), 2.97-2.94(m, 4H), 2.01(m, 2H), 1.70-1.66(m, 8H), 1.60-1.20(m, 66H), 0.95-0.83(m, 18H).

[0131] MALDI-TOF-MS for C 92 H 112 F4N6O4S3: [M+H] + m / z 계산값 1538.12; 실측값 1537.91

[0132] 1-6. BT(BO)-vT(C12)-4Cl 합성

[0133] Materials with high scalability can be synthesized from the smallest divisible monomers or / and readily available starting materials (raw materials) as shown in Reaction Scheme 1-2 below. M4 (220.0 mg, 0.198 mmol), 2-(5,6-dichloro-3-oxo-2,3-dihydro-1H-indene-1-ylidene)malononitrile (156.0 mg, 0.593 mmol), anhydrous chloroform (CF, 10.0 mL), anhydrous ethanol (EtOH, 1.0 mL), and L-proline (6.84 mg, 0.0594 mmol) were mixed in a microwave reaction vial and stirred vigorously at 25 °C for 12 hours under a sealed and inert gas atmosphere. The reaction mixture was filtered through a short silica filter and washed several times with a large amount of chloroform. The filtrate was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (Hxn:CF=1:9) to obtain 2,2'-((2Z,2'Z)-((((1E,1'E)-(5,6-bis((2-butyloctyl)oxy)benzo[c][1,2,5]thiadiazole-4,7-diyl)bis(ethene-2,1-diyl))bis(3-dodecylthiophene-5,2-diyl))bis(methanylylidene))bis(5,6-dichloro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile (compound BT(BO)-vT(C12)-4Cl, hereinafter "4Cl"; 300 mg, yield 94.7%, green solid).

[0134] [Reaction Equation 1-2]

[0135]

[0136] 1H NMR (CDCl3, 300 MHz): δ 8.87 (m, 2H), 8.68-8.67 (s, 2H), 8.43 (m, 2H), 7.84 (s, 2H), 7.64 (m, 2H), 4.12-4.11 (m, 4H), 2.92 (m, 4H), 2.07-2.04 (m, 2H), 1.69-1.21 (m, 74H), 1.03-0.83 (m, 18H).

[0137] MALDI-TOF-MS for C 92 H 112 Cl4N6O4S3: [M+H] + m / z Calculated value 1603.93; Measured value 1604.82

[0138] <Example 2> Density Functional Theory (DFT)

[0139] To analyze the molecular-level geometry and electronic properties of the M-Y6 series compounds M-Y6-MC1 and M-Y6-MC2, density functional theory (DFT) calculations were performed at the B3LYP / 6-31G(d) level. As a control, the reference Y6 type compound L8-BO was used (Fig. 1). For computational efficiency, the alkyl side chains were substituted with methyl, isobutyl, or butyl groups.

[0140] As a result, as shown in Figure 2, two energy minimums appeared at θ2 ≈ 0° and 180°, confirming that it is a thermodynamically accessible planar structure. The planar structure of the compound is stabilized by hydrogen bonding and vinylene bonding of intramolecular NH and OH, forming a C-type or U-type skeleton similar to a typical Y6-type structure.

[0141] In addition, as shown in Figure 3, the analysis of the optimized geometry confirmed that M-Y6-MC2 has an almost planar structure with a total θ = 7.52°. Compared to Y6-MC2, the backbone tilting angle of M-Y6-MC2 decreased from 15° to 10°, increasing stiffness, and the dipole moment increased from 0.08 D to 2.36 D, which can promote charge mobility in organic solar cells. Analysis of potential molecular orbitals revealed that the HOMO levels of M-Y6-MC2 and Y6-MC2 were similar at -5.555 eV and -5.585 eV, respectively; however, the LUMO levels were -3.659 eV and -3.524 eV, indicating that the band gap decreased due to increased electron delocalization in the thiadiazole portion of M-Y6-MC2.

[0142] Electrostatic surface characteristics were analyzed by generating an electrostatic potential (ESP) map on the van der Waals surface. As a result, as shown in Figures 4 and 5, both M-Y6-MC2 and Y6-MC2 exhibited localized electronegative regions around fluorine, carbonyl, and cyano groups; however, Y6-MC2 showed a more concentrated amount of ESP in the DA'D core, with an average positive ESP of 7.00 kcal / mol, compared to 5.17 kcal / mol for M-Y6-MC2. While the low average ESP of M-Y6-MC2 may reduce the formation of an interfacial electric field with the donor polymer, the broad distribution of positive ESP in the thiadiazole ring can enhance donor-acceptor charge separation through favorable π-π interactions. A similar trend was observed in M-Y6-MC2 (4Cl) containing tetrachloro-substituted IC terminals (Figure 6).

[0143] <Example 3> Photoelectric properties of an organic solar cell

[0144] 3-1. Binary Organic Solar Cell Devices

[0145] To analyze the photoelectric conversion characteristics of the M-Y6 series, organic solar cells were fabricated having a device structure of ITO / hole transport layer (PEDOT:PSS or PEDOT:PSS / Cl-2PACz) / photoactive layer / electron transport layer (PDINN or PDIN) / Ag, and organic solar cells composed of a binary (PM6:M-Y6) or ternary (PM6:L8-BO:M-Y6, D18 / L8-BO:M-Y6) mixture as the photoactive layer were fabricated (Fig. 7, Table 1 and Table 2).

[0146] PM6:BT(BO)-vT(C12)-4F (w / w)AdditiveV oc (V)J sc (mA / cm 2 )FF (%)PCE max (%)1:1-0.91019.566.411.81:1DIO (0.5 vol%)0.85819.767.611.41:1CN (0.5 vol%)0.87820.7270.312.81:2CN (0.5 vol%)0.85820.7569.412.41:2CN (0.25 vol%)0.87820.3368.812.31:1CN (0.75 vol%)0.85821.069.512.5

[0147] PM6:BT(BO)-vT(C12)-4Cl (w / w)AdditiveV oc (V)J sc (mA / cm 2 )FF (%)PCE max (%)1:1-0.89918.9164.911.01:1DIO (0.5 vol%)0.85819.1064.410.61:1CN (0.5 vol%)0.86819.4566.811.31:1CN (0.25 vol%)0.86819.3265.611.01:1CN (0.75 vol%)0.86819.1167.511.2

[0148] As a result, as shown in Fig. 8, the maximum absorption coefficient (ε) of the M-Y6 receptor in solution state max sol) was lower than L8-BO, but the absorption coefficient (ε in film state) max film ) is 4F (1.23×10 5 cm -1 ) and 4Cl (1.14 × 10⁻⁶ 5 cm -1 ) is L8-BO (1.39Х10 5 cm -1 It was confirmed that it was similar to ). Both M-Y6 acceptors exhibited characteristics of mixed J- and H-aggregation (J- / H-aggregation), with 4Cl showing H-aggregation and L8-BO showing J-aggregation (Fig. 9). In addition, the alignment of energy levels between the donor and acceptor formed a cascaded structure, promoting exciton separation and directional charge transport (Fig. 10). The power conversion efficiencies (PCE) of 4F and 4Cl in the binary organic solar cell PM6:M-Y6 were found to be 12.8% and 11.3%, respectively (Fig. 11). In particular, the open-circuit voltage (V) of the 4F-based device oc ) was 0.878 V, which was similar to the L8-BO-based device (0.874 V) (Table 4). Compared to 4F, the 4Cl-based device showed a lower short-circuit current density (J sc PCE decreased as it showed ) and filling rate (FF) (Table 3).

[0149] Photoactive layer V oc (V)J sc (mA / cm 2 )J cal (mA / cm 2 )FF (%)PCE max (%)PM6:L8-BO0.87124.3923.6479.616.9 (16.7±0.10)D18 / L8-BO0.88424.7223.9379.317.3 (17.1±0.13)

[0150] 3-2. Ternary Organic Solar Cell Devices

[0151] All ternary organic solar cell devices were fabricated and evaluated in ambient air, except for the top electrode. Based on an optimized ETL system, ternary organic solar cells (OSCs) with an M-Y6 acceptor introduced as a third component into a PM6:L8-BO bulk heterojunction (BHJ) structure were fabricated under ambient conditions (RH < 40%) (Tables 4 and 5). The optimal mixing ratio of PM6:L8-BO:4F and PM6:L8-BO:4Cl was determined to be 1.0:0.9:0.1.

[0152] PM6:L8-BO:BT(BO)-vT(C12)-4F (w / w)Annealing temperature (℃, time)V oc (V)J sc (mA / cm 2 )FF (%)PCE max (%)RH (%)1:1:0100 (10 min)0.87023.9979.716.6331:0.8:0.2100 (10 min)0.87624.5477.416.6331:0.9:0.1100 (10 min)0.86625.0778.717.2331:0.9:0.180 (10 min)0.87125.0979.017.3331:0.9:0.180 (10 min)0.87425.0578.917.3381:0.9:0.180 (5 min)0.87225.0379.717.4361:0.9:0.180 (5 min)0.87225.0179.917.4381:0.9:0.1100 (5 min)0.86925.2578.617.2381:0.9:0.180 (5 min)0.86724.8379.217.1381:1.0:0.180 (5 min)0.87325.1478.617.336

[0153] PM6:L8-BO:BT(BO)-vT(C12)-4Cl (w / w)Annealing temperature (℃, time)V oc (V)J sc (mA / cm 2 )FF (%)PCE max(%)RH (%)1:1:0100 (10 min)0.87023.9979.716.6331:0.8:0.2100 (10 min)0.83424.4876.815.7331:0.9:0.1100 (10 min)0.86724.6276.516.3331:0.9:0.180 (10 min)0.86924.5277.616.5331:0.9:0.180 (5 min)0.86924.2679.416.8361:1.0:0.180 (5 min)0.87024.2579.316.736

[0154] As a result, as shown in Fig. 12, the photoelectric conversion efficiencies (PCE) of the ternary PM6:L8-BO:4F and PM6:L8-BO:4Cl were 17.4% and 16.8%, respectively, confirming an increase compared to the binary PM6:L8-BO reference device (16.6%). In particular, a synergistic effect was observed in all photoelectric parameters upon the introduction of 4F, and the current density (J sc ) is 1.04 mA / cm 2 It increased to (Fig. 13). The optical properties of the M-Y6 acceptor were further analyzed using CF alone or a CF:CS2=8:2 (v / v) co-solvent. As a result, as shown in Fig. 14, the maximum absorption wavelength of the film was redshifted, and the optical bandgap (E g opt ) decreases, and the intensity ratio of 0-0 and 0-1 vibrational transitions (I 0-0 / I 0-1 ) increased. The photoelectric conversion efficiencies of PM6:L8-BO:4F and PM6:L8-BO:4Cl processed with CF:CS2 co-solvent were found to be 18.6% and 18.0%, respectively (Figs. 15 and 16).

[0155] In addition, D18 / L8-BO:4F and D18 / L8-BO:4Cl were prepared by introducing an M-Y6 acceptor as a third component into a ternary organic solar cell with a D18 / L8-BO-based LBL structure under atmospheric conditions of RH < 40% and setting the optimized blend ratio to 1.0:0.9:0.1 (Tables 6 and 7).

[0156] L8-BO:BT(BO)-v-T(C12)-4F (w / w)CF:CS2(v / v)V oc (V)J sc (mA / cm 2 )FF (%)PCE max (%)RH (%)1:0-0.88324.6178.317.0211:0-0.87925.0077.417.0368:2-0.88225.2080.217.8218:1-0.88925.2280.518.1219:1-0.89225.2280.818.2219:1-0.89125.5580.318.3219:1-0.89325.5880.218.33610:1-0.89525.3580.118.2219:17:30.89525.4080.618.3369:18:20.89325.7580.718.6369:19:10.89225.6980.718.536

[0157] L8-BO:BT(BO)-v-T(C12)-4Cl (w / w)CF:CS2(v / v)V oc (V)J sc (mA / cm 2 )FF (%)PCE max (%)RH (%)1:0-0.88424.7577.817.0288:2-0.88224.6678.417.1289:1-0.88724.5479.917.42810:1-0.89324.6378.917.4289:18:20.88725.3179.717.9399:18:20.89125.1880.418.0399:19:10.88324.9179.517.739

[0158] As a result, as shown in Fig. 17, the photoelectric conversion efficiencies of D18 / L8-BO:4F and D18 / L8-BO:4Cl were 18.3% and 17.4%, respectively, which increased compared to the control group (17.0%). The photoelectric conversion efficiencies of D18 / L8-BO:4F and D18 / L8-BO:4Cl processed in CF:CS2 eutectic solvent were found to be 18.6% and 18.0%, respectively (Figs. 18 and 19). To further improve the performance of 4F-based devices in CF:CS2 eutectic solvent, a bilayer HTL strategy combining PEDOT:PSS with various 2PACz derivatives was applied (Table 8).

[0159] Active layer (w / w)HTL1 (v / v)HTL2 (v / v)V oc (V)J sc (mA / cm 2 )FF (%)PCE max(%)RH (%)D18 / L8-BO:BT(BO)-v-T(C12)-4F= 1.0 / 0.9:0.1PEDOT:PSS:DI = 1:12PACz(0.28 mg / mL in EtOH)0.90125.7979.818.527PEDOT:PSS:DI = 1:1Cl-2PACz(0.34 mg / mL in EtOH)0.89226.1480.718.827PEDOT:PSS:DI = 1:1Br-2PACz(0.43 mg / mL in EtOH)0.89126.3579.518.727PEDOT:PSS:DI = 1:1Cl-2PACz(0.34 mg / mL in EtOH)0.90225.9579.118.544PEDOT:PSS:DI = 1:1Cl-2PACz(0.34 mg / mL in EtOH)0.90425.5981.518.944PEDOT:PSS:DI = 2:1Cl-2PACz(0.51 mg / mL in EtOH)0.89425.2381.818.548PEDOT:PSS:DI = 1:1Cl-2PACz(0.51 mg / mL in EtOH)0.89026.4981.219.233PEDOT:PSS:DI = 1:1Cl-2PACz(0.51 mg / mL in EtOH)0.89326.1480.718.848PEDOT:PSS:DI = 1:1Cl-2PACz(0.51 mg / mL in EtOH)0.89325.9381.618.958PEDOT:PSS:DI = 1:1Cl-2PACz(0.51 mg / mL in EtOH)0.90025.8080.118.665

[0160] As a result, the photoelectric conversion efficiencies of 2PACz, Cl-2PACz, and Br-2PACz-based devices prepared with an EtOH solution (1.0 mmol / L) under RH < 40% were 18.5%, 18.8%, and 18.7%, respectively, confirming that the Cl- and Br substitution derivatives exhibited excellent atmospheric processability and reproducibility due to improved thin film formation under atmospheric conditions. The photoelectric conversion efficiency at RH = 44% decreased slightly to 18.5%, but recovered to 18.9% by increasing the Cl-2PACz concentration. The photoelectric conversion efficiency at RH = 58% remained at 18.9%, and at RH = 65%, it exhibited improved storage stability compared to the PEDOT:PSS monolayer device. In particular, the photoelectric conversion efficiency of the Champion device fabricated under RH 33% conditions was 19.0% (maximum 19.2%), with Voc = 0.890 V and Jsc = 26.49 mA / cm². 2 and FF = 81.2% (Figs. 21 and 22), and the EQE responses of the donor and acceptor were 88% and 87%, respectively (Figs. 20 and Table 9).

[0161] Active layer (w / w)HTL1 (v / v)HTL2 (v / v)V oc (V)J sc (mA / cm 2 )FF (%)PCE max (%)RH (%)D18 / L8-BO:BT(BO)-vT(C12)-4F= 1.0 / 0.9:0.1PEDOT:PSS:DI = 1:1Cl-2PACz (0.51 mg / mL in EtOH)0.89625.9880.518.8330.88726.2980.618.80.89026.4981.219.20.88926.3181.1 19.00.88926.0980.818.80.88926.2680.918.90.89026.1480.418.70.88426.1680.218.5

[0162] Therefore, it was confirmed that the PEDOT:PSS / Cl-2PACz bilayer is very effective as a robust and scalable HTL for OSCs fabricated under atmospheric conditions (Table 10).

[0163] Active layer condition V oc (V)J sc (mA / cm 2 )J cal (mA / cm 2 )FF (%)PCE max(%)PM6:BT(BO)-vT(C12)-4FD1:A10.87820.7219.9470.312.8 (12.4±0.32)PM6:BT(BO)-vT(C12)-4ClD1:A10.86819.4518.8366.811.3 (10.8±0.44)PM6:L8-BOD1:A10.87023.9923.0479.716.6 (16.4±0.17)PM6:L8-BO:BT(BO)-vT(C12)-4FD1:A1:A20.87225.0124.4679.917.4 (17.1±0.28)PM6:L8-BO:BT(BO)-vT(C12)-4ClD1:A1:A20.86924.2623.6979.416.8 (16.5±0.29)D18 / L8-BOD1 / A10.88324.6123.6278.317.0 (16.8±0.18)D18 / L8-BO:BT(BO)-vT(C12)-4FD1 / A1:A20.89125.5524.5880.318.3 (18.0±0.20)D18 / L8-BO:BT(BO)-vT(C12)-4FD1 / A1:A20.89425.7524.6480.718.6 (18.2±0.23)D18 / L8-BO:BT(BO)-vT(C12)-4FD1 / A1:A20.89026.4925.2381.219.2 (18.8±0.19)D18 / L8-BO:BT(BO)-vT(C12)-4FD1 / A1:A20.88726.586-80.552 19.004D18 / L8-BO:BT(BO)-vT(C12)-4ClD1 / A1:A20.88724.5423.7379.917.4 (17.1±0.21)D18 / L8-BO:BT(BO)-vT(C12)-4ClD1 / A1:A20.89125.1823.9780.418.0 (17.7±0.24)

[0164] <실시예 4> 너서 정에 배하이 아이

[0165] To analyze the molecular arrangement and crystallinity of the photoactive layer material, two-dimensional broad-angle X-ray scattering (2D-GIWAXS) was measured. Scattering data were extracted as line-cut profiles along the vertical direction (out-of-plane, OOP; qz) and horizontal direction (in-plane, IP; qy), and (100) orientation characteristics were analyzed by measuring the azimuthal distribution of the scattering peaks.

[0166] As a result, as shown in Figs. 23 and 24, the pure donor polymers PM6 and D18 exhibited mainly edge-on orientations with Ayz / Az values ​​of 0.20 and 0.28, respectively, whereas L8-BO showed a π-π stacking peak (qz = 1.628 Å). -1 ) and lamellar peak (qz = 0.413 Å) -1 A distinct pattern was observed, and with an Ayz / Az value of 1.17, it was confirmed that the structure is face-on stacked, which is favorable for vertical charge transport. The pure M-Y6 films exhibited a dominant edge-on orientation, with Ayz / Az values ​​of 0.12 for 4F and 0.27 for 4Cl. In particular, BT(BO)-vT(C12)-4F displayed a long-range regular layered structure, with qz = 0.302, 0.597, and 0.890 Å. -1 A sharp diffraction peak appeared at.

[0167] In the PM6:M-Y6 binary blend film, strong diffraction was observed in both the OOP and IP directions, confirming mixed crystallinity. PM6:4F had d(010) = 3.75 Å and Ayz / Az = 1.26, exhibiting denser stacking and superior orientation compared to PM6:4Cl (4.01 Å, 0.53).

[0168] In PM6:L8-BO-based BHJ (bulk heterojunction) ternary blend films, the 4F-based ternary films have qz = 0.403 and 0.672 Å. -1A distinct OOP peak was observed, and d(100) and d(010) decreased to 15.59 Å and 3.89 Å, respectively, and Ayz / Az increased to 2.00, so compared to the control group (17.88 Å, 4.01 Å, Ayz / Az = 1.76), the introduction of M-Y6 improved the layering and π-π stacking.

[0169] In the optimized LBL (layered stacked) ternary film processed with CF:CS2=8:2 (v / v) cosolvent, the D18 / L8-BO:4F blend showed d(100) = 19.57 Å, CCL(100) = 63.54 Å, d(010) = 3.92 Å, CCL(010) = 33.86 Å and Ayz / Az = 1.20, and the 4Cl-based film showed 19.81 Å, 61.47 Å, 3.94 Å, 32.50 Å and Ayz / Az = 1.24, respectively. Both 4F and 4Cl-based films showed increased core molecular stacking and crystallinity compared to the control group (22.14 Å, 52.48 Å, 3.95 Å, 29.15 Å, Ayz / Az = 1.52). In particular, for the LBL-based ternary system containing BT(BO)-vT(C12)-4F, qz = 0.378, 0.408, 0.510, 0.627, and 0.661 Å. -1 An OOP diffraction peak appeared at.

[0170] <Example 5> Morphology

[0171] The surface and bulk morphology of the photoactive layer of the organic solar cell (OSC) were analyzed using atomic force microscopy (AFM). The photoactive layer was fabricated as binary and ternary blends by combining PM6 as a donor with respective acceptors (4F, 4Cl, L8-BO, M-Y6). All films were prepared by spin coating under the same process conditions as the optimized device. D18 / L8-BO-based layer-by-layer (LBL) films were prepared under the same solvent conditions (CF:CS2 = 8:2 v / v). Surface uniformity was evaluated by extracting root mean square (RMS) roughness from AFM height images, and domain distribution and phase separation in the binary and ternary blends were analyzed using phase images.

[0172] As a result, the PM6:4F blend exhibited a fine and uniform nanoscale structure and efficient phase separation with an RMS of 1.32 nm, whereas the PM6:4Cl blend showed relatively large domains and a rough surface with an RMS of 1.71 nm (Fig. 25). Compared to the PM6:L8-BO reference blend (RMS = 0.80 nm), the RMS of the PM6:L8-BO:4F and PM6:L8-BO:4Cl ternary blends increased to 0.91 nm and 0.94 nm, respectively. In particular, the 4F-based ternary blend formed a distinct nanofiber-like structure due to the highly crystalline BT(BO)-vT(C12)-4F, contributing to the enhancement of the charge transport pathway (percolation pathway) (Fig. 26).

[0173] The layered stacked (LBL) D18 / L8-BO film exhibited a clear fibrous network structure with an RMS of 0.90 nm, and the morphology became more refined upon the introduction of the M-Y6 receptor, while D18 / L8-BO:4F formed a uniform nanofiber network with an RMS of 0.95 nm. On the other hand, D18 / L8-BO:4Cl showed a non-optimal morphology with excessive phase separation and a low RMS (0.76 nm) (Figs. 27 and 28a-c).

[0174] The microstructure was observed using a high-resolution transmission electron microscope (HR-TEM). As a result, the reference LBL binary blend exhibited a smooth and uniform texture, and the 4F-based ternary blend formed a micro-nano scale wrinkled fiber structure, contributing to light trapping and improved short-circuit current density (Jsc); however, the 4Cl-based ternary blend showed an irregular fiber structure and large phase separation domains, which caused charge recombination and reduced device efficiency (Figs. 28d-f).

[0175] <Example 6> Physical Property Analysis

[0176] The contact angle of each photoactive layer was measured using water and diiodomethane (DIM). As a result, the water contact angles of M-Y6 receptors 4F and 4Cl were measured to be 106.49° and 103.43°, respectively, showing hydrophobicity compared to L8-BO (94.49°) (Fig. 29).

[0177] Thermal properties were analyzed using Differential Scanning Calorimetry (DSC). As a result, PM6 or D18 showed no thermal transition and were in an amorphous form, while the PM6:M-Y6 binary blend ΔH m This decreased sharply, with pure 4F and 4Cl being -39.3 J / g and -37.4 J / g, respectively, while PM6:4F and PM6:4Cl decreased to -11.0 J / g and -7.7 J / g, respectively. For both L8-BO:4F and L8-BO:4Cl blends, at a composition ratio of 0.9:0.1, the major melting transition (Tm / Hm) was 314 ℃ / -35.94 J / g and 314.6 ℃ / 34.16 J / g, and the secondary melting transition was 259.6 ℃ / -1.82 J / g and 258.1 ℃ / 1.26 J / g, confirming the alloying behavior (Fig. 30).

[0178] To investigate the cause of performance improvement in ternary organic solar cells (OSCs), organic field-effect transistors (OFETs) with a bottom-gate, bottom-contact (BGBC) structure were fabricated using pure M-Y6 acceptors and subjected to high-temperature heat treatment of over 150 °C. As a result, the saturation mobility (μ) of BT(BO)-vT(C12)-4F heat-treated at 200 °C was sat ) and critical voltage (V th ) is 2.0×10 -2 cm 2 / V·s and 18.1 V, and BT(BO)-vT(C12)-4Cl is 1.3×10 -2 cm 2 It was measured at / V·s and 20.5 V (Figs. 31 and 32). The control group L8-BO showed almost no OFET activity.

[0179] In the present invention, methods for designing, synthesizing, and applying an efficient organic semiconductor for a vinylene heterocycling-based electron donor with a highly planar electron attractor introduced through the above-described embodiments have been explained, but there is no need to specifically limit these methods, and any manufacturing method satisfying the above reaction equations is acceptable.

[0180] In addition, the organic solar cell device of the present invention may be manufactured in the order of an anode / hole transport layer / photovoltaic conversion layer / electron transport layer / cathode as described above, or it may be manufactured in the reverse order, that is, in the order of a cathode / electron transport layer / photovoltaic conversion layer / hole transport layer / anode.

[0181] As described above, specific embodiments of the present invention have been described in detail; however, those skilled in the art who understand the spirit of the present invention will be able to easily propose other inventions that are inferior or other embodiments included within the scope of the spirit of the present invention by adding, changing, or deleting other components within the same spirit. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive. The scope of the present invention is defined by the claims set forth below rather than by the detailed description above, and all modifications or variations derived from the meaning and scope of the claims and equivalent concepts should be interpreted as being included within the scope of the present invention.

Claims

1. Organic semiconductor compound represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, A' is or And, X are identical or different from each other, and each independently is O, S, Se, N, NR, CR, C-(R)2 or C=R, and D is based on vinylene linkage, is identical or different from one another, and each independently or And, The above D' is , , , , , or And, Y are identical or different from each other, and each independently is O, S, Se, NR, C-(R)2 or C=R, and A are identical or different from one another and are each independently electron withdrawing groups (EWG), said electron withdrawing groups are monomers substituted with one or more functional groups selected from nitro (-NO2), cyano (-CN), trifluoromethyl (-CF3), carboxyl (-COOH), carbonyl (-COR), ester (-COOR), sulfonic acid (-SO3H), amide (-CONH2), halogen (-F, -Cl, -Br, -I), or dicyano (-(CN)2) groups. Z are identical or different from each other, and each independently O, S, NR, C-(R)2, C=R, OR, SR, N-(R)2, C-(R)3, CR=R, C=RR, or C≡R, and The above A', D, and A are bonded to each other at arbitrary bonding sites, and The above X, Y, and Z are arbitrarily selected from among elements satisfying the number of combinations, and R is identical or different from one another, and each is independently absent, or H; O; S; Se; N; P; halogen group; alkyl group having 1 to 30 carbon atoms; aryl group having 6 to 60 carbon atoms; cycloalkyl group having 3 to 15 carbon atoms; alkenyl group having 2 to 30 carbon atoms; alkynyl group having 2 to 24 carbon atoms; alcohol having 1 to 30 carbon atoms; alkoxy group having 1 to 30 carbon atoms; alkylamino group having 1 to 30 carbon atoms; alkylthio group having 1 to 30 carbon atoms; alkylcyano group having 1 to 30 carbon atoms; alkylidenemalononitrile group having 1 to 30 carbon atoms; A heterocyclic ring having 5 to 60 carbon atoms containing one or more elements selected from the group consisting of N, O, S and Se, or two or more adjacent substituents may form a condensation ring.

2. In Paragraph 1, The above A' is an organic semiconductor compound selected from the group of compounds below. In the structure of the above group of compounds, R is identical or different from one another, and each is independently absent, or H; O; S; Se; N; P; halogen group; alkyl group having 1 to 30 carbon atoms; aryl group having 6 to 60 carbon atoms; cycloalkyl group having 3 to 15 carbon atoms; alkenyl group having 2 to 30 carbon atoms; alkynyl group having 2 to 24 carbon atoms; alcohol having 1 to 30 carbon atoms; alkoxy group having 1 to 30 carbon atoms; alkylamino group having 1 to 30 carbon atoms; alkylthio group having 1 to 30 carbon atoms; alkylcyano group having 1 to 30 carbon atoms; alkylidenemalononitrile group having 1 to 30 carbon atoms; A heterocyclic ring having 5 to 60 carbon atoms containing one or more elements selected from the group consisting of N, O, S and Se, or two or more adjacent substituents may form a condensation ring.

3. In Paragraph 1, The above D is an organic semiconductor compound selected from the group of compounds below. In the structure of the above group of compounds, R, R1, and R2 are identical or different from each other, and each is independently absent, H; O; S; Se; N; P; halogen group; alkyl group having 1 to 30 carbon atoms; aryl group having 6 to 60 carbon atoms; cycloalkyl group having 3 to 15 carbon atoms; alkenyl group having 2 to 30 carbon atoms; alkynyl group having 2 to 24 carbon atoms; alcohol having 1 to 30 carbon atoms; alkoxy group having 1 to 30 carbon atoms; alkylamino group having 1 to 30 carbon atoms; alkylthio group having 1 to 30 carbon atoms; alkylcyano group having 1 to 30 carbon atoms; alkylidenemalononitrile group having 1 to 30 carbon atoms; A heterocyclic ring having 5 to 60 carbon atoms containing one or more elements selected from the group consisting of N, O, S and Se, or two or more adjacent substituents may form a condensation ring.

4. In Paragraph 1, The above unit , , , , or Organic semiconductor compound that is.

5. In Paragraph 4, The above monomer is an organic semiconductor compound selected from the group of compounds below. In the structure of the above group of compounds, Y3 are identical or different from each other, and each is independently O, S, Se, NR, C-(R)2 or C=R, and R, R1, and R2 are identical or different from each other, and each is independently absent, H; O; S; Se; N; P; halogen group; alkyl group having 1 to 30 carbon atoms; aryl group having 6 to 60 carbon atoms; cycloalkyl group having 3 to 15 carbon atoms; alkenyl group having 2 to 30 carbon atoms; alkynyl group having 2 to 24 carbon atoms; alcohol having 1 to 30 carbon atoms; alkoxy group having 1 to 30 carbon atoms; alkylamino group having 1 to 30 carbon atoms; alkylthio group having 1 to 30 carbon atoms; alkylcyano group having 1 to 30 carbon atoms; alkylidenemalononitrile group having 1 to 30 carbon atoms; A heterocyclic ring having 5 to 60 carbon atoms containing one or more elements selected from the group consisting of N, O, S and Se, or two or more adjacent substituents may form a condensation ring.

6. In Paragraph 1, The above organic semiconductor compound comprises one or more compounds selected from the compounds represented by the following chemical formulas 2 and 3: [Chemical Formula 2] [Chemical Formula 3] 7. An organic solar cell comprising an organic semiconductor compound according to any one of paragraphs 1 to 6.

8. An organic electronic device comprising an organic semiconductor compound according to any one of paragraphs 1 to 6.

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