Patent Application
20230131130
The subject invention relates to a compound and photoelectronic components containing the subject compound. This compound comes with especially good physical and chemical properties, which can also be processed with an environment-friendly organic solvent to enhance the convenience for the production of the organic semiconducting compound that makes a lower impact on the environment, as well as organic photoelectronic components with excellent response values in the infrared range.
In recent years, there has been an increasing demand for manufacturing more versatile and lower-cost electronic components; hence, the increasing demand for organic semiconducting compounds (OSC). The reason behind this phenomenon is mainly due to the wider light absorption range, higher light absorption coefficient, and adjustable structure of the organic semiconducting compound, in comparison with the traditional semiconductor materials. In terms of the light absorption range, energy level, and solubility, they can all be adjusted according to the target requirements. In addition, in the aspect of manufacturing the organic components, organic materials have the advantages of low cost, flexibility, low toxicity, and suitability for mass production, making organic photoelectronic materials high competitiveness in various fields. Such compounds can be applied in a wide range, including organic field-effect transistors (OFETs), organic light-emitting diodes (OLEDs), organic photodetectors (OPDs), organic photovoltaics (OPVs), sensors, storage components, and various components or assemblies of logic circuits. Among them, organic semiconductor materials usually exist in the form of thin layers in the above-mentioned applications of components or assemblies, with a thickness of about 50 nm to 1 μm.
Organic photodetector (OPD) makes an emerging field of organic photoelectronic in recent years. Such devices can detect various light sources in the environment and are used in application fields such as medical care, health management, intelligent driving, unmanned aerial vehicle, or digital home, etc. Therefore, there are different material requirements for different application fields. Moreover, the use of organic materials enables the device with good flexibility. Benefit from the development of material science, OPD can not only be made into a thin layer but also can absorb light in specific wavelength bands. According to the different light sources, products on the market need to absorb light in different bands. Therefore, the use of organic materials can adjust the absorption range, which can effectively absorb the required wavelength bands to reduce interference, and the high extinction coefficient of organic materials can also effectively improve the detection efficiency. In recent years, the development of OPD has covered from ultraviolet and visible light to near-infrared (NIR).
In terms of performance, the material of the active layer in the organic photodetector directly contributes to the performance of the device, therefore the active layer plays an important role. The materials of the active layer consist of the donor and the acceptor. On the one hand, common donor materials include organic polymers, oligomers, or limited molecular units. Nowadays D-A type conjugate polymers make the mainstream among donors. Through the interaction between the electron-rich unit and the electron-deficient unit in the polymer, the push-pull electron effect formed can be used to control the energy level and energy gap of the polymer. On the other hand, the matching acceptor materials are usually fullerene derivatives with high conductivity, with a light absorption range of about 400˜600 nm. Additionally, graphene, metal oxides, or quantum dots (QDs) are also included. However, the structure of fullerene derivatives is hard to adjust, and the range of absorption wavelength bands and energy levels are limited; thus, limiting the overall matching of donor and acceptor materials. With the development of the market, the demand for materials within the near-infrared range is gradually increasing. Even though the light absorption range of the conjugate polymer donor can be adjusted to the near-infrared range, it may not be well matched due to the limit of the fullerene acceptors. In the end, the development of non-fullerene acceptor compounds to replace the traditional fullerene acceptors becomes very important in the breakthrough of active layer materials.
Nonetheless, the development of non-fullerene acceptor compounds was quite difficult in the early stages because it was not easy to control the morphology of the compound, hence resulting in low power conversion efficiency. However, since 2015, numerous studies on non-fullerene acceptors have significantly improved their electrical performance, thus making non-fullerene acceptors a competitive choice. This change is mainly attributable to the advancement of synthesis methods and the improvement of material design strategies, etc. The wide range of donor materials previously developed for matching the fullerene acceptors has also indirectly contributed to the development of non-fullerene acceptor compounds.
At present, the development of non-fullerene acceptor compound materials mainly lies in the molecular structure of A-D-A mode which consists of one electron-rich center unit with two electron-deficient units, where D is usually a molecule composed of benzene ring and thiophene, and A is usually an indanone-cyano (IC) derivatives. Another mode of molecular structure is the A′-D-A-D-A′ mode with the center of one electron-deficient unit where a molecule such as sulfur atom is often used therewith to enhance the performance.
In the field of intelligent driving and an unmanned aerial vehicle, to avoid visible light with a too strong signal, the development trend is to adopt the NIR as the absorption band. Moreover, to have the properties of better penetration and long-distance detection, the application wavelength needs to exceed 1,000 nm. In addition, in response to meeting the increasing demands in application fields, the photoelectric devices adopted need to have higher detectivity and lower leakage current. Besides, in response to the requirements of environmental protection regulations and good processing operability in various countries, environmentally friendly solvents must be used as much as possible during the material process, to be conducive to wet process operations. However, as it stands, organic semiconductor materials with relevant potential today, whether utilizing the polymer with donor-acceptor structure or small molecules, only show good performance in the light absorption range of <1,000 nm, while showing inferior performance in the light absorption range of >1,000 nm. Besides, the solvents used in solution processing are mainly organic solvents containing halogens which hurt the environment. Therefore, the need is imminent to develop an organic semiconducting compound that has superior photo-response performance and better electrical performance in the infrared range, and use halogen-free organic solvents during the solution process.
Given the problems about the deficiencies of current materials in the preceding paragraphs, the objective of the subject invention is to provide a new organic semiconducting compound, especially an n-type organic semiconducting compound, which can overcome the shortcomings of the organic semiconducting compounds based on the previous technologies, while providing one or more advantageous properties discussed above, including a photo-response greater than 1,000 nm and good device performance, as well as easy synthesis demonstrated during the production process, such as good processability and good solubility in environmentally-friendly solvents, thus facilitating the large-scale manufacturing, i.e. mass production, with the solution processing method.
Another objective of the subject invention is to provide new organic photoelectronic devices which comprise the organic semiconducting compound under the subject invention, with a photo-response greater than 1,000 nm, lower leakage current, and excellent detectivity.
To achieve the objective mentioned above, the subject invention provides an organic semiconducting compound which is represented in the following formula:
wherein,
To achieve the objective mentioned above, the subject invention further provides an organic photoelectronic component, which comprises: a substrate; an electrode module disposed on the substrate, which includes a first electrode and a second electrode; an active layer disposed between the first electrode and the second electrode, where the active layer includes at least one organic semiconducting compound as described in the present invention; where at least one of the first electrode and the second electrode is transparent or semi-transparent.
The organic semiconducting compound under the subject invention not only possesses the characteristic of easy synthesis but also exhibits good processability and solubility in common solvents during the production process, thus facilitating the large-scale manufacturing during the solution process.
The preparation of the organic semiconducting compound under the subject invention can be achieved based on the methods known to those with ordinary knowledge in the technical field covering the subject invention and described in the literature, which will be further illustrated in the experimental examples.
The organic semiconducting compound provided under the subject invention is represented by the following formula:
wherein,
In the formula for the organic semiconducting compound under the subject invention, the aromatic ring of Ar1 preferably has 4 to 30 ring C atoms, which is monocyclic or polycyclic, and may also contain fused rings, preferably with 1, 2, 3, 4 or 5 fused or unfused rings, and optionally with one or more halogen-substituents.
In the formula for the organic semiconducting compound under the subject invention, the heteroaromatic ring of Ar1 preferably has 4 to 30 ring C atoms, where one or more ring C atoms are heteroatoms preferably selected from N, O, S, Si, and Se substituent, which is monocyclic or polycyclic, and may also contain fused rings, preferably 1, 2, 3, 4 or 5 fused or unfused rings, and optionally with one or more halogen-substituents.
In the formula for the organic semiconducting compound under the subject invention, R1 can be alkyl or alkoxy (i.e. one of the CH2 groups is substituted with —O—), linear chain or branched chain. Particularly preferred linear chains come with 2, 3, 4, 5, 6, 7, 8, 12, or 16 carbon atoms, therefore are the preferred ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, dodecyl, or hexadecyl; or ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, dodecyloxy or hexadecyloxy; or methyl, nonyl, decyl, undecyl, tridecyl, tetradecyl, or pentadecyl; or nonyloxy, decyloxy, undecyloxy, tridecyloxy or tetradecyloxy.
In the formula for the organic semiconducting compound under the subject invention, R1 can be alkenyl (i.e. one or more CH2 groups in the alkyl group are substituted with —CH═CH—), linear chain or branched chain. Particularly preferred linear chain come with 2 to 10 C atoms, therefore are the preferred vinyl; propen-1-, 2-yl; buten-1-, 2- or 3-yl; penten-1-, 2-, 3- or 4-yl; hexen-1-, 2-, 3-, 4- or 5-yl; heptene-1-, 2-, 3-, 4-, 5- or 6-yl; octen-1-, 2-, 3-, 4-, 5-, 6- or 7-yl; nonen-1-, 2-, 3-, 4-, 5-, 6-, 7- or 8-yl; or decene-1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-yl.
In the formula for the organic semiconducting compound under the subject invention, R1 can preferably be thioalkyl (i.e. one of the CH2 groups is substituted with —S—). Particularly preferred linear chain include thiomethyl (—SCH3), 1-thioethyl (—SCH2CH3), 1-thiopropyl (═—SCH2CH2CH3), 1-(thiobutyl), 1-(thiopentyl), 1-(thiohexyl), 1-(thioheptyl), 1-(thiooctyl), 1-(thiononyl), 1-(thiodecyl), 1-(thioundecyl) or 1-(thiododecyl), wherein preferably the CH2 group adjacent to the sp2 hybridized vinyl carbon atom is replaced.
In the formula for the organic semiconducting compound under the subject invention, the halogen of in R1 can include F, Cl, Br or I.
In the formula for the organic semiconducting compound under the subject invention,
wherein,
In the formula for the organic semiconducting compound under the subject invention, the aromatic ring of Ar2 preferably has 4 to 30 ring C atoms, which are monocyclic or polycyclic, and may also contain fused rings, preferably with 1, 2, 3, 4 or 5 fused or unfused rings, and optionally with one or more halogen-substituents.
In the formula for the organic semiconducting compound wider the subject invention, the heteroaromatic ring of Ar2 preferably has 4 to 30 ring C atoms, where one or more ring C atoms are heteroatoms preferably selected from N, O, S, Si and Se substituent, which is monocyclic or polycyclic, and may also contain fused rings, preferably 1, 2, 3, 4 or 5 fused or unfused rings, and optionally with one or more halogen-substituents.
In the formula for the organic semiconducting compound under the subject invention, R2 can be alkyl or alkoxy (i.e. one of the CH2 groups is substituted with —O—), linear chain or branched chain. Particularly preferred linear chain come with 2, 3, 4, 5, 6, 7, 8, 12 or 16 carbon atoms, therefore are the preferred ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, dodecyl, or hexadecyl; or ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, dodecyloxy or hexadecyloxy; or methyl, nonyl, decyl, undecyl, tridecyl, tetradecyl, or pentadecyl; or nonyloxy, decyloxy, undecyloxy, tridecyloxy or tetradecyloxy.
In the formula for the organic semiconducting compound under the subject invention, R2 can be alkenyl (i.e. one or more CH2 groups in the alkyl group are substituted with —CH═CH—), linear chain or branched-chain. Particularly preferred linear chain come with 2 to 10 C atoms, therefore are the preferred vinyl; propen-1-, 2-yl; buten-1-, 2- or 3-yl; Penten-1-, 2-, 3- or 4-yl; hexen-1-, 2-, 3-, 4- or 5-yl; heptene-1-, 2-, 3-, 4-, 5- or 6-yl; octen-1-, 2-, 3-, 4-, 5-, 6- or 7-yl; nonen-1-, 2-, 3-, 4-, 5-, 6-, 7- or 8-yl; or decene-1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-yl.
In the formula for the organic semiconducting compound under the subject invention, R2 can preferably be thioalkyl (i.e. one of the CH2 groups is substituted with —S—). Particularly preferred linear chain include thiomethyl (—SCH3), 1-thioethyl (—SCH2 CH3), I-thiopropyl (═—SCH2Cl2CH3), 1-(thio butyl), 1-(thiopentyl), 1-(thiohexyl), 1-(thioheptyl), 1-(thiooctyl), 1-(thiononyl), 1-(thiodecyl), 1-(thioundecyl) or 1-(thiododecyl), wherein preferably the CH2 group adjacent to the sp2 hybridized vinyl carbon atom is replaced.
In the formula for the organic semiconducting compound under the subject invention, the halogen of in R2 can include F, Cl, Br or I.
More preferably, A2 is selected from the group consisting of the following groups:
In the organic semiconducting compound under the subject invention,
wherein,
In the formula for the organic semiconducting compound under the subject invention, the heteroaromatic ring of Ar3 preferably has 4 to 30 ring C atoms, where one or more ring C atoms are heteroatoms preferably selected from N, O, S, Si, and Se substituent, which is monocyclic or polycyclic, and may also contain fused rings, preferably 1, 2, 3, 4 or 5 fused or unfused rings, and optionally with one or more halogen-substituents.
In the formula for the organic semiconducting compound under the subject invention, R3 can be alkyl or alkoxy (i.e. one of the CH2 groups is substituted with —O—), linear chain or branched chain. Particularly preferred linear chain come with 2, 3, 4, 5, 6, 7, 8, 12 or 16 carbon atoms, therefore are the preferred ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, dodecyl, or hexadecyl; or ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, dodecyloxy or hexadecyloxy; or methyl, nonyl, decyl, undecyl, tridecyl, tetradecyl, or pentadecyl; or nonyloxy, decyloxy, undecyloxy, tridecyloxy or tetradecyloxy.
In the formula for the organic semiconducting compound under the subject invention, R3 can be alkenyl (i.e. one or more CH2 groups in the alkyl group are substituted with —CH═CH—), linear chain or branched-chain. Particularly preferred linear chain come with 2 to 10 C atoms, therefore are the preferred vinyl; propen-1-, 2-yl; buten-1-, 2- or 3-yl; Penten-1-, 2-, 3- or 4-yl; hexen-1-, 2-, 3-, 4- or 5-yl; heptene-1-, 2-, 3-, 4-, 5- or 6-yl; octen-1-, 2-, 3-, 4-, 5-, 6- or 7-yl; nonen-1-, 2-, 3-, 4-, 5-, 6-, 7- or 8-yl; or decene-1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-yl.
In the formula for the organic semiconducting compound under the subject invention, R3 can preferably be thioalkyl (i.e. one of the CH2 groups is substituted with —S—). Particularly preferred linear chain include thiomethyl (—SCH3), 1-thioethyl (—SCH2CH3), 1-thiopropyl (═—SCH2CH2CH3), 1-(thiobutyl), 1-(thiopentyl), 1-(thiohexyl), 1-(thioheptyl), 1-(thiooctyl), 1-(thiononyl), 1-(thiodecyl), 1-(thioundecyl) or 1-(thiododecyl), wherein preferably the CH2 group adjacent to the sp2 hybridized vinyl carbon atom is replaced.
In the formula for the organic semiconducting compound under the subject invention, the halogen of in R3 can include F, Cl, Br or I.
Preferably, A3 is selected from the group consisting of the following groups:
In the formula for organic semiconducting compound under the subject invention,
wherein,
and
The following examples illustrate the method for the preparation of the organic semiconducting compound under the subject invention.
Organic semiconducting compound 1 is prepared as follows:
First of all, Reaction 1:
Prepare a 250 mL three-necked flask to be stirred mechanically. Pour the gas outlet of the reaction flask into NaOH(aq), and sequentially add H2SO4 (24.6 mL), fuming H2SO4 (53 mL), and fuming HNO3 (29.2 mL) under an ice bath. Then slowly added M1 (20 g, 82.7 mmol) in portions. After adding materials, slowly bring the temperature back to room temperature and let the reaction stir for 3 hours. After the reaction, pour the reaction mixture into ice cubes and stir well. After the ice cubes are melted collect the solid by filtration and rinse the solid with water. Recrystallize the solid with MeOH to obtain the light yellow solid M2 (24 g, at a yield of 87%). In terms of identification, since the M2 molecule does not contain hydrogen atoms, no need to do the proton NMR experiment and proceed directly to the next step of the experiment.
Reaction 2:
M2 (24 g, 7.23 mmol) and Conc. HCl (240 mL) was added into a 500-mL beaker and stirred with a magnet. At 0° C., slowly add Sn (60 g, 50.6 mmol), and let the reaction stir for 3 hours After the reaction, reduce the temperature of the crude product to below −20° C. and precipitate the product. Collect the cream-colored solid by filtration and rinse the solid with water to get M3 (14 g, at a yield of 60%). No need to carry out additional identification of purity, and proceed directly to the next step of the experiment.
Reaction 3:
M3 (1.6 g, 8.55 mmol), M17 (7.0 g, 9.41 mmol), K2CO3 (2.4 g, 17.10 mmol), and EtOH (80 mL) were added into a 250-mL reaction flask and stirred with a magnet. Set the reaction temperature to 40° C., and let the reaction stir for 18 hours. After the reaction, remove the solvent and the residue was extracted three times with heptane/H2O. The organic layer was dried with MgSO4. Purified by the column chromatography (using the eluent with the ratio of heptane/dichloromethane=3/1) to obtain the yellow-green oily product M4 (3.7 g, at a yield of 53%). 1H NMR (500 MHz, CDCl3): δ 7.95 (s, 2H), 7.01 (s, 2H), 2.78 (d, J=7.0 Hz, 4H), 1.76 (s, 2H), 1.33˜1.27 (m, 48H), 0.89˜0.85 (m, 12H).
Reaction 4:
M4 (1 g, 1.22 mmol) and THF (30 mL) were added into a 100-mL three-necked flask and stirred with a magnet. At 0° C., add NBS (479 mg, 2.69 mmol). Slowly bring the temperature back to room temperature and let the reaction stir for 18 hours. After the reaction, perform the extraction for three times with heptane/H2O. The organic layer was dried with MgSO4. The crude mixture was purified by the column chromatography (using the eluent with the ratio of heptane/dichloromethane=5/1) to obtain the dark green oily product M5 (660 mg, at a yield of 47%). 1H NMR (500 MHz, CDCl3): δ 7.10 (s, 2H), 2.78˜2.78 (d, J=7.0 Hz, 4H), 1.77 (s, 2H), 1.44˜1.19 ((m, 48H)), 0.89˜0.86 (m, 12H).
Reaction 5:
M5 (330 mg, 0.34 mmol), M6 (673 mg, 0.81 mmol), and THF (10 mL) were added into a 100-mL three-neck flask and stirred with a magnet. The reaction mixture was purged with argon for 30 minutes. Add Pd2dba, (12 mg, 0.014 mmol) and P(o-tol)3 (16 mg, 0.054 mmol). At 60° C., let the reaction stir for 2 hours. After the reaction, remove the catalyst through a short celite column. The crude mixture was purified by column chromatography (using the eluent with the ratio of heptane/dichloromethane=4/1) to obtain dark green solid M7 (450 mg, at a yield of 62%). 1H NMR (500 MHz, CDCl3): δ 7.32 (s, 2H), 7.21 (d, J=5.0 Hz, 2H), 7.17 (s, 2H), 6.99 (d, J=5.0 Hz, 2H), 6.84 (s, 8H), 6.81 (s, 4H), 2.83 (d, J=7.0 Hz, 4H), 2.47 (t, J=7.5 Hz, 16H), 1.82 (m, 2H), 1.52˜0.25 (m, 112H), 0.86˜0.82 (m, 36H).
Reaction 6:
M7 (360 mg, 0.17 mmol) and DCE (10.8 mL) were added to a 100-mL three-necked reaction flask and stirred with a magnet. The reaction mixture was purged with nitrogen for 30 minutes. In another 100-mL two-necked reaction flask, add anhydrous DMF (0.65 mL, 8.38 mmol), and slowly add POCl3 (0.09 mL, 1.01 mmol) under an ice bath and stir with a magnet for 30 minutes to form the Vilsmeier-Haack reagent. Add the Vilsmeier-Haack reagent into the 100-mL three-necked flask. At room temperature, let the reaction stir for 18 hours. After the reaction, the reaction mixture was extracted three times with dichloromethane/H2O. The organic layer was dried with MgSO4. The crude mixture was purified by column chromatography (using the eluent with the ratio of heptane/dichloromethane=1/1) to obtain dark green oily product M8 (140 mg, at a yield of 30%). 1H NMR (500 MHz, CDCl3): δ 9.80 (s, 2H), 7.58 (s, 2H), 7.36 (s, 2H), 7.22 (s, 2H), 6.89 (s, 4H), 6.81˜6.81 (m, 8H), 2.83 (m, 4H), 2.48 (t, J=7.8 Hz, 16H), 1.82 (m, 2H), 1.55˜1.24 (m, 112H), 0.86˜0.80 (m, 36H).
Reaction 7:
M8 (140 mg, 0.063 mmol), 2-(5,6-dichloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene) malononitrile (67 mg, 0.254 mmol), and CHCl3 (4.2 mL) were added into a 100-mL three-necked flask and stirred with a magnet. The reaction mixture was purged with argon for 30 minutes. Add pyridine (0.07 mL), and let the reaction stir for 18 hours at room temperature. After the reaction, add MeOH (14 mL) and stir for 30 minutes. Collect the solid by filtration and rinse the solid with acetone then get the dark blue solid organic semiconducting compound 1 (100 mg, at a yield of 58%). 1H NMR (500 MHz, CDCl3): δ 8.83 (s, 2H), 8.70 (s, 2H), 7.82 (s, 2H), 7.64 (s, 2H), 7.38 (s, 2H), 7.33 (s, 2H), 6.94 (s, 4H), 6.84 (s, 8H), 2.92 (d, J=6.5 Hz, 4H), 2.51 (t, J=7.8 Hz, 16H), 1.90 (m, 2H), 1.56˜1.24 (m, 12H), 0.88˜0.80 (m, 36H).
Organic semiconducting compound 2 is prepared as follows:
Reaction 1:
M3 (3.4 g, 18.17 mmol), M10 (13.1 g, 19.99 mmol), K2CO3 (5.0 g, 36.35 mmol), and EtOH (170 mL) were added into a 250-mL reaction flask and stirred with a magnet. Set the reaction temperature at 40° C., and let the reaction stir for 18 hours. After the reaction is finished, remove the solvent, and the reaction mixture was extracted three times with heptane/H2O. The organic layer was dried with MgSO4. The crude mixture was purified by column chromatography (using the eluent with the ratio of heptane/dichloromethane=3/1) to obtain the yellow-green oily product M11 (3.4 g, at a yield of 27%). 1H NMR (500 MHz, CDCl3): δ 7.95 (s, 2H), 7.01 (s, 2H), 2.78 (d, J=7.0 Hz, 4H), 1.76 (s, 2H), 1.33˜1.27 (m, 32H), 0.89˜0.85 (m, 12H).
Reaction 2:
M11 (1 g, 1.22 mmol) and THF (30 mL) were added into a 100-mL three-necked flask and stirred with a magnet. At 0° C., add NBS (556 mg, 3.12 mmol). Slowly bring the temperature back to room temperature and let the reaction stir for 18 hours. After the reaction is finished, the reaction mixture was extracted three times with heptane/H2O. The organic layer was dried with MgSO4. The crude mixture was purified by column chromatography (using the eluent with the ratio of heptane/dichloromethane=5/1) to obtain the dark green oily product M12 (612 mg, at a yield of 50%). 1H NMR (500 MHz, CDCl3): δ 7.05 (s, 2H), 2.78-2.77 (d, J=7.0 Hz, 4H), 1.76 (s, 2H), 1.43˜1.20 (m, 32H), 0.88˜0.85 (m, 12H).
Reaction 3:
M12 (440 mg, 0.51 mmol), M13 (582 mg, 1.27 mmol), and THF (13.2 mL) were added into a 100-mL three-necked flask and stirred with a magnet. The reaction mixture was purged with argon for 30 minutes. Add Pd2dba3 (19 mg, 0.020 mmol) and P(o-tol)3 (25 mg, 0.082 mmol). At 60° C., let the reaction stir for 2 hours. After the reaction is finished, remove the catalyst through a short celite column. The crude mixture was purified by column chromatography silica gel (using the eluent with the ratio of heptane/dichloromethane=5/1) to obtain dark green solid M14 (300 mg, at a yield of 46%). 1H NMR (600 MHz, CDCl3): δ 7.81 (s, 2H), 7.20 (s, 2H), 7.00 (s, 2H), 2.82 (d, J=7.2 Hz, 4H), 2.75 (t, J=7.5 Hz, 4H), 1.82˜1.79 (m, 6H), 1.39˜1.26 (m, 64H), 0.93˜0.86 (m, 18H).
Reaction 4:
M14 (150 mg, 0.12 mmol) and DCE (7.5 mL) were added to a 100-mL three-necked reaction flask and stirred with a magnet. The reaction mixture was purged with nitrogen for 30 minutes. In another 100-mL two-necked reaction flask, add anhydrous DMF (0.45 mL, 5.81 mmol), and slowly add POCl3 (0.07 mL, 0.70 mmol) under an ice bath and stir with a magnet for 30 minutes to form the Vilsmeier-Haack reagent. Add the Vilsmeier-Haack reagent into the 100-mL three-necked flask. Heat the flask to 60° C., and let the reaction stir for 22 hours. After the reaction is finished, remove the flask from the oil bath. Bring the temperature back to room temperature, the reaction mixture was extracted three times with dichloromethane/H2O. The organic layer was dried with MgSO4. The crude mixture was purified by column chromatography (using the eluent with the ratio of heptane/dichloromethane=1/4) to obtain the dark green oily product M15 (130 mg, at a yield of 83%). 1H NMR (500 MHz, CDCl3): δ 10.10 (s, 2H), 7.90 (s, 2H), 7.29 (s, 2H), 3.17˜3.14 (m, 4H), 2.85˜2.84 (m, 4H), 1.91˜1.89 (m, 4H), 1.88˜1.88 (m, 2H), 1.25˜1.24 (m, 64H), 0.93˜0.84 (m, 18H).
Reaction 5:
M15 (140 mg, 0.104 mmol), 2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene) malononitrile (120 mg, 0.520 mmol) and CHCl3 (4.2 mL) were added into a 100-mL three-necked flask and stirred with a magnet. The reaction mixture was purged with argon for 30 minutes. Add pyridine (0.07 mL). Heat the reaction to 60° C. and let the reaction stir for 22 hours. After the reaction is finished, remove the flask from the oil bath and cool it to room temperature. Add MeOH (14 mL) into the flask and stir for 30 mins. Collect solid by filtration and rinse the solid with acetone to get the dark blue solid
organic semiconducting compound 2 (130 mg, at a yield of 71%). 1H NMR (500 MHz, 100° C., Cl2 CDCDCl2): δ 8.96 (s, 2H), 8.49˜8.47 (m, 2H), 7.90 (s, 2H), 7.67 (m, 2H), 7.39 (s, 2H), 3.13 (t, J=7.0 Hz, 4H), 2.93 (d, J=7.5 Hz, 4H), 2.03˜1.88 (m, 6H), 1.47˜1.31 (m, 64H), 0.98˜0.88 (m, 18H).
Organic semiconducting compound 3 is prepared as follows:
Reaction 1:
M15 (130 mg, 0.097 mmol), tributyl (1,3-dioxolan-2-ylmethyl) phosphonium (143 mg, 0.386 mmol) and anhydrous THF (6.5 mL) were added into a 100-mL of three-necked flask and stirred with a magnet. At 0° C., add 60% NaH (23 mg, 0.579 mmol). The reaction mixture was slowly warmed to room temperature and stirred for 18 hours. Slowly add dilute hydrochloric acid (10%, 0.39 mL), and reacted at room temperature for 30 mins. After the reaction is finished, the reaction mixture was extracted three times with chloroform/H2O. The organic layer was dried with MgSO4. The crude mixture was purified by column chromatography (using the eluent with the ratio of heptane/chloroform=1/9) to obtain the dark blue solid M16 (100 mg, at a yield of 74%). 1H NMR (500 MHz, CDCl3): δ 9.66 (d, J=7.5 Hz, 2H), 7.77 (s, 2H), 7.67 (d, J=15.5 Hz, 2H), 7.25 (s, 2H), 6.49˜6.44 (m, 2H), 6.79˜6.70 (m, 6H), 2.92˜2.89 (m, 4H), 2.83 (d, J=7.0 Hz, 4H), 1.82˜1.80 (m, 6H), 1.39˜1.24 (m, 64H), 0.94˜0.84 (m, 18H).
Reaction 2:
M16 (100 mg, 0.071 mmol), 2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene) malononitrile (82 mg, 0.357 mmol) and CHCl3 (3 mL) were added into a 100-mL three-necked flask and stirred with a magnet. The reaction mixture was purged with argon for 30 minutes. Add pyridine (0.05 mL) to the reaction mixture, and react at room temperature for 1 hour. After the reaction is finished, add MeOH (10 mL) and stir for 30 minutes. Collect the solid by filtration and rinse the solid with acetone to get the dark blue solid organic semiconducting compound 3 (80 mg, at a yield of 61%). 1H NMR (500 MHz, CDCl3): δ 8.52˜8.48 (s, 4H), 8.38˜8.36 (m, 2H), 7.84 (s, 2H), 7.67˜7.65 (m, 2H), 7.60˜7.57 (m, 2H), 7.35 (s, 2H), 2.98˜2.95 (m, 4H), 2.92˜2.90 (m, 4H), 1.90˜1.88 (m, 6H), 1.52˜1.26 (m, 64H), 1.00˜0.89 (m, 18H).
Experimental examples of organic semiconducting compounds under the subject invention are shown in Table 1.
Furthermore, the organic semiconducting compounds under the subject invention can be used as materials for charge transporting, semiconducting, conducting, photo-conducting, or light-emitting in components or devices such as optics, electro-optics, electronics, electroluminescence (EL), or photoluminescence (PL). In such components or devices, the organic semiconducting compounds under the subject invention are generally applied as thin layers or films.
Furthermore, the organic semiconducting compounds under the subject invention are suitable to act as electron acceptors or n-type semiconductors for organic photoelectronic components, as well as suitable for preparing admixtures of n-type and p-type semiconductors for applications in fields such as organic photodetector (OPD) devices, etc. Wherein, the term “n-type” or “n-type semiconductors” refer to as extrinsic semiconductors in which the density of conducting electrons exceeds the density of mobile holes, whereas the term “p-type” or “p-type semiconductors” refers to mean Refers to extrinsic semiconductors in which the density of mobile holes exceeds the density of conducting electrons (see also J. Thewlis, Concise Dictionary of Physics, Pergamon Press, Oxford, 1973).
When the organic semiconducting compound under the subject invention is to be processed, it is necessary to introduce one or more small molecular compounds and/or polymers of the characteristics of charge transport, semi-conductivity, conductivity, photoconductivity, hole blocking, electron blocking, to be mixed therein for the preparation of the first constituent.
Furthermore, the organic semiconducting compound under the subject invention can be mixed with one or more organic solvents (preferable solvents such as aliphatic hydrocarbons, chlorinated hydrocarbons, aromatic hydrocarbons, ketones, ethers) and admixtures thereof (such as toluene, o-xylene, p-xylene, 1,3,5-trimethylbenzene or 1,2,4-trimethylbenzene, tetrahydrofuran, 2-methyltetrahydrofuran), to be mixed therein for the preparation of the second constituent.
Note that the organic semiconducting compounds under the subject invention may also be used in patterned OSC layers in devices as described herein. For microelectronic applications nowadays, it is generally desirable to produce small structures or patterns to reduce cost (i.e., more devices produced per unit area), and power consumption. The patterning of thin layers comprising the organic semiconducting compounds under the subject invention can be carried out, for example, through lithography, electron beam etching techniques, or laser patterning.
As for the application of the organic semiconducting compounds under the subject invention as the thin layers in electronic or electro-optical devices, the first constituent or the second constituent containing the organic semiconducting compounds, as prepared in the preceding paragraphs, can be deposited by any suitable methods. Solution process coating of the device is better than vacuum deposition technology. The second constituent consisting of the organic semiconducting compound under the subject invention enables the use of several solution process coating techniques.
Preferably, the deposition techniques include, but are not limited to, dip coating, spin coating, inkjet printing, nozzle printing, letterpress printing, screen printing, gravure printing, knife coating, roll printing, reverse roll printing, lithographic printing, dry offset (letterset) printing, flexographic printing, web printing, spray coating, curtain coating, brush coating, slot-dye coating, or pad printing (transfer printing).
Therefore, the subject invention also provides organic photoelectronic components comprising the organic semiconducting compound or the first constituent or the second constituent consisting of the organic semiconducting compound.
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The above-mentioned substrate 100 preferably provides a transparent glass substrate or transparent flexible substrate with mechanical strength and thermal strength, wherein the material of the transparent flexible substrate can be, namely: polyethylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polypropylene, polystyrene, polymethyl methacrylate, polyvinyl chloride, polyvinyl alcohol, polyvinyl butyraldehyde, nylon, polyetheretherketone, polysulfone, polyethersulfone, tetrafluoroethylene ethylene-pentafluoroalkyl trifluorovinyl ether copolymer, polyvinyl fluoride, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, polyvinylidene difluoride, polyester, poly carbonate, polyurethane, polyimide, etc.
The above-mentioned first electrode 110 is preferably made of transparent metal oxides such as indium oxide, tin oxide, etc.; as well as their derivatives doped with halogens (e.g., fluorine doped tin oxide (FTO)), or composite metal oxides (e.g. indium tin oxide (ITO), indium zinc oxide (OZO), etc.
The above-mentioned second electrode 130 is a metal oxide, a metal (silver, aluminum, or gold), a conductive polymer, a carbon-based conductor, a metal compound, or a conductive film alternately composed of the above-mentioned materials.
Preferably, the active layer 120 of the organic photoelectronic component 10 includes at least one n-type organic semiconducting compound which is the organic semiconducting compound under the subject invention, as well as at least one p-type organic semiconducting compound.
More preferably, the p-type organic semiconducting compound of the organic photoelectronic component 10 is selected from the group consisting of the following chemical groups:
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In the aforementioned third to sixth implementation approach, the first carrier transporting layer may be selected from conjugated polymer electrolytes, such as PEDOT:PSS; or polymer acids, such as polyacrylates; or conjugated polymers, such as polytriarylamine (PTAA); or insulating polymers, such as Nafion films, polyethyleneimine, or polystyrene sulfonate; or polymer-doped metal oxides, such as MoOx, NiOx, WOx, SnOx; or organic small molecule compounds, such as N, N′-diphenyl-N, N′-bis(1-naphthyl)(1,1′-biphenyl)-4,4′-diamine (NPB), N, N′-diphenyl-N, N′-(3-methylphenyl)-1,1′-biphenyl-4,4′-diamine (TPD); or a combination of one or more of the above-mentioned materials.
In the aforementioned third to sixth implementation approach, the second carrier transporting layer can be selected from conjugated polymer electrolytes, such as polyethyleneimine; or conjugated polymers, such as poly[3-(6-trimethyl) ammoniumhexyl)thiophene], poly(9,9)-bis(2-ethylhexyl-fluorene)-b-poly[3-(6-trimethylammoniumhexyl)thiophene], and poly[(9,9-bis(3′-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)]; or small organic compounds, such as tris (8-quinolinyl)-aluminum (III)(Alq3), 4,7-diphenyl-1,10-phenanthroline; or metal oxides, such as ZnOx, aluminum-doped ZnO (AZO), TiOx or its nanoparticles; or salts such as LiF, NaF, CsF, CsCO3; or amines such as primary, secondary, or tertiary amines.
To illustrate the efficacy improvement brought by the organic semiconducting compound under the subject invention applied to an organic photoelectronic component, the organic photoelectronic components comprising the organic semiconducting compound under the subject invention will be prepared for property testing and efficacy performance. The test results are as follows:
Use a UV-visible spectrometer to detect the absorption spectrum of the samples. First, apply chloroform to dissolve the samples before the measurement of samples. When the solid state is measured, the samples must be prepared into a thin film before the measurement can be taken. To preparation of thin film samples: Configure the concentration of the sample to be 5 wt %. Use the glass as the substrate and coat the thin film on the glass by spin coating, then measure the absorption of the solid thin film. The absorption spectra of each sample are shown in
Organic semiconducting compound I and organic semiconducting compound 2 can be dissolved at more than 14 mg/ml with o-xylene, whereas organic semiconducting compound 3 can be dissolved 5 mg/mL with o-xylene. All three organic semiconducting compounds have good solubility with non-halogen solvents. The onset of the absorption spectrum for organic semiconducting compound 1 and organic semiconducting compound 3 is 1,120 nm and 1,113 nm, respectively, which means that the materials have a light absorption capacity greater than 1,000 nm, thus covering wide ranges of applications such as 1,050 nm and 1,100 nm. Comparative Example 1 (Table 2 above) is cited from J. Mater. Chem. C, 2019, 7, 8820˜8824; whereas Comparative Example 2 is cited from Appl. Phys. Lett. 2006, 89, 081106. In Comparative Example 1, the onset of the absorption spectrum is only located at 847 nm, which is smaller than the spectral range of the subject invention. In Comparative Example 2, the onset of the absorption spectrum can reach 1,220 nm, however, the maximum absorption peak is only at 865 nm, which means that the intensity of the absorption range over 1,000 nm is relatively insufficient.
Use an electrochemical analyzer to record the oxidation and reduction potentials. Take 0.1 M Bu4NPF6 (tetra-1-butylammonium hexafluorophosphate) acetonitrile solution as the electrolyte. 0.01 M AgNO3 (silver nitrate) and 0.1 M TBAP (tetrabutylammonium perchlorate) in acetonitrile solution was added into the Ag/AgCl reference electrode. Take platinum (Pt) as the counter electrode, and carbon glass electrode as the working electrode. Using chloroform to dissolve the materials and drop them onto the working electrode, after drying, a thin film was formed. During the measurement, adopt the scan rate of 50 mV/sec and record the redox curve at the same time. When making a CV figure, its redox potential can be obtained. Take ferrocene/ferrocenium (Fc/Fc+) as an internal reference potential, and with the correction, and derive the HOMO and LUMO values. The calculation formula is as follows:
HOMO=−(4.71 eV+(Eox−Eref)))
LUMO=HOMO+Egopt
The test results for each sample are shown in Table 2.
Take a pre-patterned ITO-coated glass with sheet resistivity as the substrate. Sonicate sequentially the substrate in a neutral detergent, deionized water, acetone, and isopropanol. In each of such step, carry out the rinsing for 15 minutes. The washed substrate was further treated with a UV-O3 cleaner for 15 minutes. Apply the top coating of AZO (aluminum doped zinc oxide nanoparticle) on the ITO substrate at a spin rate of 2,000 rpm for 40 seconds. Dry the substrate with heat at 120° C. in the air for 5 minutes. Prepare the active layer solution in o-xylene (where the weight ratio of the donor. i.e., polymer, to the acceptor, i.e. small molecule, is 1:1). The concentration of the polymer is 20 mg/ml. To completely dissolve the polymer. the active layer solution should be stirred on a hot plate at 100° C. for at least 3 hours. Filter the active layer solution through a PTFE membrane filter (with pore size 0.45˜1.2 μm), and heat the active layer solution for 1 hour. Then, let the solution cool down to room temperature before coating. Control the coating speed so that film thickness is within the range of 100˜300 nm. Once done, the thin films were annealed at 100° C. for 5 minutes and then transfer the thin films to an evaporator. Deposit of a thin layer (8 nm) of molybdenum trioxide as a hole transporting layer under 3×10−6 torr. Use a Keithley™ 2,400 source meter to record the dark current (ID, bias voltage at −8V) in the absence of light. Next, use a solar simulator (a xenon lamp with an AM 1.5G filter, 100 mW cm−2) to measure photocurrent (Iph) characteristics of the component in air and at room temperature. Use a standard silicon diode with a KG5 filter is used as a reference cell for the calibration of the light intensity so that the mismatched portion on the spectrum can reach consistency. Use an external quantum efficiency meter for the measurement of the external quantum efficiency (EQE), with a measurement range of 300˜1,800 nm (bias voltage of 0˜−8V). Use silicon (300˜1,100 nm) and germanium (1,100˜1,800 nm) for calibration of the light source.
The current density and external quantum efficiency of each sample are shown in
In these experimental examples, the dark current and external quantum efficiency (EQE) of the organic photoelectronic components under the subject invention are measured, and their responsivity (R) and detectivity (D) thereof are calculated by the following formulas:
where
λ is the wavelength,
q is the unit charge,
h is Planck constant,
c is the speed of light, and
JD is the dark current density.
Comparative Example 2 in the subject invention is cited from the experimental results in the literature Appl. Phys. Let. 2006, 89, 081106. Since the test values of responsivity and detectivity are not directly listed in Comparative Example 2, the values in Table 3 are calculated based on the experimental data of this article.
It can be seen from the experimental results that in the wavelength band over 1,000 nm, the organic photoelectronic components containing the organic semiconducting compounds under the subject invention demonstrate good EQE performance. The dark current can reach 7.22×10−9 A/cm2 at −4V bias. In addition, in the wavelength band of 1,050 nm, the responsivity is 0.125 A/W and the detectivity is 1.70×1012 Jones, which is a significantly enhanced performance compared with the responsivity (<0.01 A/W) in Comparative Example 2. In Comparative Example 1, the EQE of the material disclosed shows a responsivity of only 300˜850 nm, whereas, in the experimental examples for the subject invention, the EQE has been extended a responsivity to more than 1,000 nm. Except for the applications under bias voltage −4V, the organic photoelectronic components demonstrate an effective dark current under bias voltage −8V as well as a responsivity or detectivity of 2.15×1012 Jones under the condition of 1,050 nm, which is superior in characteristics in comparison with those materials of a light absorption ability with onset value at over 1,000 nm.
| Number | Date | Country | |
|---|---|---|---|
| 63235875 | Aug 2021 | US |
