Non-fullerene acceptor compound containing benzoselenadiazole, and organic optoelectronic device containing the same

Abstract

To provide a non-fullerene acceptor compound containing benzoselenadiazole excellent in the light absorption wavelength region and the photoelectric conversion efficiency, and organic optoelectronic devices such as an OPD or OPV comprising the same.SOLUTION: A non-fullerene acceptor compound containing benzoselenadiazole has the structure in the figure, where Ar1 is a five-membered heterocyclic ring; Ar2 is a monocyclic or polycyclic C5-C20 heteroaromatic derivative; π is a monocyclic or polycyclic C5-C20 heteroaromatic derivative; m=0 to 5; and EG is a monocyclic or polycyclic derivative containing a ketone group and electron-withdrawing group.SELECTED DRAWING: Figure 8

Description

Technical Field

[0001] The present invention relates to a compound, and particularly to a non-fullerene acceptor compound containing benzoselenadiazole and an organic optoelectronic device including the same.

Background Art

[0002] In recent years, in order to manufacture electronic devices with higher versatility and lower cost, the demand for organic semiconducting compounds (OSCs) has been increasing day by day. The reason for this phenomenon is that compared with conventional semiconductor materials, organic semiconducting compounds have a wider light absorption range, a larger light absorption coefficient, and a tunable structure, and any of their light absorption range, energy level, and solubility can be adjusted according to the target and demand. In addition, since organic materials have advantages such as low cost, flexibility, low toxicity, and the ability to be produced in large areas in the manufacture of devices, they have enhanced competitiveness in various fields of organic optoelectronic materials. Such compounds have a very wide range of applications and are included in various devices or devices such as organic field-effect transistors (OFETs), organic light-emitting diodes (OLEDs), organic photodetectors (OPDs), organic photovoltaic (OPV) cells, sensors, memory elements, and logic circuits. It should be noted that organic semiconductor materials usually exist in the form of a thin layer with a thickness of about 50 nm to 1 μm in each of the above devices or devices to which they are applied.

[0003] Organic photodetectors (OPDs) are emerging technologies in recent years in the field of organic optoelectronics. Such devices have different requirements for their materials according to demand. Benefiting from the development of modern materials science and technology, OPDs can be fabricated as thin layers, and the spectral range of the light they absorb extends from ultraviolet (UV) to near-infrared (NIR), and absorption in a specific wavelength range is also possible. For example, in the case of biological identification, infrared-absorbing materials are required to avoid interference with visible light. Also, among current commercially available products, some have a wavelength range of absorbed light of 850 nm or 940 nm depending on the light source.

[0004] In addition, the material of the active layer included in the organic photodetector plays an important role because it directly affects the function of the device. The material can be divided into two parts: a donor and an acceptor. Commonly seen materials for donor materials include organic polymers, organic oligomers, or limited molecular units. Currently, the development of D-A type conjugated polymers is the mainstream. By utilizing the electron-donating and electron-withdrawing effects formed by the interaction between the electron-donating unit and the electron-deficient unit (electron-deficient unit) in the polymer, the energy level and bandgap of the polymer can be tuned. And the acceptor material combined with the D-A type conjugated polymer is usually a high-conductivity fullerene derivative with an absorption range of about 400 - 600 nm. Also, the fullerene derivative may include graphene, metal oxide, or quantum dots, etc. However, due to the difficulty of tuning from its structure and the limited range of absorption wavelength and energy level, overall, the combination of donor material and acceptor material is limited. Although the demand for materials in the near-infrared region is gradually increasing due to market changes, even if the absorption range of the conjugated polymer serving as the donor material can be tuned to the near-infrared region, those that can be suitably combined with fullerene-based acceptors are limited. Therefore, the development of non-fullerene-based acceptor compounds to replace conventional fullerene-based acceptors is very important in solving the problems of active layer materials. SUMMARY OF THE INVENTION

Problems to be Solved by the Invention

[0005] However, non-fullerene acceptor compounds have been difficult to develop initially and it has not been easy to control the form of the compounds, so the energy conversion rate has been low. However, since 2015, due to numerous studies on non-fullerene acceptors, the PCE of non-fullerene acceptor compounds has been remarkably improved to have sufficient competitiveness to compete. Such changes are mainly due to the progress of synthesis methods, the improvement of material design strategies, etc. Also, donor materials that have been widely developed for fullerene-type acceptors have also indirectly contributed to the research on non-fullerene acceptor compounds.

[0006] The research on non-fullerene acceptor compound materials mainly concerns molecules with an A-D-A structure mode formed by an electron-donating center and electron-deficient units on both sides thereof. Here, D is usually a molecule composed of a benzene ring and thiophene, and A is usually an IC derivative. Also, in another structure mode of A’-D-A-D-A’, a sulfur atom-containing molecule is often used as the central electron-deficient unit to enhance its efficacy.

[0007] As described above, the non-fullerene acceptor compound materials in this field have overcome the initial development stage and the bottleneck stage and are currently in the development stage, but there are still many room for improvement or solution in terms of material selectivity or performance improvement. Therefore, how to improve existing non-fullerene acceptor compounds and realize excellent material properties such as a narrower bandgap, more suitable electrical characteristics, and photoelectric conversion efficiency is indeed a problem that those skilled in the art should solve.

Means for Solving the Problems

[0008] An object of the present invention is to provide a non-fullerene acceptor compound having a narrower bandgap and realizing reduction of leakage current and improvement of photoelectric conversion efficiency when applied to OPD and OPV devices.

[0009] In order to achieve the above object, the present invention provides a non-fullerene acceptor compound containing benzoselenadiazole, as shown in the following formula:

[0010] [ka]

[0011] (In the formula, Ar 1 is a heterocyclic five-membered ring, and Ar 2 is a C5-C20 monocyclic or polycyclic heteroaromatic derivative, π is a C5-C20 monocyclic or polycyclic heteroaromatic derivative, m=0-5, and EG is a monocyclic or polycyclic derivative containing a ketone group and an electron-withdrawing group. In one embodiment of the present invention, Ar 1 teeth,

[0012] [ka]

[0013] At least one selected from the group consisting of The substituent R in the formula 1 is at least one selected from the group consisting of a C1 to C30 linear alkyl group, a branched alkyl group, a silane group, an ester group, an alkoxy group, an alkylthio group, a halogenated alkyl group, an alkenyl- or alkynyl-containing alkyl group, a cyano group, a nitro group, a hydroxyl or ketone group-containing or substituted alkyl group, and a halogen.

[0014] In one embodiment of the present invention, Ar 2 teeth,

[0015] [ka]

[0016] At least one selected from the group consisting of Substituent R in the formula 2 is at least one selected from the group consisting of a linear alkyl group having 1 to 30 carbon atoms, a branched alkyl group, a silane group, an ester group, an alkoxy group, an alkylthio group, a halogenated alkyl group, an alkenyl-containing or alkynyl-containing alkyl group, a cyano group, a nitro group, a hydroxy group or a ketone group-containing or substituted alkyl group, a halogen, and R 1 substituted benzene ring, hetero five-membered ring and hetero six-membered ring

[0017] In one embodiment provided by the present invention, π is

[0018]

Chemical formula

[0019] at least one selected from the group consisting of Substituent R in the formula 1 is at least one selected from the group consisting of a linear alkyl group having 1 to 30 carbon atoms, a branched alkyl group, a silane group, an ester group, an alkoxy group, an alkylthio group, a halogenated alkyl group, an alkenyl-containing or alkynyl-containing alkyl group, a cyano group, a nitro group, a hydroxy group or a ketone group-containing or substituted alkyl group, and a halogen

[0020] In one embodiment provided by the present invention, EG is

[0021]

Chemical formula

[0022] at least one selected from the group consisting of Substituent R in the formula 3 is at least one selected from the group consisting of a hydrogen atom, a halogen, an alkyl group having 1 to 20 carbon atoms, an oxyalkyl group having 1 to 20 carbon atoms, a carbonyl group, an ester group, and a cyano group

[0023] Another object of the present invention is an organic optoelectronic device including a non-fullerene acceptor compound containing benzoselenadiazole according to the present invention, which includes a substrate, a lower electrode provided on the substrate, an upper electrode provided opposite to the lower electrode, and an intermediate layer provided between the lower electrode and the upper electrode. The intermediate layer includes a first carrier transport layer, an active layer, and a second carrier transport layer. The active layer is provided between the first carrier transport layer and the second carrier transport layer and contains a non-fullerene acceptor compound containing benzoselenadiazole according to the present invention. It is to provide an organic optoelectronic device.

[0024] In one embodiment provided by the present invention, the first carrier transport layer is located on the second carrier transport layer.

[0025] In one embodiment provided by the present invention, the second carrier transport layer is located on the active layer.

[0026] In one embodiment provided by the present invention, the first carrier transport layer contains molybdenum oxide (MoO3) or PEDOT:PSS.

[0027] In one embodiment provided by the present invention, the second carrier transport layer contains zinc oxide (ZnO) or PFNBr.

Advantages of the Invention

[0028] As a result of measuring the properties, compared with conventional acceptors, the present invention has an improved HOMO value, maintains a certain LUMO value, and the band gap is reduced so that a red shift effect in the light absorption of the material can be obtained. In addition, the non-fullerene acceptor compound containing benzoselenadiazole according to the present invention shows good leakage prevention performance when applied to OPD, and the applicable range in the optical spectrum reaches 940 nm and has a high external quantum efficiency (EQE). Further, when applied to OPV, it shows a similarly good effect in terms of photoelectric conversion efficiency and the like by combination with a P-type polymer.

Brief Description of the Drawings

[0029]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

Figure 10

Figure 11

Figure 12

Figure 13

Figure 14

Embodiments for Carrying Out the Invention

[0030] Examples and their detailed content will be described below so that the features and effects of the present invention can be more clearly understood and recognized.

[0031] The non-fullerene acceptor compound containing benzoselenadiazole according to the present invention adopts a structural mode of A’-D-A-D-A’, and uses a polycyclic structure based on benzoselenadiazole as the central electron-deficient unit. This unit has the following characteristics. That is, regarding the selenium atom contained in benzoselenadiazole, compared with the sulfur atom in ordinary benzoselenadiazole, the atomic radius is relatively large, and the intermolecular Se-Se interaction is stronger than the S-S interaction by the thio group. Therefore, the carrier mobility is improved, and in the absorption spectrum, the absorption wavelength range of the selenium-based non-fullerene material is red-shifted compared with the thio-based non-fullerene material, having a greater advantage in device manufacturing. In addition, since the leakage prevention performance of the selenium-based non-fullerene acceptor compound is superior to that of the thio-based non-fullerene acceptor compound, the photoelectric conversion efficiency of the OPV is also improved.

[0032] As the structure bonded to both sides of benzoselenadiazole, Ar in the present invention 1 is a monocyclic heterocyclic unit. As the atoms contained in the heterocyclic unit, S, Se, O, N, and Te are preferred. Among them, the nitrogen atom-containing unit improves the solubility by bonding with different carbon chains. Oxygen, sulfur, selenium, and tellurium atoms can tune the energy level of the molecule, the intermolecular interaction, the carrier mobility, and the absorption range due to the differences in their electronegativity and atomic radius.

[0033] In the present invention, Ar 1 adjacent to Ar 2Preferably, a monocyclic or polycyclic aromatic heterocyclic derivative containing S, Se, O, N, or Te atoms is used. If necessary, such units may vary in the combination of atoms and monocyclic / polycyclic structures, and in some cases, there may be multiple variations. Among them, the nitrogen atom-containing unit has the property of improving solubility by bonding with different carbon chains. The remaining oxygen, sulfur, selenium, and tellurium atoms can impart different energy levels and carrier mobilities to the unit due to differences in their electronegativity and atomic radius. In the case of a monocyclic ring, since the structure is simple, there are few sites where functional groups can be modified. In the case of a polycyclic ring, there are more sites for tuning the molecular structure than in a monocyclic ring, making it easier to adjust the properties of the material. The selection of different atoms and monocyclic / polycyclic rings has a significant impact on the energy level, absorption spectrum, and solubility of the material's molecules. As the number of rings increases, the length of the conjugated bond increases, and the bandgap of the molecule becomes narrower, indirectly tuning the absorption spectrum.

[0034] In the non-fullerene acceptor compound containing benzoselenadiazole according to the present invention, π, which is an acceptor unit, is a monocyclic or polycyclic derivative, and the number of connections of the unit π in such a structure is preferably 0 to 5. If necessary, such units may vary in the combination of atoms and monocyclic / polycyclic structures, and in some cases, there may be multiple variations. Among them, the nitrogen atom-containing unit has the property of improving solubility by bonding with different carbon chains. The remaining oxygen, sulfur, selenium, and tellurium atoms can impart different energy levels and carrier mobilities to the unit due to differences in their electronegativity and atomic radius, and can also affect the absorption range. In the case of a monocyclic ring, since the structure is simple, there are few sites where functional groups can be modified. In the case of a polycyclic ring, there are more sites for tuning the molecular structure than in a monocyclic ring, making it easier to adjust the properties of the material. The selection of different atoms and monocyclic / polycyclic rings has a significant impact on the energy level, absorption spectrum, and solubility of the material's molecules. As the number of rings increases, the length of the conjugated bond increases, and the bandgap of the molecule of the unit becomes narrower, indirectly tuning the absorption spectrum.

[0035] At both ends of the non-fullerene acceptor compound containing benzoselenadiazole according to the present invention, the bonding portions are electron-withdrawing groups, preferably monocyclic or polycyclic derivatives containing a ketone group and an electron-withdrawing group. If necessary, such units vary in plurality in the combination of atoms and monocyclic / polycyclic rings. Among them, in materials containing a ketone group or an electron-withdrawing group, the action by non-covalent bonds between molecules is effectively promoted, and the molecular alignment and carrier mobility are improved. Further, as the electron-withdrawing intensity and the number of electron-withdrawing group units increase, the carrier transferability between molecules also increases remarkably. Therefore, the carrier mobility and the light absorption property of the material are further improved, the red shift of the absorption spectrum is tuned, and the application range is further widened. The selection of monocyclic and polycyclic rings has the effect of increasing the sites for modification by functional groups and tuning the intermolecular action and the electron-withdrawing group.

[0036] As the organic optoelectronic device 10 including a diazole-type non-fullerene acceptor compound according to the present invention, an organic photodetector (OPD), an organic photovoltaic (OPV) cell, etc. are often seen. Its structure includes a substrate 110, a lower electrode 120, an intermediate layer 12, and an upper electrode 160 in order. The intermediate layer 12 includes a first carrier transmission layer 130, an active layer 140, and a second carrier transmission layer 150. The active layer 140 is provided between the first carrier transmission layer 130 and the second carrier transmission layer 150, and the active layer 140 includes a non-fullerene acceptor compound containing benzoselenadiazole according to the present invention.

[0037] According to the application field of the organic optoelectronic device according to the present invention, the installation order of the first carrier transmission layer 130 and the second carrier transmission layer 150 in the intermediate layer 12 may be reversed. For example, the first carrier transmission layer 130 may be installed on the second carrier transmission layer 150, or the second carrier transmission layer 150 may be installed on the first carrier transmission layer 130.

[0038] The material of the substrate 110 in the organic optoelectronic device according to the present invention may be glass or plastic. The lower electrode 120 employed is a metal conductive layer exhibiting a high work function, preferably indium-tin oxide or a derivative thereof. The upper electrode 160 is a metal conductive layer exhibiting a low work function, preferably using silver, aluminum, or gold.

[0039] The first carrier transport layer 130 in the organic optoelectronic device according to the present invention is used to control the transport of carriers generated by light irradiation on the optoelectronic device, and a metal oxide or a conductive polymer is used, preferably molybdenum oxide (MoO3) or PEDOT:PSS. Similarly, the second carrier transport layer 150 is used to control the transport of carriers generated by light irradiation on the optoelectronic device, and a metal oxide or a conductive polymer is used, preferably zinc oxide (ZnO) or PFNBr.

[0040] Hereinafter, the manufacturing method according to the present invention will be described in detail. Compounds N1 to N10 listed below are non-fullerene acceptor compounds containing benzoselenadiazole according to the present invention. (Example 1: Preparation of Compounds N1 and N2) As shown below, Compounds M1 to M7 were synthesized.

[0041]

Chemical formula

[0042] a) Synthesis of M1 The weighed DBBT (8 g, 27.2 mmol) was charged into a 500 mL three-necked flask, ethanol (120 mL) and THF (200 mL) were added, and it was stirred under an ice bath using a magnetic stirrer until completely dissolved. NaBH4 (21 g, 544 mmol) was slowly added thereto, and after stirring for 30 minutes under the ice bath, the ice bath was removed, and the reaction was carried out at room temperature for 1 hour. Thereafter, the crude product was acidified and extracted three times with ethyl acetate / H2O (aq). MgSO4 was added to the recovered organic phase to remove water, the solvent was removed by centrifugation, and a white solid M1 (6.5 g, 90%) was obtained as a product. For the white solid M1 1 1H NMR (500 MHz, CDCl3) measurement results: δ 6.82 (s, 2H), 3.88 (s, 4H).

[0043] b) Synthesis of M2 The weighed M1 (7 g, 26.3 mmol) and SeO2 (3.5 g, 31.6 mmol) were charged into a 500 mL three-necked flask, ethanol (210 mL) was added, and the temperature was raised to 75 °C with stirring using a magnetic stirrer and refluxed for 1 hour. The reaction flask was placed in an ice bath to precipitate a white solid. After degassing and filtration, it was washed with EtOH, and a white solid M2 (8 g, 90%) was obtained as a product. For the white solid M2 1 1H NMR (500 MHz, CDCl3) measurement results: δ 7.62 (s, 2H).

[0044] c) Synthesis of M3 A magnetic stirrer was placed in a prepared 250 mL three-necked flask, and H2SO4 (42 mL), fuming H2SO4 (14 mL) and fuming HNO3 (35 mL) were added in order under an ice bath, and further M2 (6.5 g, 18.1 mmol) was added. Nitrogen gas was blown in, and the reaction was carried out at room temperature slowly for 18 hours. After completion of the reaction, the reaction solution was poured into ice cubes, and after the ice cubes melted, the solid was recovered through degassing, filtration and washing with water, and a yellowish-brown solid M3 (3.5 g, 43%) was obtained as a product. As a result of the measurement, since the molecule of M3 did not contain hydrogen atoms, 1 the next experiment was carried out without measuring the 1H spectrum.

[0045] d) Synthesis of M4 Weighed M3 (3.5 g, 8.1 mmol) and TT-Sn (8.9 g, 17.9 mmol) were added to a 250 mL three-necked flask, THF (105 mL) was added, and the mixture was stirred using a magnetic stir bar. It was deoxygenated with argon gas for 30 minutes at room temperature. Under an argon atmosphere, Pd2dba3 (298 mg, 0.33 mmol) and P(O-tolyl)3 (396 mg, 1.30 mmol) were added, and the temperature was raised to 70 °C and refluxed for 2 hours. The catalyst was removed using a short column with silica gel and Celite, and the solvent was removed by centrifugation. After dissolving in THF and heptane with stirring, methanol was added dropwise for recrystallization and precipitation, followed by degassing and filtration to recover the solid. A red solid M4 (4.9 g, 70%) was obtained as the product. The 1 1H NMR (500 MHz, CDCl3) measurement results: δ 7.64 (s, 2H), 7.16 (s, 2H), 2.77 (t, J = 7.5 Hz, 4H), 1.80 - 1.77 (m, 4H), 1.41 - 1.26 (m, 32H), 0.88 (t, J = 7.0 Hz, 6H).

[0046] e) Synthesis of M5 Weighed M4 (6 g, 8.0 mmol) and PPh3 (21 g, 80.4 mmol) were added to a 500 mL three-necked flask, ODCB (173 mL) was added, and after deoxygenating with argon gas for 30 minutes at room temperature, the temperature was raised to 180 °C and refluxed for 22 hours. After completion of the reaction, it was taken out from the sand bath and returned to room temperature, methanol was added to precipitate the solid, and a suspension was obtained. It was stirred for 30 minutes, and the solid was recovered through degassing and filtration. This was applied to a silica gel short column, and weakly polar impurities were removed using an eluent of DCM / heptane = 1 / 1, and then the product was eluted using THF as the eluent. The solvent was removed by centrifugation, and a brown solid M5 (3.3 g, 64%) was obtained as the product (as a result of the measurement, since M5 had poor solubility, 1 1H spectrum measurement was omitted and the process directly proceeded to the next step).

[0047] f) Synthesis of M6 In a prepared 250 mL three-necked flask, M5 (4.1 g, 8.0 mmol) and 60% NaH (2.6 g, 64.2 mmol) were weighed, dry DMF (123 mL) was injected, and the mixture was stirred at room temperature for 30 minutes using a magnetic stir bar. Subsequently, 1-iodo-2-hexyldecane (25.5 g, 72.3 mmol) was injected at room temperature, the temperature was raised to 80 °C and refluxed for 5 hours. Then, water was slowly added until no bubbles were generated in the flask to terminate the reaction. The mixture was extracted three times with ethyl acetate / H2O. MgSO4 was added to the recovered organic phase to remove water, and the solvent was removed by centrifugation. Chromatography using a silica gel column (the injection solution was heptane / dichloromethane = 5 / 1) gave a red solid M6 (4.5 g, 70%) as the product. For the red solid M6 1 1H NMR (500 MHz, CDCl3) measurement results: δ 6.97 (s, 2H), 4.52 (d, J = 8.0 Hz, 4H), 2.79 (t, J = 7.8 Hz, 4H), 2.09 - 2.04 (m, 2H), 1.83 (p, J = 7.6 Hz, 4H), 1.45 - 0.79 (m, 92H), 0.66 (d, J = 7.0 Hz, 6H).

[0048] g) Synthesis of M7 In a prepared 100 mL three-necked flask, M6 (800 mg, 0.64 mmol) was weighed, dry THF (32 mL, 40V) was injected, and the mixture was stirred with a magnetic stir bar under an ice bath. LDA (2.6 mL, 5.15 mmol) was slowly injected under the ice bath, and the reaction was carried out for 30 minutes under the ice bath. Subsequently, 1-formylpiperidine (0.71 mL, 6.44 mmol) was slowly injected under the ice bath. After the addition was complete, the ice bath was removed, the reaction temperature was returned to room temperature, and the reaction was carried out for 30 minutes. MeOH was slowly added until no bubbles were generated to terminate the reaction. The mixture was extracted three times with ethyl acetate / H2O. MgSO4 was added to the recovered organic phase to remove water, and the solvent was removed by centrifugation. Chromatography using a silica gel column (the injection solution was heptane / dichloromethane = 5 / 1) gave a red oily product M7 (470 mg, 60%) as the product. For the red oily product M7 11H NMR (500 MHz, CDCl3) measurement results: δ 10.11 (s, 2H), 4.55 (d, J = 8.0 Hz, 4H), 3.17 (t, J = 7.8 Hz, 4H), 2.04 - 2.01 (m, 2H), 1.90 (p, J = 7.6 Hz, 4H), 1.48 - 0.78 (m, 92H), 0.66 (d, J = 7.0 Hz, 6H).

[0049] h) Preparation of Compound N1

[0050]

Chemical formula

[0051] Weighed M7 (510 mg, 0.39 mmol), 2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene) malononitrile (452 mg, 1.96 mmol), and chloroform (15 mL) into a 100 mL three-necked flask, stirred using a magnetic stir bar, and deoxygenated with argon gas for 30 minutes. Injected pyridine (0.5 mL), heated to 60 °C and refluxed for 30 minutes. After completion of the reaction, removed it from the oil bath and returned it to room temperature, and removed the solvent by centrifugation. Washed once with MeOH and twice with acetone under ultrasonic oscillation. After degassing and filtration, the solid was recovered, and a dark blue solid N1 (406 mg, 60%) was obtained as the product. The 1 1H NMR (500 MHz, CDCl3) measurement results: δ 9.12 (s, 2H), 8.55 - 8.52 (m, 2H), 7.68 - 7.66 (m, 2H), 4.70 (d, J = 7.0 Hz, 4H), 3.19 (t, J = 7.3 Hz, 4H), 2.21 - 2.17 (m, 2H), 1.85 (p, J = 6.8 Hz, 4H), 1.49 - 0.75 (m, 92H), 0.68 (d, J = 6.3 Hz, 6H).

[0052] i) Preparation of Compound N2

[0053]

Chemical formula

[0054] In a 100 mL three-necked flask, M7 (510 mg, 0.39 mmol) and 2-(5,6-dichloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene) malononitrile were weighed, stirred using a magnetic stir bar, and deoxygenated with argon gas for 30 minutes. Pyridine (0.5 mL) was injected, the temperature was raised to 60 °C and refluxed for 30 minutes. After completion of the reaction, it was taken out from the oil bath and returned to room temperature, and the solvent was removed by centrifugation. It was washed once with MeOH and twice with acetone under ultrasonic oscillation. After degassing and filtration, the solid was recovered to obtain a dark blue solid N2 (421 mg, 60%) as the product. The 1 1H NMR (500 MHz, CDCl3) measurement results: δ 9.15 (s, 2H), 8.77 (s, 4H), 7.93 (s, 2H), 4.70 (d, J = 7.5 Hz, 4H), 3.20 (t, J = 8 Hz, 4H), 2.14 - 2.09 (m, 2H), 1.85 (p, J = 7.8 Hz, 4H), 1.51 - 0.75 (m, 92H), 0.67 (d, J = 6.8 Hz, 6H).

[0055] (Example 2: Preparation of Compounds N3 and N4)

[0056]

Chemical Structure

[0057] (Example 3: Preparation of Compounds N5 and N6)

[0058]

Chemical Structure

[0059] (Example 4: Preparation of Compounds N7 and N8)

[0060]

Chemical Structure

[0061] (Example 5: Preparation of Compounds N9 and N10)

[0062] [Chem.]

[0063] In the following examples, the performance test results when an organic optoelectronic device containing a diazole-type non-fullerene acceptor compound according to the present invention is used in an organic photodetector (OPD) and an organic photovoltaic (OPV) cell will be described.

[0064] (Example 6: Performance Test; UV Absorption and CV Energy Levels of Materials) Regarding UV absorption, an ultraviolet / visible light spectrometer was used to measure the absorption spectrum of the sample. The sample to be measured was used for measurement in a solution state dissolved in chloroform. When measuring in a solid state, it was necessary to prepare the sample as a thin film and use it for measurement. The thin film was prepared by spin-coating a sample prepared at a concentration of 5 wt% on a glass substrate and then measuring it in a solid state.

[0065] Regarding the CV energy levels, the oxidation and reduction potentials were recorded using an electrochemical analyzer. A 0.1 M acetonitrile solution of Bu4NPF6 (tetra-1-butylammonium hexafluorophosphate) was used as the electrolyte, a 0.01 M acetonitrile solution of silver nitrate (AgNO3) and 0.1 M TBAP (tetrabutylammonium perchlorate) was used as the Ag / AgCl reference electrode, platinum (Pt) was used as the counter electrode, and a glassy carbon electrode was used as the working electrode. Also, the measurement target was dissolved in chloroform and dropped onto the working electrode to form a thin film. The measurement was performed while scanning at a rate of 50 mV / sec to record the oxidation and reduction curves. The CV graph was generated by plotting the oxidation and reduction potentials, calibrating using ferrocene / ferrocenium (Fc / Fc+) as the internal reference potential, and obtaining the values of the HOMO and LUMO. The calculation formula is as follows.

[0066] HOMO = -(4.71 eV + (E ox -E ref )) LUMO = HOMO + Eg opt The measurement results are shown in Table 1.

[0067]

Table 1

[0068] (Example 7: OPD Performance Test) An ITO-coated glass with thin-film electrical resistance and pre-patterned was used as the substrate. The substrate was processed for 15 minutes each in neutral detergent, deionized water, acetone, and isopropanol under ultrasonic oscillation. The washed substrate was further processed in a UV-O3 cleaning device for 15 minutes. An AZO (Aluminum doped zinc oxide nanoparticle) topcoat layer was spin-coated on the ITO substrate at a rotational speed of 2000 rpm for 40 seconds and then baked in an air atmosphere at 120 °C for 5 minutes. Using o-xylene, an active layer solution with a polymer concentration of 12 - 16 mg / mL was prepared (the weight ratio of the donor polymer to the acceptor small molecule was 1:1.2 - 1:1.5). In order to completely dissolve the polymer, the active layer solution was stirred on a heating plate at 100 °C for at least 3 hours, then filtered through a PTFE permeable membrane (pore size 0.45 - 1.2 μm), and the active layer solution was heated for another 1 hour. Then, the solution was cooled to room temperature, and coating was carried out while controlling the film thickness in the range of about 500 nm to about 1000 nm using the coating rotational speed. Subsequently, the mixed film was annealed at 100 °C for 5 minutes and then fed into an evaporation device, and a thin layer (8 nm) of MoO3 was deposited by vacuum evaporation at 3×10 -6 Torr to form an anode intermediate layer. Using a source meter Keithley TM 2400, the dark current (I D ; the bias voltage was -8V) in the absence of light was recorded. Subsequently, using a solar light simulator (a xenon arc lamp with an AM1.5G color filter, 100 mW / cm 2 ), the photocurrent (I ph ) characteristics of the device were measured in an air atmosphere at room temperature. In addition, a standard silicon diode with a KG5 color filter was used as a reference cell to calibrate the light intensity so as to match the non-matching parts in the optical spectrum. For the external quantum efficiency (EQE), an external quantum efficiency meter with a measurement range of 300 - 1100 nm (bias voltage 0 - -8V) was used. Silicon (300 - 1100 nm) and germanium (1100 - 1800 nm) were used for the calibration of the light source. The measurement results are shown in Table 2.

[0069]

Table 2

[0070] In Table 2, the chemical formula of compound P1 to be mixed with N2 is as follows.

[0071] [Chemical formula]

[0072] In addition, the compound structure of P1 is the same as that of polymer 10A disclosed in US8772442B2.

[0073] (Example 8: OPV Performance Measurement) ITO-coated glass with thin-film electrical resistance and pre-patterned was used as the substrate. The substrate was treated in neutral detergent, deionized water, acetone, and isopropanol for 15 minutes each under ultrasonic oscillation. The washed substrate was further treated in a UV-O3 cleaning device for 15 minutes. On the ITO substrate, a ZnO (a solution obtained by diluting a 15 wt% toluene solution of diethylzinc with tetrahydrofuran) top coat layer was spin-coated at a rotational speed of 5000 rpm for 30 seconds and then baked in an air atmosphere at 120 °C for 20 minutes. Using o-xylene, an active layer solution with a polymer concentration of 8 - 10 mg / mL was prepared, and an appropriate amount of an additive for adjusting the thin-film morphology was added (the weight ratio of the donor polymer to the acceptor small molecule was 1:1.2 - 1:1.5). In addition, in order to completely dissolve the polymer, the active layer solution was stirred on a heating plate at 100 °C for at least 3 hours. Then, the active layer solution was cooled to room temperature, and coating was carried out while controlling the film thickness to be in the range of about 100 nm using the coating rotational speed. Subsequently, the mixed film was annealed at 120 °C for 5 minutes and then fed into an evaporation device, and a thin layer (8 nm) of MoO3 was deposited by vacuum evaporation at 3 × 10 -6 Torr. A xenon arc lamp with an AM1.5G color filter (100 mW / cm 2) was used to measure the J-V characteristics of the device in an air atmosphere at room temperature. A standard silicon diode with a KG5 color filter was used as a reference cell to calibrate the light intensity so as to match the non-matching part in the optical spectrum. The J-V characteristics were recorded using a source meter Keithley TM 2400. A typical cell has an active area of 4 mm 2 , and the area is defined by the aperture area that matches the metal cover in the device. The PCE is obtained by averaging the measurement results at four effective points on each device.

[0074] The measurement results are shown in Table 3.

[0075]

Table 3

[0076] In Table 2, the chemical formula of the compound P2 mixed with N1 is as follows.

[0077]

Chem.

[0078] The compound structure of P2 is disclosed in the publication Joule 2020, 4, 189-206.

[0079] As can be seen from the above measurement results, compared with the conventional acceptor, the non-fullerene acceptor compound containing benzoselenadiazole according to the present invention has an increased HOMO value, maintains a certain LUMO value, and has a reduced bandgap. In addition, when the non-fullerene acceptor compound containing benzoselenadiazole according to the present invention is applied to OPD, it exhibits good leakage prevention performance, shows a high EQE value in the optical spectrum region of 940 nm, and also shows good photoelectric conversion efficiency when applied to OPV.

[0080] Therefore, the present invention can be provided to the industry as having novelty and inventiveness, and it conforms to the purpose of the patent application system. Therefore, the present invention is expected to be patented.

[0081] The content described above is merely a preferred embodiment of the present invention and does not limit the scope of implementation of the present invention. Also, all equivalent changes and modifications made based on the shape, structure, features, and spirit described in the claims of the present invention are included in the claims of the present invention.

Description of Reference Numerals

[0082] 10 Photoelectric element 110 Substrate 120 Lower electrode 130 First carrier transmission layer 140 Active layer 150 Second carrier transmission layer 160 Upper electrode 12 Intermediate layer

Claims

1. A non-fullerene acceptor compound containing benzoselenadiazole represented by the following formula. 【Chemical Formula 1】 (In the formula, Ar １ is 【Chemical Formula 2】 and The substituent R in the formula １ is selected from the group consisting of C1-C30 linear alkyl, C1-C30 branched alkyl, C1-C30 alkoxy, C1-C30 alkylthio, C1-C30 halogenated alkyl, C1-C30 unsaturated alkyl, C1-C30 cyanoalkyl, C1-C30 nitroalkyl, C1-C30 hydroxyalkyl, and halogen. Ar ２ is 【Chemical Formula 3】 and is at least one selected from the group consisting of The substituent R in the formula ２ is selected from the group consisting of C1-C30 linear alkyl, C1-C30 branched alkyl, C1-C30 alkoxy, C1-C30 alkylthio, C1-C30 halogenated alkyl, C1-C30 unsaturated alkyl, C1-C30 cyanoalkyl, C1-C30 nitroalkyl, C1-C30 hydroxyalkyl, halogen, benzene ring substituted by R １ , hetero five-membered ring substituted by R １ , and hetero six-membered ring substituted by R １ . π is 【Chemical Formula 4】 and is at least one selected from the group consisting of The substituent R in the formula １is at least one selected from the group consisting of linear alkyls having C1 to C30 carbon atoms, branched alkyls having C1 to C30 carbon atoms, alkoxys having C1 to C30 carbon atoms, alkylthios having C1 to C30 carbon atoms, halogenated alkyls having C1 to C30 carbon atoms, unsaturated alkyls having C1 to C30 carbon atoms, cyanoalkyls having C1 to C30 carbon atoms, nitroalkyls having C1 to C30 carbon atoms, hydroxyalkyls having C1 to C30 carbon atoms, and halogens, and m = 0 to 5, EG is 【Chemical Formula 5】 at least one selected from the group consisting of In the formula, the substituent R ３ is at least one selected from the group consisting of a hydrogen atom, a halogen, an alkyl having C1 to C20 carbon atoms, an alkoxy having C1 to C20 carbon atoms, an aldehyde having C1 to C20 carbon atoms, a carboxylic acid having C1 to C20 carbon atoms, and cyano. )

2. a substrate, a lower electrode provided on the substrate, an upper electrode provided facing the lower electrode, and an intermediate layer provided between the lower electrode and the upper electrode, and includes the intermediate layer includes a first carrier transport layer, an active layer, and a second carrier transport layer, the active layer is provided between the first carrier transport layer and the second carrier transport layer, and contains a non-fullerene acceptor compound containing benzoselenadiazole represented by the following formula An organic optoelectronic device including a septa compound. 【Chemical Formula 6】 (In the formula, Ar １ is 【Chemical Formula 7】 and In the formula, the substituent R １is selected from the group consisting of linear alkyls having C1 - C30, branched alkyls having C1 - C30, alkoxys having C1 - C30, alkylthios having C1 - C30, halogenated alkyls having C1 - C30, unsaturated alkyls having C1 - C30, cyanoalkyls having C1 - C30, nitroalkyls having C1 - C30, hydroxyalkyls having C1 - C30, and halogens, Ar ２ is 【Chemical formula 8】 at least one selected from the group consisting of, substituent R in the formula ２ is selected from the group consisting of linear alkyls having C1 - C30, branched alkyls having C1 - C30, alkoxys having C1 - C30, alkylthios having C1 - C30, halogenated alkyls having C1 - C30, unsaturated alkyls having C1 - C30, cyanoalkyls having C1 - C30, nitroalkyls having C1 - C30, hydroxyalkyls having C1 - C30, halogens, benzene ring substituted by R １ , hetero five - membered ring substituted by R １ , and hetero six - membered ring substituted by R １ selected from the group consisting of, π is 【Chemical formula 9】 at least one selected from the group consisting of, substituent R in the formula １ is at least one selected from the group consisting of linear alkyls having C1 - C30, branched alkyls having C1 - C30, alkoxys having C1 - C30, alkylthios having C1 - C30, halogenated alkyls having C1 - C30, unsaturated alkyls having C1 - C30, cyanoalkyls having C1 - C30, nitroalkyls having C1 - C30, hydroxyalkyls having C1 - C30, and halogens, m = 0 - 5, EG is 【Chemical formula 10】 at least one selected from the group consisting of, substituent R in the formula ３is at least one selected from the group consisting of a hydrogen atom, a halogen, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 aldehyde, C1-C20 carboxylic acid, and cyano. )

3. The active layer is disposed on the first carrier transport layer, and the second carrier transport layer is disposed on the active layer. The organic optoelectronic device according to claim 2.

4. The active layer is disposed on the second carrier transport layer, and the first carrier transport layer is disposed on the active layer. The organic optoelectronic device according to claim 2.

5. The first carrier transport layer contains molybdenum oxide (MoO ３ ), or PEDOT:PSS. The organic optoelectronic device according to claim 2.

6. The second carrier transport layer contains zinc oxide (ZnO) or PFNBr. The organic optoelectronic device according to claim 2.

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