Non-fused ring n-type organic semiconductor material, preparation method and application thereof
By designing an amide core and electron-withdrawing end groups from non-fused-ring n-type organic semiconductor materials, the synthesis challenges of fused-ring structures were solved, enabling the development of organic field-effect transistor devices with high yield and high electron mobility, which have commercial potential.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2023-09-25
- Publication Date
- 2026-04-14
AI Technical Summary
The synthetic routes for fused-ring n-type organic semiconductor small molecules are long, difficult to purify, and have low yields, which is not conducive to commercial production. Furthermore, the fused-ring structure affects charge transport performance.
Using non-fused-ring n-type organic semiconductor materials, organic field-effect transistor devices are prepared by maintaining the planar conjugated structure through the interaction of non-covalent bonds between the amide core and the electron-withdrawing end group, and by introducing 2-ethylhexyl groups to improve solubility.
Rapid film formation of organic semiconductor materials was achieved, improving electron mobility by an order of magnitude, exhibiting good solubility and film formation performance, reducing preparation costs, and demonstrating excellent electrical properties.
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Figure CN117343084B_ABST
Abstract
Description
Technical Field
[0001] This application belongs to the field of organic semiconductor materials technology, and particularly relates to a non-fused ring n-type organic semiconductor material, its preparation method and application. Background Technology
[0002] Organic semiconductor materials are functional materials composed of organic conjugated molecules. Based on their charge transport characteristics, they can be classified into hole-type (p-), electron-type (n-), and bipolar types. Among them, n-type organic semiconductor small molecules have the advantage of a defined molecular weight and can complement p-type organic semiconductor materials. Therefore, developing high-performance n-type organic semiconductor small molecules is crucial.
[0003] Currently, most n-type organic semiconductor small molecules are designed based on large conjugated fused ring structures. This is mainly because large fused ring structures can provide large π delocalized electron clouds, enabling electron delocalization and transport. Furthermore, fused ring structures facilitate the coupling of electron clouds between molecules, enabling π-π stacking between molecules and promoting charge transfer and transport between molecules.
[0004] However, common fused ring structures generally result in problems such as long synthetic routes, difficult purification, and low yield, which are not conducive to commercial production and application. Furthermore, the intramolecular tension brought about by fused ring structures may affect molecular stacking and easily affect charge transport performance. Summary of the Invention
[0005] This application discloses a non-fused-ring n-type organic semiconductor material, its preparation method, and its application, which solves the technical problems of small molecules of fused-ring n-type organic semiconductors being unfavorable for molecular stacking, as well as the complex synthesis and low yield.
[0006] To achieve the above objectives, the technical solution of this application is:
[0007] The first aspect of this application discloses a non-fused-ring n-type organic semiconductor material. The non-fused-ring n-type organic semiconductor material of this application possesses the structure of formula i:
[0008]
[0009] R is one of H, F, and Cl.
[0010] In some embodiments, the non-fused-ring n-type organic semiconductor material contains compounds of formulas i-1, i-2, and i-3:
[0011]
[0012] A second aspect of this application discloses a method for preparing a non-fused-ring n-type organic semiconductor material, the method comprising:
[0013] Compound 3 is shown in formula ii;
[0014] In the presence of pyridine and under the protection of an inert gas, compound 3 undergoes a condensation reaction with indanedione malononitrile / dihalonedindanedione malononitrile in an alkaline organic solvent;
[0015] After the reaction is complete, the reactants are cooled, concentrated, and purified sequentially to obtain the final product.
[0016]
[0017] In some embodiments, the molar ratio of compound 3 to indanedione malononitrile / dihalogenated indanedione malononitrile is 1:2-6.
[0018] In some embodiments, the condensation reaction occurs at a temperature of 40-70°C for 6-12 hours.
[0019] In some embodiments, the alkaline organic solvent includes chloroform, 1,2-dichloroethane, tetrahydrofuran, acetonitrile, 1,4-dioxane, and toluene.
[0020] The third aspect of this application discloses the application of a non-fused ring n-type organic semiconductor material in the fabrication of semiconductor layers including organic field-effect transistor devices.
[0021] The fourth aspect of this application discloses an organic field-effect transistor device having a bottom-gate top-contact structure, comprising:
[0022] Substrate;
[0023] An insulating layer disposed on the first surface of the substrate;
[0024] A semiconductor layer disposed on the surface of the substrate opposite to the insulating layer;
[0025] And, a source electrode and a drain electrode disposed on the surface of the semiconductor layer opposite to the insulating layer;
[0026] The semiconductor layer is prepared from the non-fused-ring n-type organic semiconductor material described in claim 1 or 2.
[0027] The fifth aspect of this application discloses a method for fabricating an organic field-effect transistor device, the method comprising:
[0028] After the insulating layer is deposited on the first surface of the substrate, it is cleaned and dried;
[0029] After modifying the surface of the insulating layer away from the substrate with octadecylsilane and covering it with the non-fused ring n-type organic semiconductor material, it is annealed to form a semiconductor layer.
[0030] The source electrode and drain electrode are prepared on the surface of the semiconductor layer opposite to the insulating layer.
[0031] In some embodiments, the annealing treatment is performed at a temperature of 50-180°C for a time of 30-60 minutes.
[0032] Compared with the prior art, the advantages or beneficial effects of the embodiments of this application include at least the following:
[0033] The non-fused-ring n-type organic semiconductor material disclosed in this application, through its amide core and electron-withdrawing end groups, achieves intramolecular non-covalent interactions based on the interaction between the carbonyl group in the amide core and the sulfur atom in the adjacent thiophene. This maintains a good planar conjugated structure, effectively releasing intramolecular tension and enabling π-π stacking between organic semiconductor molecules via the 3-(dicyanomethylene)indophenone end groups, thus achieving rapid film formation in OFETs. Simultaneously, the 2-ethylhexyl group introduced into the organic semiconductor material's molecular structure effectively increases its solubility, significantly improving its film-forming performance. Furthermore, the results of the examples show that the electron mobility of this non-fused-ring n-type organic semiconductor material in OFET devices is 1.1 × 10⁻⁶. -3 cm 2 V -1 s -1 It has an electron mobility that is an order of magnitude higher than that of similar structures with fused rings, and has great application potential in the field of semiconductor materials. Attached Figure Description
[0034] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments recorded in this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0035] Figure 1 This is a schematic diagram of the structure of an organic field-effect transistor device provided in an embodiment of this application;
[0036] Figure 2 The compound IMIC provided in the embodiments of this application 1 H NMR spectrum;
[0037] Figure 3 The compound number of the compound IMIC provided in the embodiments of this application;
[0038] Figure 4Electron transfer characteristic curves of an organic field-effect transistor device based on IMIC provided for embodiments of this application;
[0039] Figure 5 The output characteristic curve of the organic field-effect transistor device based on IMIC provided in the embodiments of this application. Detailed Implementation
[0040] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of this application. All other embodiments obtained by those skilled in the art based on the embodiments of this application without creative effort are within the scope of protection of this application.
[0041] In the relevant descriptions of this embodiment, the terms "including," "containing," and "possessing" are open terms, meaning to include but not limited to; the term "at least one" means one or more, where "multiple" means two or more; the term "at least one of the following" or similar expressions refer to any combination of these items, including any combination of single or multiple items, for example, "at least one of a, b, or c", or "at least one of a, b, and c", which can all represent: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple; the symbol "A / B" is used to describe the selection relationship of associated objects, generally indicating an "or" relationship.
[0042] In the following description of the embodiments, the terminology used in the embodiments of this application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The singular forms "a" and "the" as used in the embodiments of this application and the appended claims are also intended to include the plural forms, unless the context clearly indicates otherwise.
[0043] Those skilled in the art should understand that, in the following description of the embodiments of this application, the sequence of numbers does not imply the order of execution. Some or all steps may be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of this application.
[0044] Those skilled in the art will understand that the numerical ranges in the embodiments of this application should be understood to specifically disclose each intermediate value between the upper and lower limits of the range. Each smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included within the scope of this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.
[0045] Unless otherwise stated, the technical / scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains. While this application describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this application. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.
[0046] In a first aspect, embodiments of this application provide a non-fused-ring n-type organic semiconductor material having the structure of formula i:
[0047]
[0048] R is one of H, F, and Cl.
[0049] The n-type organic semiconductor material provided in this application is an A-DA'DA type organic semiconductor small molecule. Specifically, through the structural design of the contained amide core and electron-withdrawing end groups, non-covalent interactions are formed within the molecule based on the electron-withdrawing effect of the carbonyl group in the amide core and the electron-donating effect of the sulfur atom in the adjacent thiophene. This allows the organic semiconductor material molecule to maintain a good planar conjugated structure, thereby effectively releasing intramolecular tension. This enables π-π stacking between organic semiconductor material molecules through the 3-(dicyanomethylene)indophenone end groups, achieving rapid film formation of the organic semiconductor material molecule in OFET. Simultaneously, the 2-ethylhexyl group introduced into the organic semiconductor material molecule structure effectively increases the solubility of the organic semiconductor material, significantly improving its film-forming performance. Particularly important is that the electron mobility of this non-fused-ring n-type organic semiconductor material in OFET devices is 1.1 × 10⁻⁶. -3 cm 2 V -1 s -1 Compared to similar structures with fused rings, its electron mobility is increased by an order of magnitude, which has great application potential in the field of semiconductor materials.
[0050] Based on the general structure described in formula i above, the non-fused-ring n-type organic semiconductor materials of this application contain compounds of formulas i-1, i-2, and i-3:
[0051]
[0052] These compounds possess excellent electron mobility, and are characterized by readily available raw materials, simple synthesis, high yield, good light absorption performance, and solution processability. When used to prepare organic field-effect transistor devices, they can not only exhibit excellent electrical performance, but also have advantages such as flexibility, bendability, low cost and power consumption, and environmental friendliness, showing promising prospects for commercial application.
[0053] In a second aspect, embodiments of this application provide a method for preparing the non-fused-ring n-type organic semiconductor material described in the first aspect, wherein the method preferably includes:
[0054] Compound 3 is shown in formula ii;
[0055] In the presence of pyridine and under the protection of an inert gas, compound 3 undergoes a condensation reaction with indanedione malononitrile / dihalonedindanedione malononitrile in an organic solvent;
[0056] After the reaction is complete, the reactants are cooled, concentrated, and purified sequentially to obtain the final product.
[0057]
[0058] Compound 3 is synthesized according to methods known in the art, and this application embodiment does not impose any particular limitations on this method. For example, this application embodiment can synthesize it according to the following method, which includes:
[0059] After reacting dihalomaleic anhydride with 2-ethylhexylamino via ammonolysis, the organic phase was separated, dried, and purified to obtain compound 1.
[0060] Under inert gas protection and palladium catalysis, compound 1 was coupled with a tributyltin alkylthiophene-thiophene derivative, and the reactants were sequentially cooled, concentrated, and purified to obtain compound 2.
[0061] Under the protection of an inert gas and the action of phosphorus oxychloride, compound 2 undergoes a formylation reaction with 1,2-dichloroethane and N,N-dimethylformamide. The organic phase is then separated, dried, and purified to obtain compound 3.
[0062] The preparation method provided in this application uses dihalomaleic anhydride as the starting material and proceeds sequentially through ammonolysis, Stille coupling, Vilsmeier-Haack reaction and dehydration condensation reaction to prepare non-fused-ring n-type organic semiconductor materials. The preparation process avoids photocatalytic cyclization, thereby simplifying the synthesis method and significantly improving the yield. It has the advantages of simple synthesis and high yield.
[0063] In a specific embodiment, the molar ratio of compound 3 to indanedione malononitrile / dihalogenated indanedione malononitrile is preferably 1:2-6.
[0064] In a specific embodiment, the temperature at which the condensation reaction occurs is preferably 40-70°C, and the time is preferably 6-12 hours.
[0065] In a specific embodiment, the alkaline organic solvent is preferably one of chloroform, 1,2-dichloroethane, tetrahydrofuran, acetonitrile, 1,4-dioxane, and toluene.
[0066] Thirdly, embodiments of this application provide the application of the aforementioned non-fused-ring n-type organic semiconductor material in the fabrication of semiconductor layers for organic field-effect transistor devices. Given that the aforementioned non-fused-ring n-type organic semiconductor material possesses advantages such as good electron mobility, simple synthesis, and high yield, the use of this material in the fabrication of semiconductor layers for organic field-effect transistor devices can significantly reduce fabrication costs and enhance their commercial application value while enabling the devices to exhibit excellent electrical performance.
[0067] Fourthly, embodiments of this application provide an organic field-effect transistor device. Please refer to... Figure 1 As shown, the organic field-effect transistor device has a bottom-gate top-contact structure, which includes:
[0068] Single-crystal Si substrate;
[0069] A SiO2 insulating layer disposed on the first surface of the single-crystal Si wafer substrate;
[0070] An IMIC semiconductor layer disposed on the surface of the single-crystal Si substrate opposite to the SiO2 insulating layer;
[0071] In addition, an Au source electrode and an Au drain electrode are disposed on the IMIC semiconductor layer opposite to the SiO2 insulating layer;
[0072] The IMIC semiconductor layer is made of the non-fused ring n-type organic semiconductor material described above.
[0073] Based on the excellent electron mobility of the non-fused-ring n-type organic semiconductor material described above, the organic field-effect transistor device of this application embodiment exhibits superior electrical performance. Performance testing shows that the electron mobility of the organic field-effect transistor device of this application embodiment can reach 1.1 × 10⁻⁶. -3 cm 2 V -1 s -1 .
[0074] Fifthly, embodiments of this application provide a method for fabricating an organic field-effect transistor device, the method comprising:
[0075] After the insulating layer is deposited on the first surface of the substrate, it is cleaned and dried;
[0076] After modifying the surface of the insulating layer away from the substrate with octadecylsilane and covering it with the non-fused ring n-type organic semiconductor material, it is annealed to form a semiconductor layer.
[0077] The source electrode and drain electrode are prepared on the surface of the semiconductor layer opposite to the insulating layer.
[0078] In a specific embodiment, the annealing treatment temperature is 50-180℃ and the time is 30-60min.
[0079] Annealing at this temperature can eliminate internal stress in materials, improve the orderliness of crystal structures, and enhance material properties.
[0080] The technical solution of this application will be further described below with reference to specific embodiments.
[0081] Example 1
[0082] This embodiment provides the synthetic route and specific preparation method of compound IMIC, wherein the synthetic route is as follows:
[0083]
[0084] The preparation method based on the aforementioned synthetic route includes steps S101-S104:
[0085] Synthesis of S101-Compound 1:
[0086] 10 mmol of dihalomaleic anhydride, 15 mmol of 2-ethylhexylamino, and 25 mL of acetic acid were added to a reaction flask. After reflux overnight, the reaction mixture was cooled to room temperature and quenched in a saturated aqueous solution of NaHCO3. The organic phase was extracted with CH2Cl2 and dried over anhydrous Na2SO4. The crude product was purified by silica gel column chromatography to give compound 1 (2.96 g, 81%) as a pale yellow solid with the following structure:
[0087]
[0088] Among them, compound 1 1H NMR (400MHz, CDCl3; δ, ppm): 3.49 (d, J = 6.8Hz, 2H), 1.72 (m, 1H), 1.25 (m, 8H), 0.89 (t, 6H).13C NMR (100MHz, CDCl3; δ, ppm): 164.1, 129.1, 43.5, 38.2, 30.3, 28.3, 23.6, 22.8, 13.8, 10.2.MS (TOF-MS, m / z): Calcd for C 12 H 17 Br2NO2: 366.961, found 366.957.
[0089] Synthesis of S102-compound 2:
[0090] Under nitrogen protection, 1 mmol of compound 2, 2.5 mmol of tributyl(6-undecylthiopheno[3,2-b]thiophen-2-yl)stanane, and 0.05 mmol of Pd(PPh3)4 were dispersed in 20 mL of toluene. After stirring overnight at 100 °C, the reaction mixture was cooled to room temperature and concentrated under reduced pressure. The crude product was purified by thin-layer chromatography to give compound 2 (95%) as a red oil with the following structure:
[0091]
[0092] Among them, compound 2 1 H NMR (400MHz, CDCl3; δ, ppm): 8.08 (s, 2H), 7.12 (s, 2H), 3.53 (d, J = 7.2Hz, 2H), 2.70 (t, 4H), 1.72 (m, 7H), 1.26 (m, 38H), 0.88 (m, 12H).13C NMR (100MHz, CDCl3; δ, ppm): 170.3, 144.1, 138.9, 135.3, 130.9, 127.0, 125.1, 124.2, 42.4, 38.3, 31.77, 30.5 3,29.73,29.48,29.42,29.22,28.49,27.71,23.88,22.83,22.53,17.39,13.92,10.3.MS(TOF-MS,m / z):Calcd for C 46 H 67 NO2S4:793.405, found 793.407.
[0093] Synthesis of S103-compound 3:
[0094] Under nitrogen protection, at 0°C, 0.63 mmol of compound 2, 20 mL of 1,2-dichloroethane, and 5 mL of N,N-dimethylformamide (DMF) were added sequentially, followed by the slow addition of 0.8 mL of phosphorus oxychloride. The mixture was stirred for 1 h while maintaining the temperature. Next, the mixture was refluxed overnight at 85°C. The reaction mixture was poured into 100 mL of ice water, quenched with Na₂CO₃, and the organic phase was extracted with CH₂Cl₂. The mixture was then washed with brine and dried over anhydrous Na₂SO₄. The crude product was purified with silica gel to give a red oily compound 3 (82%), with the following structure:
[0095]
[0096] Among them, compound 3 1 H NMR (400MHz, CDCl3; δ, ppm): 10.14 (s, 2H), 8.10 (s, 2H), 3.56 (d, J = 7.2Hz, 2H), 3.09 (t, 4H), 1.82 (m, 7H), 1.24 (m, 38H), 0.85 (m, 12H).13C NMR (100MHz, CDCl3; δ, ppm): 182.6, 169.5, 144.9, 144.6, 143.7, 141.6, 135.9, 127.9, 124.8, 42.8, 38. 4,31.9,30.5,30.0,29.6,29.5,29.3,28.6,28.3,23.9,23.0,22.7,14.1,10.4.MS(TOF-MS,m / z):Calcd for C 48 H 67 NO4S4:849.395, found 849.397.
[0097] Synthesis of S104-compound IMIC:
[0098] Under nitrogen protection, 0.24 mmol of compound 3 and 1.44 mmol of 2-(3-oxo-2,3-dihydroindene-1-yl)malononitrile were dissolved in 100 mL of chloroform, followed by the addition of 2 mL of pyridine. The mixture was stirred overnight at 65 °C. After cooling to room temperature and concentrating under reduced pressure, the mixture was recrystallized from methanol. The crude crystallized product was purified by column chromatography to give a purplish-black solid, compound IMIC (95%), with the following structure:
[0099]
[0100] Among them, compound IMIC 1H NMR (400MHz, CDCl3; δ, ppm):9.07(s,2H),8.71-8.67(m,2H),8.21(s,2H),7.96-7.92(m,2H),7.82-7.74(m ,4H),3.59(d,J=8.0Hz,2H),3.18-3.07(m,4H),1.79-1.73(m,7H),1.48-1.28(m,38H),0.98-0.90(m,12H).
[0101] Figure 2 The image shows the compound IMIC. 1 H NMR spectrum; Figure 3 This is the compound number for compound IMIC.
[0102] according to Figure 2 and Figure 3 From the combination of these, we can see that C 12 C 25 A singlet appears at 9.07 ppm; C20 peaks occur between 8.68 and 8.7 ppm. 45 C 50 The peak is a multiple peak; 8.21 ppm is C 32 C 33 The peak is a single peak; 7.74-7.95 ppm is C 44 C 46 C 47 C 48 C 49 C 51 The peak at 3.58-3.6 ppm is the methylene peak of C8, exhibiting a doublet; the peak at 3.10-3.14 ppm is the C8 peak. 66 C 77 The peak is a triplet; 0.83-1.77 ppm is hydrogen from the remaining alkyl groups.
[0103] Example 2
[0104] This embodiment provides the synthetic route and specific preparation method of compound IMIC-4F, wherein the synthetic route is as follows:
[0105]
[0106] The preparation method based on the aforementioned synthetic route includes steps S201-S204:
[0107] Synthesis of S201-Compound 1:
[0108] 10 mmol of dihalomaleic anhydride, 15 mmol of 2-ethylhexylamino and 25 mL of acetic acid were added to a reaction flask and refluxed overnight. The reaction mixture was then cooled to room temperature and quenched in a saturated NaHCO3 aqueous solution. The organic phase was extracted with CH2Cl2 and dried over anhydrous Na2SO4. The crude product was purified by silica gel column chromatography to give compound 1 as a pale yellow solid.
[0109] Synthesis of S202-compound 2:
[0110] Under nitrogen protection, 1 mmol of compound 2, 2.5 mmol of tributyl(6-undecylthiopheno[3,2-b]thiophen-2-yl)stanane and 0.05 mmol of Pd(PPh3)4 were dispersed in 20 mL of toluene. After stirring overnight at 100 °C, the reaction mixture was cooled to room temperature and concentrated under reduced pressure. The crude product was purified by thin-layer chromatography to obtain compound 2 as a red oil.
[0111] Synthesis of S203-compound 3:
[0112] Under nitrogen protection, at 0°C, 0.63 mmol of compound 2, 20 mL of 1,2-dichloroethane, and 5 mL of N,N-dimethylformamide (DMF) were added sequentially, followed by the slow addition of 0.8 mL of phosphorus oxychloride. The mixture was stirred for 1 h while maintaining the temperature. Next, the mixture was refluxed overnight at 85°C. The reaction mixture was then poured into 100 mL of ice water, quenched with Na₂CO₃, and the organic phase was extracted with CH₂Cl₂. The mixture was washed with brine and dried over anhydrous Na₂SO₄. The crude product was purified with silica gel to give compound 3, which was a red oil.
[0113] Synthesis of S204-compound IMIC-4F:
[0114] Under nitrogen protection, 0.24 mmol of compound 3 and 1.44 mmol of 2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-yl)malononitrile were dissolved in 100 mL of chloroform, followed by the addition of 2 mL of pyridine. The mixture was stirred overnight at 65 °C. After cooling to room temperature and concentrating under reduced pressure, the mixture was recrystallized from methanol. The crude crystallized product was purified by column chromatography to give a purplish-black solid, compound IMIC-4F (90%), with the following structure:
[0115]
[0116] Elemental analysis: (C 72 H 71F4N5O4S4) Theoretical values: C, 67.85; H, 5.61; N, 5.49; O, 5.02; S, 10.06; Measured values: C, 67.90; H, 5.58; N, 5.51; O, 4.99; S, 10.05. HRMS (ESI) m / z: Theoretical value: 1274.4403; Measured value: 1274.4679 (M+H).
[0117] Example 3
[0118] This embodiment provides the synthetic route and specific preparation method of compound IMIC-4Cl, wherein the synthetic route is as follows:
[0119]
[0120] The preparation method based on the aforementioned synthetic route includes steps S301-S304:
[0121] Synthesis of S301-Compound 1:
[0122] 10 mmol of dihalomaleic anhydride, 15 mmol of 2-ethylhexylamino and 25 mL of acetic acid were added to a reaction flask and refluxed overnight. The reaction mixture was then cooled to room temperature and quenched in a saturated NaHCO3 aqueous solution. The organic phase was extracted with CH2Cl2 and dried over anhydrous Na2SO4. The crude product was purified by silica gel column chromatography to give compound 1 as a pale yellow solid.
[0123] Synthesis of S302-Compound 2:
[0124] Under nitrogen protection, 1 mmol of compound 2, 2.5 mmol of tributyl(6-undecylthiopheno[3,2-b]thiophen-2-yl)stanane and 0.05 mmol of Pd(PPh3)4 were dispersed in 20 mL of toluene. After stirring overnight at 100 °C, the reaction mixture was cooled to room temperature and concentrated under reduced pressure. The crude product was purified by thin-layer chromatography to obtain compound 2 as a red oil.
[0125] Synthesis of S303-Compound 3:
[0126] Under nitrogen protection, at 0°C, 0.63 mmol of compound 2, 20 mL of 1,2-dichloroethane, and 5 mL of N,N-dimethylformamide (DMF) were added sequentially, followed by the slow addition of 0.8 mL of phosphorus oxychloride. The mixture was stirred for 1 h while maintaining the temperature. Next, the mixture was refluxed overnight at 85°C. The reaction mixture was then poured into 100 mL of ice water, quenched with Na₂CO₃, and the organic phase was extracted with CH₂Cl₂. The mixture was washed with brine and dried over anhydrous Na₂SO₄. The crude product was purified with silica gel to give compound 3, which was a red oil.
[0127] Synthesis of S304-compound IMIC-4F:
[0128] Under nitrogen protection, 0.24 mmol of compound 3 and 1.44 mmol of 2-(5,6-dichloro-3-oxo-2,3-dihydro-1H-inden-1-yl)malononitrile were dissolved in 100 mL of chloroform, followed by the addition of 2 mL of pyridine. The mixture was stirred overnight at 65 °C. After cooling to room temperature and concentrating under reduced pressure, the mixture was recrystallized from methanol. The crude crystallized product was purified by column chromatography to give a purplish-black solid, compound IMIC-4Cl (84%), with the following structure:
[0129]
[0130] Elemental analysis: (C 72 H 71 Theoretical values for Cl4N5O4S4: C, 64.47; H, 5.41; N, 5.22; O, 4.77; S, 9.56. Measured values: C, 64.44; H, 5.38; N, 5.20; O, 4.79; S, 9.55. HRMS (ESI) m / z: Theoretical value: 1338.3221; Measured value: 1338.0014 (M+H).
[0131] Example 4
[0132] This embodiment provides a method for fabricating an organic field-effect thin-film transistor device 1, specifically including:
[0133] S401: After depositing the SiO2 insulating layer on the first surface of the single crystal Si wafer substrate according to the preparation method known in the art, the substrate is sequentially cleaned with hydrogen peroxide, isopropanol and ultrapure water, and then baked in a clean environment until all moisture is removed.
[0134] S402: Octadecylsilane is modified on the surface of the SiO2 insulating layer facing away from the single-crystal Si substrate, and a compound IMIC of approximately 50 nm is spin-coated. The thin-film device is annealed at 50-180°C for 30-60 min. Then, using a copper mesh as a template, gold (Au) with a thickness of approximately 20-50 nm is deposited as the source / drain electrodes. The structure of the organic field-effect thin-film transistor device is shown below. Figure 1 As shown.
[0135] according to Figure 1 As shown, the organic field-effect thin-film transistor device of this application has a bottom-gate top-contact structure, which includes:
[0136] Single-crystal Si substrate;
[0137] A SiO2 insulating layer disposed on the first surface of the single-crystal Si wafer substrate;
[0138] An IMIC semiconductor layer disposed on the surface of the single-crystal Si substrate opposite to the SiO2 insulating layer;
[0139] In addition, an Au source electrode and an Au drain electrode are disposed on the surface of the IMIC semiconductor layer opposite to the SiO2 insulating layer.
[0140] Organic field-effect thin-film transistor devices 2 and 3, based on IMIC-4F semiconductor layers and IMIC-4Cl semiconductor layers, were fabricated according to the method in Example 4.
[0141] Example 5
[0142] The performance testing of organic field-effect thin-film transistor devices was conducted by using a Keithly type digital source meter on a probe station to test the transfer and output curves of the devices. All organic field-effect thin-film transistor devices were tested in an atmospheric environment.
[0143] The performance parameter test results are shown in Table 1.
[0144] Table 1 - Performance parameters of different devices
[0145] Organic semiconductor layer <![CDATA[Hole mobility (cm 2 V -1 s -1 )]]> <![CDATA[Electron mobility (cm 2 V -1 s -1 )]]> Device 1 IMIC none <![CDATA[1.1×10 -3 ]]> Device 2 IMIC-4F none <![CDATA[3.7×10 -3 ]]> Device 3 IMIC-4Cl none <![CDATA[3.3×10 -3 ]]>
[0146] As shown in Table 1, the electron mobility of the organic field-effect transistor device based on IMIC in air is 1.1 × 10⁻⁶. -3 cm 2 V -1 s -1 The electron mobility of the organic field-effect transistor device based on IMIC-4F in air is 3.7 × 10⁻⁶. - 3 cm 2 V -1 s -1 The electron mobility of the organic field-effect transistor device based on IMIC-4Cl in air is 3.7 × 10⁻⁶. - 3 cm 2 V -1 s -1 All of them possess excellent electron mobility.
[0147] Furthermore, embodiments of this application also tested the electron transfer characteristic curves and output characteristic curves of an IMIC-based organic field-effect transistor device, and the results were as follows: Figures 4 to 5 As shown. Among them, Figure 4 The electron transfer characteristic curves of an IMIC-based organic field-effect transistor device are shown. Figure 5 The output characteristic curves of an IMIC-based organic field-effect transistor device are shown.
[0148] according to Figures 4 to 5 It can be seen that IMIC exhibits unipolar electron transport characteristics in air, with an electron mobility of 1.1 × 10⁻⁶ in the saturation region. -3 cm 2 V -1 s -1 The threshold voltage is 39.5V, and the on / off ratio reaches 1.8×10⁻⁶. 6 The output characteristic curves show that the IMIC, as an n-type semiconductor, can successfully achieve field-effect switching.
[0149] As can be seen from the performance tests described above, the non-fused-ring n-type organic semiconductor material provided in this application embodiment is composed of A-DA'DA type (A is the donor and D is the acceptor), which exhibits excellent performance while reducing structural conjugation and has good commercial prospects.
[0150] The various embodiments in this specification are described in a progressive manner. The same or similar parts between the various embodiments can be referred to each other. Each embodiment focuses on describing the differences from other embodiments.
[0151] The above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit this application. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of this application.
Claims
1. A non-fused-ring n-type organic semiconductor material, characterized in that, The structure of expression i: i R is one of H, F, and Cl.
2. The non-fused-ring n-type organic semiconductor material according to claim 1, characterized in that, Compounds containing formulas i-1, i-2, and i-3: i-1; i-2; i-3.
3. A method for preparing a non-fused-ring n-type organic semiconductor material according to claim 1 or 2, characterized in that, include: Compound 3, represented by formula ii; In the presence of pyridine and under the protection of an inert gas, compound 3 undergoes a condensation reaction with indanedione malononitrile / dihalonedindanedione malononitrile in an organic solvent; After the reaction is complete, the reactants are cooled, concentrated, and purified sequentially to obtain the final product. ii.
4. The preparation method according to claim 3, characterized in that, The molar ratio of compound 3 to indanedione malononitrile / dihalogenated indanedione malononitrile is 1:2-6.
5. The preparation method according to claim 3, characterized in that, The condensation reaction occurs at a temperature of 40-70℃ for 6-12 hours.
6. The preparation method according to claim 3, characterized in that, The organic solvents include chloroform, 1,2-dichloroethane, tetrahydrofuran, acetonitrile, 1,4-dioxane, and toluene.
7. The use of the non-fused-ring n-type organic semiconductor material according to claim 1 or 2 in the fabrication of semiconductor layers comprising organic field-effect transistor devices.
8. An organic field-effect transistor device having a bottom-gate top-contact structure, comprising: Substrate; An insulating layer disposed on the first surface of the substrate; A semiconductor layer disposed on the surface of the substrate opposite to the insulating layer; And, a source electrode and a drain electrode disposed on the surface of the semiconductor layer opposite to the insulating layer; The semiconductor layer is characterized in that it is prepared from the non-fused-ring n-type organic semiconductor material as described in claim 1 or 2.
9. A method for fabricating an organic field-effect transistor device according to claim 8, characterized in that, include: After the insulating layer is deposited on the first surface of the substrate, it is cleaned and dried; After modifying the surface of the insulating layer away from the substrate with octadecylsilane and covering it with the non-fused ring n-type organic semiconductor material, it is annealed to form a semiconductor layer. The source electrode and drain electrode are prepared on the surface of the semiconductor layer opposite to the insulating layer.
10. The preparation method according to claim 9, characterized in that, The annealing process is performed at a temperature of 50-180℃ for 30-60 minutes.