NOVEL ORGANIC SEMICONDUCTOR COMPOUND, PRODUCTION METHOD THEREOF, AND ORGANIC ELECTRONIC DEVICE USING THE SAME

Abstract

Provided are a novel organic semiconductor compound, a production method thereof, and an organic electronic device using the same, wherein the organic semiconductor compound includes a thiazolidine functional group introduced into a heteroaromatic ring to thereby remarkably improve photovoltaic characteristics of an organic electronic device including the same.

Claims

1. An organic semiconductor compound represented by Chemical Formula 1 below: ##STR00070## in Chemical Formula 1, Z.sub.1 and Z.sub.2 are each independently O, S, or Se; Y.sub.1 to Y.sub.4 are each independently O, S, Se or CR.sup.aR.sup.b, and R.sup.a and R.sup.b are each independently cyano, a carboxyl group, (C1-C20)alkyl, (C1-C20)alkoxy or (C1-C20)alkoxycarbonyl; R.sub.1 and R.sub.2 are each independently halogen, (C1-C20)alkyl, halo(C1-C20)alkyl, (C1-C20)alkoxy group, (C1-C20)alkylthio, (C1-C20)alkoxycarbonyl or (C6-C20)ar(C1-C20)alkyl; p and q are each independently 0 or an integer of 1 to 2, and when p and q are 2, R.sub.1 and R.sub.2 each may be the same as or different from each other; and R.sub.3 and R.sub.4 are each independently hydrogen or (C1-C20)alkyl.

2. The organic semiconductor compound of claim 1, wherein Z.sub.1 and Z.sub.2 are equally O, S, or Se; Y.sub.1 to Y.sub.4 are each independently O, S, or Se; R.sub.1 and R.sub.2 are each independently halogen, (C1-C20)alkyl, halo(C1-C20)alkyl or (C1-C20)alkoxycarbonyl; p and q are each independently 0 or an integer of 1 to 2, and when p and q are 2, R.sub.1 and R.sub.2 each may be the same as or different from each other; and R.sub.3 and R.sub.4 are each independently (C1-C20)alkyl.

3. The organic semiconductor compound of claim 1, wherein the organic semiconductor compound is represented by Chemical Formula 2 below: ##STR00071## in Chemical Formula 2, Z.sub.1 and Z.sub.2 are each independently O, S, or Se; R.sub.1 and R.sub.2 are each independently halogen, (C1-C20)alkyl, halo(C1-C20)alkyl or (C1-C20)alkoxycarbonyl; p and q are each independently 0 or an integer of 1 to 2, and when p and q are 2, R.sub.1 and R.sub.2 each may be the same as or different from each other; and R.sub.3 and R.sub.4 are each independently (C1-C20)alkyl.

4. The organic semiconductor compound of claim 3, wherein Z.sub.1 and Z.sub.2 are the same as each other, and are O, S, or Se.

5. The organic semiconductor compound of claim 3, wherein the organic semiconductor compound is selected from the following compounds: ##STR00072## ##STR00073## ##STR00074## ##STR00075## ##STR00076## ##STR00077## ##STR00078## ##STR00079## ##STR00080##

6. A production method of an organic semiconductor compound comprising: producing an organic semiconductor compound represented by Chemical Formula 1 below by reacting a dicarbaldehyde compound represented by Chemical Formula 3 below, a thiazolidine compound represented by Chemical Formula 4 below, and a thiazolidine compound represented by Chemical Formula 5 below: ##STR00081## in Chemical Formulas 1, 3 to 5, Z.sub.1 and Z.sub.2 are each independently O, S, or Se; Y.sub.1 to Y.sub.4 are each independently O, S, Se or CR.sup.aR.sup.b, and R.sup.a and R.sup.b are each independently cyano, a carboxyl group, (C1-C20)alkyl, (C1-C20)alkoxy or (C1-C20)alkoxycarbonyl; R.sub.1 and R.sub.2 are each independently halogen, (C1-C20)alkyl, halo(C1-C20)alkyl, (C1-C20)alkoxy, (C1-C20)alkylthio, (C1-C20)alkoxycarbonyl or (C6-C20)ar(C1-C20)alkyl; p and q are each independently 0 or an integer of 1 to 2, and when p and q are 2, R.sub.1 and R.sub.2 each may be the same as or different from each other; and R.sub.3 and R.sub.4 are each independently hydrogen or (C1-C20)alkyl.

7. An organic electronic device comprising the organic semiconductor compound of claim 1.

8. The organic electronic device of claim 7, wherein the organic electronic device is an organic solar cell.

9. The organic electronic device of claim 8, wherein the organic semiconductor compound is included in a photoactive layer of the organic solar cell.

10. The organic electronic device of claim 9, wherein the organic semiconductor compound is used as an electron acceptor.

Description

DETAILED DESCRIPTION OF EMBODIMENTS

[0040] The present disclosure provides a novel organic semiconductor compound that is useful as various photoelectric conversion materials, wherein the organic semiconductor compound is represented by Chemical Formula 1 below:

##STR00013##

[0041] in Chemical Formula 1,

[0042] Z.sub.1 and Z.sub.2 are each independently O, S, or Se;

[0043] Y.sub.1 to Y.sub.4 are each independently O, S, Se or CR.sup.aR.sup.b, and R.sup.a and R.sup.b are each independently cyano, a carboxyl group, (C1-C20)alkyl, (C1-C20)alkoxy or (C1-C20)alkoxycarbonyl;

[0044] R.sub.1 and R.sub.2 are each independently halogen, (C1-C20)alkyl, halo(C1-C20)alkyl, (C1-C20)alkoxy, (C1-C20)alkylthio, (C1-C20)alkoxycarbonyl or (C6-C20)ar(C1-C20)alkyl;

[0045] p and q are each independently 0 or an integer of 1 to 2, and when p and q are 2, R.sub.1 and R.sub.2 each may be the same as or different from each other; and

[0046] R.sub.3 and R.sub.4 are each independently hydrogen or (C1-C20)alkyl.

[0047] The organic semiconductor compound represented by Chemical Formula 1 of the present disclosure has a wide absorption spectrum in a panchromatic region, excellent light absorption, and a low lowest unoccupied molecular orbital energy level (LUMO) to be very efficiently usable as an electron acceptor by introducing a thiazolidine functional group into a heteroaryl central backbone, specifically, a 5-membered heteroaromatic ring.

[0048] Further, the organic semiconductor compound represented by Chemical Formula 1 of the present disclosure has a high crystallinity to have high charge mobility. In particular, the organic semiconductor compound is used as a compound for replacing a fullerene derivative according to the related art, thereby having high electron affinity while simultaneously having excellent miscibility with the electron donor to have high photoelectric conversion efficiency.

[0049] Preferably, in Chemical Formula 1 according to an exemplary embodiment of the present disclosure, Z.sub.1 and Z.sub.2 are equally O, S, or Se; Y.sub.1 to Y.sub.4 are each independently O, S or Se; R.sub.1 and R.sub.2 are each independently halogen, (C1-C20)alkyl, halo(C1-C20)alkyl or (C1-C20)alkoxycarbonyl; p and q are each independently 0 or an integer of 1 to 2, and when p and q are 2, R.sub.1 and R.sub.2 each may be the same as or different from each other; and R.sub.3 and R.sub.4 may be each independently (C1-C20)alkyl.

[0050] In order to obtain a more improved effect, Y.sub.1 and Y.sub.2 may be different from each other, and Y.sub.3 and Y.sub.4 may be different from each other, and more preferably, the organic semiconductor compound of the present disclosure may be represented by Chemical Formula 2 below:

##STR00014##

[0051] in Chemical Formula 2,

[0052] Z.sub.1 and Z.sub.2 are each independently O, S, or Se;

[0053] R.sub.1 and R.sub.2 are each independently halogen, (C1-C20)alkyl, halo(C1-C20)alkyl or (C1-C20)alkoxycarbonyl;

[0054] p and q are each independently 0 or an integer of 1 to 2, and when p and q are 2, R.sub.1 and R.sub.2 each may be the same as or different from each other; and

[0055] R.sub.3 and R.sub.4 are each independently (C1-C20)alkyl.

[0056] The organic semiconductor compound represented by Chemical Formula 2 has an absorption spectrum in a broader region by introducing a rhodanine functional group into the central backbone of two 5-membered heteroaromatic rings and has an excellent light absorption coefficient, and thus an organic electronic device obtained by employing the organic semiconductor compound has an extremely improved photoelectric conversion efficiency.

[0057] Preferably, in Chemical Formula 2 of the present disclosure, Z.sub.1 and Z.sub.2 may be equally O, S, or Se.

[0058] The organic semiconductor compound of the present disclosure may be selected from the following compounds, but is not limited thereto:

##STR00015## ##STR00016## ##STR00017## ##STR00018## ##STR00019## ##STR00020## ##STR00021## ##STR00022## ##STR00023##

[0059] Terms .sup.?alkyl.sub.?, .sup.?alkoxy.sub.?, and other substituents including .sup.?alkyl.sub.? part described in the present disclosure include all linear or branched forms.

[0060] Term: .sup.?aryl.sub.? described in the present disclosure is an organic radical derived from aromatic hydrocarbon by removal of one hydrogen, and includes a single ring system or a fused ring system including 4 to 7 ring atoms, preferably, 5 or 6 ring atoms in each ring, and even includes a form in which a plurality of aryls are connected by a single bond.

[0061] Arylalkyl described in the present disclosure means a substituent in which at least one hydrogen present on the alkyl is substituted with aryl.

[0062] Haloalkyl means a substituent in which at least one hydrogen present on the alkyl is substituted with halogen.

[0063] Further, the (C1-C20)alkyl group described in the present disclosure is preferably (C1-C15)alkyl, and more preferably (C1-C10)alkyl. The (C6-C20)aryl group is preferably (C6-C18)aryl, and more preferably (C6-C12)aryl. (C1-C20)alkoxy group is preferably (C1-C15)alkoxy, and more preferably (C1-C10)alkoxy. (C6-C20)aryl(C1-C20)alkyl group is preferably (C6-C18)aryl(C1-C15)alkyl, and more preferably (C6-C12)aryl(C1-C10)alkyl.

[0064] The organic semiconductor compound represented by Chemical Formula 1 according to the present disclosure may be produced by including: reacting a dicarbaldehyde compound represented by Chemical Formula 3 below, a thiazolidine compound represented by Chemical Formula 4 below, and a thiazolidine compound represented by Chemical Formula 5 below to produce the organic semiconductor compound represented by Chemical Formula 1:

##STR00024##

[0065] in Chemical Formulas 3 to 5,

[0066] Z.sub.1 and Z.sub.2 are each independently O, S, or Se;

[0067] Y.sub.1 to Y.sub.4 are each independently O, S, Se or CR.sup.aR.sup.b, and R.sup.a and R.sup.b are each independently cyano, a carboxyl group, (C1-C20)alkyl, (C1-C20)alkoxy or (C1-C20)alkoxycarbonyl;

[0068] R.sub.1 and R.sub.2 are each independently halogen, (C1-C20)alkyl group, a halo(C1-C20)alkyl, (C1-C20)alkoxy, (C1-C20)alkylthio, (C1-C20)alkoxycarbonyl or (C6-C20)ar(C1-C20)alkyl;

[0069] p and q are each independently 0 or an integer of 1 to 2, and when p and q are 2, R.sub.1 and R.sub.2 each may be the same as or different from each other; and

[0070] R.sub.3 and R.sub.4 are each independently hydrogen or (C1-C20)alkyl.

[0071] The organic semiconductor compound of the present disclosure is easy to be produced with a high purity and a high yield by a simple process to thereby have very high industrial applicability.

[0072] A solvent used in the production method of the present disclosure may be any conventional organic solvent, and may be preferably at least one selected from the group consisting of dichloromethane (DCM), dichloroethane (DCE), toluene, acetonitrile (MeCN), nitromethane, tetrahydrofuran (THF), N,N-dimethylformamide (DMF), and N,N-dimethylacetamide (DMA).

[0073] A reaction temperature is any temperature as long as it is a temperature used in general organic synthesis, but may vary according to a reaction time, a reaction material, and an amount of a starting material. After complete consumption of a starting material is confirmed by TLC, etc., the reaction is completed. When the reaction is completed, an extraction process is performed, then the solvent is distilled under reduced pressure, and a target material may be separated and purified by general methods such as column chromatography, and the like.

[0074] In addition, there is provided an organic electronic device including the organic semiconductor compound of the present disclosure.

[0075] The organic electronic device of the present disclosure may be any device as long as it is a device in which the organic semiconductor compound of the present disclosure is usable. For example, the organic electronic device may be an organic solar cell, an organic light emitting device, and an organic thin film transistor, and preferably, an organic solar cell. The organic semiconductor compound of the present disclosure may be included in a photoactive layer of the organic solar cell.

[0076] Preferably, the organic semiconductor compound of the present disclosure is an electron acceptor and is used as a compound for replacing a fullerene derivative that is conventionally used in the organic solar cell, and the organic solar cell in which the organic semiconductor compound is employed has improved photoelectric conversion efficiency.

[0077] Hereinafter, representative compounds of the present disclosure are described in detail through Examples and Comparative Examples for a detailed understanding of the present disclosure. Accordingly, the following Examples according to the present disclosure may be modified into various other forms, and the scope of the present disclosure should not be construed as being limited to Examples to be described below. These Examples of the present disclosure are provided to enable those skilled in the art to more fully understand the present disclosure.

[Example 1] Production of Small Molecular Organic Semiconductor Compound 1

[0078] ##STR00025##

[0079] Piperidine (0.1 mL) was added to a chlorobenzene (5 mL) solution in which (2,2-bithiophene)-5,5-dicarbaldehyde (0.0111 g, 0.05 mmol) and 3-octylrhodanine (0.061 g, 0.25 mmol) were dissolved, refluxed under argon atmosphere for 13 hours, and cooled to room temperature. When a reaction solution was dropped into methanol (20 mL), a precipitate was formed, the resulting precipitate was filtered, and dissolved again with a minimum amount of chloroform, and then precipitated again with methanol. The obtained product was separated by column chromatography, thereby obtaining an organic semiconductor compound 1.

[0080] .sup.1H-NMR (300 MHz, CDCl.sub.3): ? 7.82 (s, 2H), 7.38 (d, 2H), 7.35 (d, 2H) 4.11 (t, 4H) 1.71 (m, 4H) 1.30 (m, 20H), 0.88 (t, 6H).

[Example 2] Production of Small Molecular Organic Semiconductor Compound 2

[0081] ##STR00026##

[0082] Piperidine (0.1 mL) was added to a chlorobenzene (5 mL) solution in which 3-fluoro-(2,2-bithiophene)-5,5-dicarbaldehyde (0.012 g, 0.05 mmol) and 3-octylrhodanine (0.061 g, 0.25 mmol) were dissolved, refluxed under argon atmosphere for 13 hours, and cooled to room temperature. When a reaction solution was dropped into methanol (20 mL), a precipitate was formed, the resulting precipitate was filtered, and dissolved again with a minimum amount of chloroform, and then precipitated again with methanol. The obtained product was separated by column chromatography, thereby obtaining an organic semiconductor compound 2.

[0083] .sup.1H-NMR (300 MHz, CDCl.sub.3): ? 7.84 (s, 1H), 7.69 (s, 1H), 7.42 (s, 1H), 7.39 (s, 1H), 7.38 (s, 1H), 7.26 (s, 1H), 4.11 (t, 4H) 1.71 (m, 4H) 1.34 (m, 20H), 0.88 (t, 6H).

[Example 3] Production of Small Molecular Organic Semiconductor Compound 3

[0084] ##STR00027##

[0085] Piperidine (0.1 mL) was added to a chlorobenzene (5 mL) solution in which (2,2-biselenophene)-5,5-dicarbaldehyde (0.015 g, 0.05 mmol) and 3-octylrhodanine (0.061 g, 0.25 mmol) were dissolved, refluxed under argon atmosphere for 13 hours, and cooled to room temperature. When a reaction solution was dropped into methanol (20 mL), a precipitate was formed, the resulting precipitate was filtered, and dissolved again with a minimum amount of chloroform, and then precipitated again with methanol. The obtained product was separated by column chromatography, thereby obtaining an organic semiconductor compound 3.

[0086] .sup.1H-NMR (300 MHz, CDCl.sub.3): ? 7.82 (s, 2H), 7.35 (d, 2H), 7.32 (d, 2H) 4.11 (t, 4H) 1.71 (m, 4H) 1.30 (m, 20H), 0.88 (t, 6H)

Examples 4 to 44

[0087] Organic semiconductor compounds 4 to 44 were produced by using the production methods of Examples 1 to 3, and structures and 1H NMR of the produced organic semiconductor compounds are shown in Table 1 below.

TABLE-US-00001 TABLE 1 Structure of organic semiconductor .sup.1H NMR Example compound [300 MHz, CDCl.sub.3] 4 [00028] ? 7.89 (d, 2H), 7.86 (d, 2H), 7.42 (s, 2H), 4.11 (d, 4H), 1.92 (m, 2H), 1.55 (m, 4H), 1.31-1.25 (m, 8H), 1.19 (m, 4H), 0.88 (t, 12H) 5 [00029] ? 7.89 (d, 2H), 7.86 (d, 2H), 7.42 (s, 2H), 4.11 (d, 4H), 1.92 (m, 2H), 1.31- 1.25 (m, 32H), 0.88 (t, 12H) 6 [00030] ? 7.89 (d, 1H), 7.86 (d, 1H), 7.43 (d, 1H), 7.42 (s, 2H), 4.11 (d, 4H), 1.92 (m, 2H), 1.55 (m, 4H), 1.31-1.19 (m, 12H), 0.88 (t, 12H) 7 [00031] ? 7.89 (d, 1H), 7.86 (d, 1H), 7.43 (d, 1H), 7.42 (s, 2H), 4.11 (d, 4H), 1.92 (m, 2H), 1.31-1.19 (m, 32H), 0.88 (t, 12H) 8 [00032] ? 7.43 (s, 2H), 7.42 (s, 2H), 4.03 (d, 4H), 1.63 (m, 2H), 1.28-1.26 (m, 20H), 0.88 (t, 6H) 9 [00033] ? 7.43 (s, 2H), 7.42 (s, 2H), 4.03 (d, 4H), 1.92 (m, 2H), 1.55 (m, 2H), 1.31- 1.19 (m, 12H), 0.88 (t, 12H) 10 [00034] ? 7.43 (s, 2H), 7.42 (s, 2H), 4.03 (d, 4H), 1.92 (m, 2H), 1.31-1.19 (m, 28H), 0.88 (t, 12H) 11 [00035] ? 7.28 (s, 2H), 7.14 (s, 3H), 4.03 (d, 4H), 1.63 (m, 4H), 1.28-1.26 (m, 20H), 0.88 (t, 6H) 12 [00036] ? 7.28 (s, 2H), 7.14 (s, 2H), 4.03 (d, 4H), 1.63 (m, 4H), 1.28-1.26 (m, 20H), 0.88 (t, 6H) 13 [00037] ? 7.52 (d, 2H), 7.42 (d, 2H), 7.37 (s, 2H), 4.03 (d, 4H), 1.63 (m, 4H), 1.28- 1.26 (m, 20H), 0.88 (t, 6H) 14 [00038] ? 7.52 (d, 2H), 7.42 (d, 2H), 7.37 (s, 2H), 4.11 (d, 4H), 1.92 (m, 2H), 1.55 (m, 4H), 1.31-1.19 (m, 12H), 0.88 (t, 12H) 15 [00039] ? 7.52 (d, 2H), 7.42 (d, 2H), 7.37 (s, 2H), 4.11 (d, 4H), 1.92 (m, 2H), 1.31- 1.19 (m, 32H), 0.88 (t, 12H) 16 [00040] ? 7.28 (s, 2H), 7.14 (s, 4H), 4.11 (d, 4H), 1.92 (m, 2H), 1.55 (m, 4H), 1.31-1.19 (m, 12H), 0.88 (t, 12H) 17 [00041] ? 7.28 (d, 2H), 7.14 (s, 4H), 4.11 (d, 4H), 1.92 (m, 2H), 1.31-1.19 (m, 32H), 0.88 (t, 12H) 18 [00042] ? 7.56 (s, 2H), 7.42 (s, 2H), 4.07 (q, 4H), 2.68 (t, 4H), 1.50 (m, 4H), 1.30-1.20 (m, 18H), 0.88 (t, 6H) 19 [00043] ? 7.56 (s, 2H), 7.42 (s, 2H), 4.11 (d, 4H), 2.68 (t, 4H), 1.92 (m, 2H), 1.55-1.50 (m, 8H), 1.31-1.19 (m, 24H), 0.88 (t, 18H) 20 [00044] ? 7.56 (s, 2H), 7.42 (s, 2H), 4.11 (d, 4H), 2.68 (t, 4H), 1.92 (m, 2H), 1.50 (m, 4H), 1.31- 1.19 (m, 44H), 0.88 (t, 18H) 21 [00045] ? 7.52 (d, 2H), 7.42 (d, 2H), 7.37 (s, 2H), 4.03 (t, 4H), 1.63 (m, 4H), 1.28-1.26 (m, 28H), 0.88 (t, 6H) 22 [00046] [300 MHz, CHCl.sub.3]: ? 7.52 (d, 2H), 7.42 (d, 2H), 7.37 (s, 2H), 4.03 (t, 4H), 1.63 (m, 4H), 1.28- 1.26 (m, 36H), 0.88 (t, 6H) 23 [00047] ? 7.89-7.86 (m, 4H), 7.42 (s, 2H), 4.03 (t, 4H), 1.63 (m, 4H), 1.28-1.26 (m, 28H), 0.88 (t, 6H) 24 [00048] ? 7.89-7.86 (m, 4H), 7.42 (s, 2H), 4.03 (t, 4H), 1.63 (m, 4H), 1.28-1.26 (m, 36H), 0.88 (t, 6H) 25 [00049] ? 7.89-7.86 (m, 2H), 7.43 (d, 1H), 7.42 (s, 2H), 4.03 (t, 4H), 1.63 (m, 4H), 1.28-1.26 (m, 28H), 0.88 (t, 6H) 26 [00050] ? 7.89-7.86 (m, 2H), 7.43 (d, 1H), 7.42 (s, 2H), 4.03 (t, 4H), 1.63 (m, 4H), 1.28-1.26 (m, 36H), 0.88 (t, 6H) 27 [00051] ? 7.43 (s, 2H), 7.42 (s, 2H), 4.03 (t, 4H), 1.63 (m, 4H), 1.28-1.26 (m, 28H), 0.88 (t, 6H) 28 [00052] ? 7.43 (s, 2H), 7.42 (s, 2H), 4.03 (t, 4H), 1.63 (m, 4H), 1.28-1.26 (m, 36H), 0.88 (t, 6H) 29 [00053] ? 8.10 (s, 2H), 7.42 (s, 2H), 4.33 (t, 4H), 4.03 (t, 4H), 1.78 (m, 4H), 1.63 (m, 4H), 1.39-1.37 (m, 12H), 1.28-1.26 (m, 28H), 0.88 (t, 12H) 30 [00054] ? 8.10 (s, 2H), 7.42 (s, 2H), 4.33 (t, 4H), 4.03 (t, 4H), 1.78 (m, 4H), 1.63 (m, 4H), 1.39-1.37 (m, 12H), 1.28-1.26 (m, 36H), 0.88 (t, 12H) 31 [00055] ? 8.10 (s, 2H), 7.42 (s, 2H), 4.33 (t, 4H), 4.11 (t, 4H), 1.92 (m, 2H), 1.78 (m, 4H), 1.55 (m, 4H), 1.39-1.37 (m, 12H), 1.31-1.25 (m, 12H), 0.88 (t, 18H) 32 [00056] ? 8.10 (s, 2H), 7.42 (s, 2H), 4.33 (t, 4H), 4.11 (t, 4H), 1.92 (m, 2H), 1.78 (m, 4H), 1.55 (m, 4H), 1.39-1.37 (m, 12H), 1.31-1.25 (m, 12H), 0.88 (t, 18H) 33 [00057] ? 8.10 (s, 2H), 7.42 (s, 2H), 4.66 (d, 4H), 4.03 (t, 4H), 1.89 (m, 2H), 1.63 (m, 4H), 1.55 (m, 4H), 1.31-1.25 (m, 44H), 0.88 (t, 18H) 34 [00058] ? 8.10 (s, 2H), 7.42 (s, 2H), 4.66 (d, 4H), 4.11 (t, 4H), 1.92-1.89 (m, 4H), 1.55 (m, 8H), 1.31- 1.19 (m, 24H), 0.88 (t, 24H) 35 [00059] ? 7.37 (s, 2H), 6.94 (s, 2H), 4.07 (q, 4H), 2.63 (t, 4H), 1.59 (m, 4H), 1.30- 1.29 (m, 12H), 1.20 (t, 6H), 0.88 (t, 6H) 36 [00060] ? 7.37 (s, 2H), 6.94 (s, 2H), 4.03 (t, 4H), 2.63 (t, 4H), 1.63-1.59 (m, 8H), 1.30-1.26 (m, 32H), 0.88 (t, 12H) 37 [00061] ? 7.37 (s, 2H), 6.94 (s, 2H), 4.03 (t, 4H), 2.63 (t, 4H), 1.63-1.59 (m, 8H), 1.30-1.26 (m, 40H), 0.88 (t, 12H) 38 [00062] ? 7.37 (s, 2H), 6.94 (s, 2H), 4.03 (t, 4H), 2.63 (t, 4H), 1.63-1.59 (m, 8H), 1.30-1.26 (m, 48H), 0.88 (t, 12H) 39 [00063] ? 7.59 (s, 2H), 7.37 (s, 2H), 4.33 (t, 4H), 4.03 (t, 4H), 1.78 (m, 4H), 1.63 (m, 4H), 1.39-1.26 (m, 40H), 0.88 (t, 12H) 40 [00064] ? 7.59 (s, 2H), 7.37 (s, 2H), 4.33 (t, 4H), 4.03 (t, 4H), 1.78 (m, 4H), 1.63 (m, 4H), 1.39-1.26 (m, 48H), 0.88 (t, 12H) 41 [00065] ? 7.59 (s, 2H), 7.37 (s, 2H), 4.33 (t, 4H), 4.11 (t, 4H), 1.92 (m, 2H), 1.78 (m, 4H), 1.55 (m, 4H), 1.39-1.19 (m, 24H), 0.88 (t, 18H) 42 [00066] ? 7.59 (s, 2H), 7.37 (s, 2H), 4.66 (t, 4H), 4.03 (t, 4H), 1.89 (m, 2H), 1.63 (m, 4H), 1.55 (m, 4H), 1.39-1.19 (m, 40H), 0.88 (t, 18H) 43 [00067] ? 7.59 (s, 2H), 7.37 (s, 2H), 4.66 (t, 4H), 4.03 (t, 4H), 1.89 (m, 2H), 1.63 (m, 4H), 1.55 (m, 4H), 1.31-1.19 (m, 48H), 0.88 (t, 18H) 44 [00068] ? 7.59 (5, 2H), 7.37 (s, 2H), 4.66 (d, 4H), 4.11 (t, 4H), 1.92-1.89 (m, 4H), 1.55 (m, 8H), 1.31- 1.19 (m, 24H), 0.88 (t, 24H)

[Examples 45 to 64] Production of Organic Solar Cell Including Small Molecular Organic Semiconductor Compound

[0088] An organic substrate coated with indium tin oxide (ITO), which is a positive electrode transparent electrode (first electrode), was immersed in deionized water including a washing solution, washed in an ultrasonic cleaner for 15 minutes, and washed again with deionized water, acetone and IPA three times, and then dried in an oven at 130 for 5 hours. The cleaned ITO glass substrate was subjected to ultraviolet/ozone treatment for 15 minutes, and ZnO.NPs having a thickness of 30 nm was spin-coated on the ITO substrate. Further, the substrate coated with ZnO.NPs was heat treated on a hot plate at 100 for 10 minutes. In addition, in order to coat a photoactive layer, the device was then transferred to a glove box filled with argon. The photoactive layer was produced by applying an organic semiconductor solution on the ZnO layer at a thickness of 100 nm by a spin coating method, the organic semiconductor solution being obtained by dissolving the organic semiconductor compound of the present disclosure described in Table 2 below and PTB7-TH(Poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b;4,5-b]dithiophene-2,6-diyl-alt-(4-(2-ethylhexyl)-3-fluorothieno[3,4-b]thiophene-)-2-carboxylate-2-6-diyl)]) donor polymer in a chloroform solvent at a weight ratio of 1:1, followed by filtering using a 0.45 ?m (PTFE) syringe filter. On the photoactive layer of the obtained device structure, MoO.sub.3 having a thickness of 10 nm was deposited, and a 100 nm thick Ag electrode as a top electrode was deposited under 3?10.sup.?6 torr vacuum in a thermal evaporator to complete an organic solar cell.

[0089] Open cell voltage (Voc), short circuit current (Jsc), fill factor (FF) and power conversion efficiency (PCE) which are electrical characteristics of the produced organic solar cell are shown in Table 2 below.

[Comparative Examples 1 and 2] Production of Organic Solar Cell

[0090] ##STR00069##

[0091] An organic solar cell was produced by the same method as Example 45 except that the fullerene compound A having the above structure (Comparative Example 1) and a conventionally known non-fullerene-based compound ITIC (Comparative Example 2) were used instead of the organic semiconductor compound of the present disclosure, and electrical characteristics thereof are shown in Table 2 below.

TABLE-US-00002 TABLE 2 Organic Electron Voc Jsc FF PCE solar cell acceptor [V] [mA/cm.sup.2] [%] [%] Example 45 Example 1 1.05 14.70 59 9.02 Example 46 Example 2 1.07 13.20 59 8.33 Example 47 Example 3 1.01 15.10 57 8.69 Example 48 Example 4 1.00 14.50 58 8.41 Example 49 Example 5 1.00 14.30 57 8.15 Example 50 Example 6 1.02 14.54 58 8.60 Example 51 Example 7 1.01 14.21 57 8.18 Example 52 Example 9 1.01 14.20 57 8.17 Example 53 Example 11 1.02 14.80 58 8.76 Example 54 Example 12 1.03 14.60 57 8.57 Example 55 Example 13 1.04 14.20 56 8.27 Example 56 Example 14 1.02 14.00 56 8.00 Example 57 Example 16 0.99 14.80 58 8.50 Example 58 Example 17 1.00 14.70 57 8.38 Example 59 Example 18 1.03 14.10 57 8.28 Example 60 Example 21 1.04 14.07 55 8.05 Example 61 Example 23 1.02 14.10 57 8.03 Example 62 Example 24 1.02 14.07 56 8.04 Example 63 Example 25 1.05 14.23 57 8.52 Example 64 Example 26 1.04 14.19 56 8.26 Comparative Fullerene 0.80 16.13 57 7.35 Example 1 compound A Comparative ITIC 0.82 14.08 65 7.46 Example 2

[0092] As shown in Table 2, it may be appreciated that the organic semiconductor compound of the present disclosure in which the rhodanine functional group is introduced into the central backbone of two 5-membered heteroaromatic rings may be used as a compound for replacing a conventional fullerene derivative to thereby have high electron affinity while simultaneously having excellent miscibility with the electron acceptor, thereby having high photoelectric conversion efficiency.

[0093] In addition, it may be appreciated that the organic semiconductor compound of the present disclosure may have the electron affinity higher than that of the conventionally known non-fullerene-based compound ITIC, and simultaneously, may also be excellent in miscibility with the electron donor, and thus the organic semiconductor compound may have a high photoelectric conversion efficiency.

[0094] The organic semiconductor compound of the present disclosure has high light absorption and absorption spectrum in almost all wavelength (panchromatic) regions in a visible light region to thereby be usable as various organic semiconductor compounds and to be very useful as a photoelectric conversion material.

[0095] Further, the novel organic semiconductor compound of the present disclosure has a low lowest unoccupied molecular orbital energy level (LUMO) to be usable as an electron acceptor, thereby being very useful as a photoelectric conversion material.

[0096] Further, the novel organic semiconductor compound of the present disclosure may have high crystallinity to have high charge mobility, and thus the organic electronic device including the organic semiconductor compound may have high efficiency.

[0097] In addition, the novel organic semiconductor compound of the present disclosure is a small molecule and may be produced with a high purity and a high yield by a simple process to thereby have very high industrial applicability. In particular, the organic semiconductor compound of the present disclosure is used as the compound for replacing the fullerene derivative in an organic solar cell device using fullerene the electron acceptor according to the related art, thereby remarkably improving stability and efficiency of the organic solar cell to have very high utilization possibility as a non-fullerene-based electron acceptor.