Blue light organic semiconductor material of a class of aromatic and sila polyheterocyclic ring and preparation method and application thereof
By preparing aromatic and silicon-hexane multi-cyclic blue light-emitting organic semiconductor materials, the problem of reduced luminescence in aggregated blue light-emitting organic materials was solved, enabling efficient and low-cost fabrication of undoped OLED devices and simplifying the process.
Patent Information
- Application Number
- CN202210926124.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2022-08-02
- Publication Date
- 2026-02-13
- Estimated Expiration
- 2042-08-02
AI Technical Summary
Existing blue organic light-emitting materials exhibit reduced or quenched luminescence in the aggregated state, making them difficult to apply to high-efficiency undoped OLED devices. Furthermore, devices prepared by solution spin coating have unsatisfactory performance, high cost, and complex processes.
A blue organic semiconductor material with aggregation-induced emission properties was prepared by using aromatic and silicon-hexane multi-cyclic blue light-emitting organic semiconductor materials and reacting diphenyl-naphthylsilane with a diarylacetylene derivative catalyzed by tris(triphenylphosphine)carbonyl dihydroruthenium. The material is suitable for spin coating and vacuum evaporation processes.
It achieves efficient blue light emission, reduces manufacturing costs, simplifies processes, improves device performance and stability, is suitable for various processing techniques, overcomes aggregation quenching, and is applicable to undoped OLED devices.
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Figure CN115403606B_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application belongs to the technical field of organic optoelectronic materials, and particularly relates to a kind of blue light organic semiconductor material of aromatic and sila-heteropolycyclic ring and its preparation method and application. BACKGROUND
[0002] Display technology, as one of the important information carriers, promotes the progress of human civilization. Organic light-emitting diode (OLED) is a kind of electroluminescence technology, which is considered to be the next generation of display and lighting technology due to its lightness, self-emission, fast response speed and other advantages. Its commercial application will change people's life. The core technology of OLED device is organic light-emitting layer material, which plays a decisive role in the performance of color, efficiency, etc. of the device. At the same time, OLED is a kind of solid-state light-emitting technology, so in addition to the molecular structure of organic light-emitting material, its aggregation behavior will also have a significant impact on the device results. Many organic light-emitting materials will exhibit very different light-emitting behavior from the dispersed state and the polymerized state. It often happens that the light-emitting of organic light-emitting materials in the aggregated state will be weakened or even quenched, which is commonly known as the aggregation-caused quenching (ACQ) phenomenon, so that these light-emitting materials usually need to be doped in the matching host to prepare high-efficiency OLED devices, but this also brings problems such as complex device process, increased preparation cost and unstable device operation.
[0003] Moreover, after nearly three decades of development in the field of OLED, great progress has been made in material preparation, process optimization and related theoretical research. With intramolecular or intermolecular energy transfer or conjugation effect, high-efficiency green and red light materials have been reported and gradually moved towards commercial field, but there is a relative lack of blue fluorescent materials with excellent performance.
[0004] Aggregation-induced emission (AIE) is a concept overturned by Tang's group in 2001, which refers to the phenomenon that the molecule emits little light in solution state, but emits light significantly enhanced in aggregated state or solid film. AIE materials can be applied in non-doped OLED devices, and have high efficiency and brightness. Therefore, non-doped OLED based on AIE materials usually has the characteristics of high device efficiency and low efficiency roll-off. However, due to too many torsional groups of most AIE molecules, the number of stable conformations is relatively large, which leads to relatively large half-peak width of the molecules, and the application in the field of blue light has not found a good solution (Cai, Y.; Qin, A.; Tang, B. Z. Siloles in optoelectronic devices. J. Mater. Chem. C 2017, 5, 7375-7389.).
[0005] In addition, the current film forming process of OLEDs mainly includes solution spin coating method and vacuum evaporation method. Although the performance and stability of the device prepared by the former are not ideal, the preparation cost of the organic electroluminescent device can be greatly reduced, which is more conducive to commercialization and mass production. Therefore, it is urgent to develop a blue light electroluminescent material system with AIE performance, high efficiency and multiple processing methods. SUMMARY
[0006] In order to overcome the above-mentioned deficiencies existing in the prior art, the purpose of the present application is to provide a kind of aromatic and silicon hetero multi-ring blue light aggregation induced emission organic semiconductor material and its preparation method and application.
[0007] The purpose of the present application is to overcome the deficiencies of the prior art, and to provide a kind of aromatic and silicon hetero multi-ring blue light organic semiconductor material system. The luminescent material has the advantages of simple preparation method, obvious aggregation induced emission characteristics and good solid-state fluorescence quantum yield.
[0008] The purpose of the present application is also to provide a preparation method of the aromatic and silicon hetero multi-ring blue light organic semiconductor material.
[0009] The purpose of the present application is also to provide the application of the aromatic and silicon hetero multi-ring blue light organic semiconductor material in preparing the light-emitting layer of spin-coated organic light-emitting diode.
[0010] The purpose of the present application is achieved at least by one of the following technical solutions.
[0011] A kind of aromatic and silicon hetero multi-ring blue light organic semiconductor material, the chemical structure formula is as follows:
[0012]
[0013] wherein, Ar1, Ar2 are functional control groups, and Ar3 is H or a functional control group. Ar1, Ar2 and Ar3 can be the same or different.
[0014] Preferably, the functional control group is phenyl, p-tert-butylphenyl, p-methoxyphenyl, p-fluorophenyl, p-trifluoromethylphenyl, p-cyanophenyl, furanylthienyl, biphenyl, terphenyl, carbazolyl, N-ethylcarbazolyl, dibenzofuranyl, naphthyl, isoquinolyl, phenanthrolinyl, p-tolyl, N-methylindolyl, diphenylamino, triphenylamino, t-butylphenylcarbazolyl or phenylcarbazolyl.
[0015] Preferably, the functional control group is one of the following structural formulae a-y:
[0016]
[0017] The preparation method of the aromatic and sila polyheterocyclic blue light organic semiconductor material includes the following steps:
[0018] Under the catalysis of tris(triphenylphosphine)carbonyl dihydrogen ruthenium (II), the diphenyl mononaphthyl silane derivative and the diaryl acetylene derivative are subjected to cyclization naphthosila six-membered ring in an organic solvent to obtain the aromatic and sila polyheterocyclic blue light organic semiconductor material.
[0019] The structural formula of the diaryl acetylene derivative is as follows:
[0020]
[0021] The structural formula of the diphenyl mononaphthyl silane derivative is as follows:
[0022]
[0023] Preferably, the molar ratio of the diphenyl mononaphthyl silane derivative and the diaryl acetylene derivative is 1.5:1-1:1.5.
[0024] Preferably, the organic solvent is toluene; and the molar volume ratio of the diphenyl mononaphthyl silane derivative and the organic solvent is 1:1.5-1:3 mmol / mL.
[0025] Preferably, the molar ratio of the diphenyl mononaphthyl silane derivative and tris(triphenylphosphine)carbonyl dihydrogen ruthenium (II) is 1:0.05-1:0.10.
[0026] Preferably, the reaction temperature is 110-130°C, and the reaction time is 15-30h.
[0027] The application of the above-mentioned blue light organic semiconductor material of aromatic and sila-hetero multicyclic ring in preparing electroluminescent or electrochemiluminescent devices.
[0028] Preferably, the blue light organic semiconductor material of aromatic and sila-hetero multicyclic ring is used as a light-emitting layer material, and the preparation of the light-emitting layer comprises the following steps: dissolving the blue light organic semiconductor material of aromatic and sila-hetero multicyclic ring with an organic solvent, and forming a film by spin coating to obtain the light-emitting layer.
[0029] The application of the above-mentioned blue light organic semiconductor material of aromatic and sila-hetero multicyclic ring in preparing metal phosphorescent compound devices, organic fluorescent compound devices and organic fluorescent compound sensitized devices, wherein the blue light organic semiconductor material is used as a host material.
[0030] The blue light organic semiconductor material of aromatic and sila-hetero multicyclic ring provided by the application has good photo-thermal stability and solubility, and can be used to prepare electroluminescent or electrochemiluminescent devices by solution spin coating and vacuum evaporation according to the needs of device structure; and can also be used as a host material of many material systems, and applied to the use of metal phosphorescent compound, organic fluorescent compound doping, sensitization and other devices.
[0031] Compared with the prior art, the application has the following advantages and beneficial effects:
[0032] (1) The blue light emitting material based on the aromatic and sila-hetero multicyclic ring unit of the application has a simpler synthesis route, more convenient raw materials and lower cost compared with the preparation method of the previous sila-heterocyclic compound, which greatly expands the applicable range of the molecule;
[0033] (2) The aggregation-induced emission material based on the aromatic and sila-hetero multicyclic ring unit of the application has efficient blue or deep blue light emission in the aggregated state, overcoming the difficulty of deep blue light emission of the aggregation-induced emission material;
[0034] (3) The blue light emitting material based on the aromatic and sila-hetero multicyclic ring unit of the application has obvious aggregation-induced emission properties, although it has weak light emission in the solution state, but has high fluorescence quantum yield in the aggregated state, so it can be used to prepare efficient non-doped OLED devices, and at the same time overcome the problems of device process complexity, increased preparation cost and unstable device operation caused by host-guest doping;
[0035] (4) The blue light emitting material based on the aromatic and sila-hetero multicyclic ring unit of the application has high solubility and good film forming property and stable film morphology, and is suitable for processing by spin coating, which will greatly help to reduce the cost;
[0036] (5) The blue light emitting material based on the aromatic and silyl polybasic ring unit of the present application has higher maximum brightness, maximum current efficiency and external quantum efficiency. BRIEF DESCRIPTION OF DRAWINGS
[0037] Figure 1 The graph of the test results of the aggregation-induced emission property of the blue light organic semiconductor material containing tetraphenyl naphthasilahexacyclic ring prepared in Examples 2, 3, 4, 6, 7;
[0038] Figure 2 The cyclic voltammogram of the blue light organic semiconductor material containing tetraphenyl naphthasilahexacyclic ring prepared in Examples 2, 3, 4, 6, 7;
[0039] Figure 3 The graph of the change of the brightness and current density of the electroluminescent device prepared from the blue light organic semiconductor material containing tetraphenyl naphthasilahexacyclic ring in Example 10 with the applied voltage;
[0040] Figure 4 The graph of the change of the external quantum efficiency of the electroluminescent device prepared from the blue light organic semiconductor material containing tetraphenyl naphthasilahexacyclic ring in Example 10 with the brightness of the device;
[0041] Figure 5 The electroluminescent emission wavelength of the electroluminescent device prepared from the blue light organic semiconductor material containing tetraphenyl naphthasilahexacyclic ring in Example 10. DETAILED DESCRIPTION
[0042] The present application will be further described in conjunction with the examples below, but the implementation and protection of the present application are not limited thereto. It should be noted that if the following processes are not specifically described in detail, they can be implemented or understood by those skilled in the art with reference to the prior art. If the reagents or instruments used are not marked with the manufacturer, they are considered to be conventional products that can be purchased on the market.
[0043] Example 1
[0044] Preparation of diphenylnaphthylsilane (DPNS)
[0045]
[0046] Reaction equation (I):
[0047]
[0048] A two-necked round bottom flask was charged with 1-bromonaphthalene (40 mmol, 8.283 g) and 70 mL of freshly distilled super-dry tetrahydrofuran, then the system was purged with nitrogen for 30 min to remove the nitrogen in the system, then n-butyllithium (50 mmol, 2.5 M, 20 mL) was added dropwise into the two-necked flask at -78 °C for 30 min, and the reaction was carried out for 3 h. Diphenylsilane chloride (44 mmol, 9.625 g) and 50 mL of freshly distilled super-dry tetrahydrofuran were added to a single-necked round bottom flask, then the system was purged with nitrogen for 30 min to remove the nitrogen in the system, then it was taken out and slowly dropped into the two-necked flask reaction system, and the two-necked flask was placed at room temperature and stirred overnight. After the reaction was completed, 30 mL of H2O was added to quench the residual n-butyllithium, then tetrahydrofuran was removed by distillation under reduced pressure, and then extracted with dichloromethane / water three times, and the obtained organic layer solution was washed with brine, and finally dried with anhydrous sodium sulfate. The dried organic solution was distilled under reduced pressure to remove the solvent, and then purified by silica gel chromatography to obtain a white solid (wherein petroleum ether was selected as the eluent). 1 H NMR (400 MHz, CDC13) δ 8.05 (d, J = 8.0 Hz, 1H), 7.93 (d, J = 8.2 Hz, 1H), 7.87 (d, J = 7.6 Hz, 1H), 7.62-7.56 (m, 5H), 7.49-7.34 (m, 9H), 5.90 (s, 1H).
[0049] Example 2
[0050] Preparation of blue light organic semiconductor material containing tetraphenyl naphthosilacyclohexane ring (TPNS-H)
[0051]
[0052] Reaction equation (two):
[0053]
[0054] Into a single necked round bottom flask, 8 mL of toluene was added, then the system was purged with nitrogen for 30 min to remove oxygen in the system. Into a double necked round bottom flask, DPNS (1.240 g, 4 mmol), tris(triphenylphosphine)carbonyl dihydrido ruthenium(II) (0.1832 g, 0.2 mmol) and diphenylacetylene (1.068 g, 6 mmol) were added, the system was purged with nitrogen for three times to make sure the system was under nitrogen protection, then the mixture in the single necked round bottom flask was added dropwise into the double necked round bottom flask, the reaction was heated under reflux at 125 °C for 20 h. After the reaction was completed, the reaction mixture was extracted with dichloromethane / water for three times, the obtained organic layer was washed with brine completely, then dried over anhydrous sodium sulfate. The dried organic solution was distilled under reduced pressure to remove the solvent, then the white solid powder was obtained by silica gel chromatography with petroleum ether as the eluent, the yield was 52%. 1 H NMR (400 MHz, CDC13) δ 7.99 (dt, J = 7.3, 3.6 Hz, 1H), 7.92 - 7.77 (m, 2H), 7.63 - 7.43 (m, 5H), 7.37 - 7.24 (m, 8H), 7.21 - 7.05 (m, 5H), 6.91 - 6.79 (m, 3H), 6.69 - 6.57 (m, 2H). 13 C NMR (101 MHz, CDC13) δ 154.09, 142.24, 141.68, 139.15, 136.74, 136.31, 135.16, 134.75, 133.37, 131.60, 131.31, 130.63, 130.18, 129.80, 129.45, 129.38, 127.72, 127.48, 127.02, 126.16, 125.42, 124.80.
[0055] Example 3
[0056] Preparation of blue light organic semiconductor material containing tetraphenyl naphtho-silacyclohexane ring (TPNS-F)
[0057]
[0058] Reaction equation (three):
[0059]
[0060] Into a single necked round bottom flask, 8 mL of toluene was added and then the system was purged with nitrogen for 30 min to remove oxygen from the system. Into a double necked round bottom flask, DPNS (1.240 g, 4 mmol), tris(triphenylphosphine)carbonyl dihydrido ruthenium (II) (0.1832 g, 0.2 mmol) and 1,2-di(4-fluorophenyl)acetylene (1.284 g, 6 mmol) were added and the system was purged with nitrogen three times to ensure that the system was under nitrogen atmosphere. Then the mixture in the single necked round bottom flask was added drop wise into the double necked round bottom flask and stirred at 125 °C for 20 h. After completion of the reaction, the reaction mixture was extracted with dichloromethane / water three times and the organic layer was washed with brine and dried over anhydrous sodium sulfate. The organic layer was distilled under reduced pressure to remove the solvent and the residue was purified by silica gel column chromatography to obtain white solid powder in 59% yield (eluent: petroleum ether). 1 H NMR (400 MHz, CDC13) δ 8.01 (dd, J = 8.2, 1.3 Hz, 1H), 7.90-7.78 (m, 2H), 7.63-7.43 (m, 5H), 7.38-7.23 (m, 8H), 7.09-6.98 (m, 2H), 6.93-6.82 (m, 2H), 6.68-6.40 (m, 4H). 13 C NMR (101 MHz, CDC13) δ 138.99, 138.00, 137.97, 137.39, 137.34, 136.87, 136.23, 134.89, 134.36, 133.96, 133.41, 132.05, 131.97, 131.53, 131.43, 130.71, 130.64, 130.49, 129.62, 129.43, 127.84, 125.54, 125.38, 114.76, 114.54, 114.26, 114.05.
[0061] Example 4
[0062] Preparation of blue light organic semiconductor material containing tetraphenyl naphtho-silacyclohexane ring (TPNS-M)
[0063]
[0064] Reaction Scheme (IV):
[0065]
[0066] Into a single necked round bottom flask, 8 mL of toluene was added, then the system was purged with nitrogen for 30 min to remove oxygen in the system. Into a double necked round bottom flask, DPNS (1.240 g, 4 mmol), tris(triphenylphosphine)carbonyl dihydrido ruthenium (II) (0.1832 g, 0.2 mmol) and di(4-methoxyphenyl)acetylene (1.429 g, 6 mmol) were added, the system was purged with nitrogen for three times to make sure the system was under nitrogen protection, then the mixture in the single necked round bottom flask was added dropwise, the reaction was heated at 125 °C for 20 h. After the reaction was completed, the reaction mixture was extracted with dichloromethane / water for three times, then the organic layer was washed with brine completely, finally dried over anhydrous sodium sulfate. The dried organic solution was distilled under reduced pressure to remove the solvent, then purified by silica gel chromatography to obtain white solid powder, the yield was 48% (the eluent was petroleum ether:dichloromethane = 1:1, v:v). 1 HNMR (400 MHz, CDC13) δ 7.98 (d, J = 8.0 Hz, 1H), 7.82 (dd, J = 15.1, 7.1 Hz, 2H), 7.67 - 7.40 (m, 5H), 7.31 (ddd, J = 20.0, 12.9, 6.3 Hz, 8H), 7.00 (d, J = 8.5 Hz, 2H), 6.73 (d, J = 8.5 Hz, 2H), 6.55 (d, J = 8.6 Hz, 2H), 6.43 (d, J = 8.6 Hz, 2H), 3.76 (s, 3H), 3.63 (s, 3H). 13 C NMR (101 MHz, CDC13) δ 157.73, 156.72, 153.98, 138.65, 136.61, 136.29, 135.66, 135.02, 134.84, 134.23, 134.06, 133.33, 131.70, 131.37, 131.20, 130.39, 130.03, 129.96, 129.35, 127.68, 125.37, 125.32, 112.98, 112.57, 55.09, 54.91.
[0067] Example 5
[0068] Preparation of blue organic semiconductor material containing tetraphenyl naphtho-silacyclohexane ring (TPNS-B)
[0069]
[0070] Reaction equation (five):
[0071]
[0072] Into a single-necked round-bottom flask, 8 mL of toluene was added, and then the system was purged with nitrogen for 30 min to remove oxygen in the system. Into a two-necked round-bottom flask, DPNS (1.240 g, 4 mmol), tris(triphenylphosphine)carbonyl dihydrido ruthenium (II) (0.1832 g, 0.2 mmol) and di(4-tert-butylphenyl)acetylene (1.743 g, 6 mmol) were added, and the system was purged with nitrogen three times to ensure that the system was under nitrogen protection. Then, the mixture in the single-necked round-bottom flask was added dropwise, and the system was heated to reflux at 125 °C for 20 h with stirring. After the reaction was completed, the system was extracted with dichloromethane / water three times, and the obtained organic layer solution was washed with brine and dried over anhydrous sodium sulfate. The dried organic solution was distilled under reduced pressure to remove the solvent, and then the white solid powder was obtained by silica gel chromatography with petroleum ether:dichloromethane = 15:1, v:v as the eluent, and the yield was 58%.
[0073] Example 6
[0074] Preparation of blue light organic semiconductor material containing tetraphenyl naphtho-silacyclohexane ring (TPA-NA-H)
[0075]
[0076] Reaction equation (V):
[0077]
[0078] The preparation method of TPA-NS was the same as that in Reference Example 1, except that 1-bromo naphthalene was replaced by 1-bromo, 4-triphenylamine naphthalene, the molar ratio of the substrate was the same as that in Example 1, and the other operations were the same as those in Example 1.
[0079] Into a single-necked round-bottom flask, 8 mL of toluene was added, and then the system was purged with nitrogen for 30 min to remove oxygen in the system. Into a two-necked round-bottom flask, TPA-NS (2.212 g, 4 mmol), tris(triphenylphosphine)carbonyl dihydrido ruthenium (II) (0.1832 g, 0.2 mmol) and diphenylacetylene (1.068 g, 6 mmol) were added, and the system was purged with nitrogen three times to ensure that the system was under nitrogen protection. Then, the mixture in the single-necked round-bottom flask was added dropwise, and the system was heated to reflux at 125 °C for 20 h with stirring. After the reaction was completed, the system was extracted with dichloromethane / water three times, and the obtained organic layer solution was washed with brine and dried over anhydrous sodium sulfate. The dried organic solution was distilled under reduced pressure to remove the solvent, and then the white solid powder was obtained by silica gel chromatography with petroleum ether:dichloromethane = 15:1, v:v as the eluent, and the yield was 70%.
[0080] Example 7
[0081] Preparation of blue light organic semiconductor material containing tetraphenyl naphtho-silacyclohexane ring (CZ-NA-H)
[0082]
[0083] Reaction equation (seven):
[0084]
[0085] The preparation method of CZ-NS is the same as that in Reference Example 1, except that 1-bromonaphthalene is replaced by 1-bromo, 4-phenylcarbazoyl naphthalene, the molar ratio of the substrates is the same as in Example 1, and the remaining operations can be referred to Example 1.
[0086] 8 mL of toluene was added into a single-port round-bottom flask, and then nitrogen was blown into the closed system for 30 min to remove oxygen in the system. CZ-NS (2.204 g, 4 mmol), tris (triphenylphosphine) carbonyl dihydrogen ruthenium (II) (0.1832 g, 0.2 mmol) and diphenylacetylene (1.068 g, 6 mmol) were added into a double-port round-bottom flask, and nitrogen was exchanged for three times to ensure that the closed system was under nitrogen protection, and then the mixture in the single-port round-bottom flask after oxygen removal was added dropwise, and stirred at 125℃ under reflux for 20 h. After the reaction was completed, it was extracted with dichloromethane / water three times, and the obtained organic layer solution was washed with brine and then dried with anhydrous sodium sulfate. The dried organic solution was distilled under reduced pressure to remove the solvent, and purified by silica gel chromatography to obtain a white solid powder with a yield of 53% (wherein the eluent is selected to be petroleum ether:dichloromethane = 15:1, v:v).
[0087] Example 8
[0088] Test of the aggregation-induced emission properties of TPNS-H (Example 2), TPNS-F (Example 3), TPNS-M (Example 4), TPA-NA-H (Example 6) and CZ-NA-H (Example 7) materials
[0089] TPNS-H compound 2.18 mg was weighed and dissolved in 5 mL of re-distilled tetrahydrofuran (THF) to prepare a test sample with a concentration of 10 -3 mol / L, numbered as A.
[0090] In the TPNS-H sample, 30 μL of liquid was taken into a 5 mL centrifuge tube, and the operation was repeated seven times. Then, 0 μL THF / 2970 μL H2O, 270 μL THF / 2700 μL H2O, 570 μL THF / 2400 μL H2O, 1170 μL THF / 1800 μL H2O, 1770 μL THF / 1200 μL H2O, 2370 μL THF / 600 μL H2O, and 2970 μL THF / 0 μL H2O were sequentially added into the seven centrifuge tubes to prepare AIE curve test samples with water contents of 99%, 90%, 80%, 60%, 40%, 20%, and 0%. The emission spectra of the AIE curve test samples were tested at the corresponding excitation wavelengths, and the AIE property curve of the compound TPNS-H was obtained through data processing.
[0091] The AIE properties of TPNS-F, TPNS-M, TPA-NA-H, and CZ-NA-H were tested in the same manner as TPNS-H, and the samples were sequentially numbered as B, C, E, and F.
[0092] The AIE properties of blue light organic semiconductor materials containing tetraphenyl naphtho-silacyclohexane were tested in the same manner as TPNS-H, and the samples were sequentially numbered as A, B, C, E, and F. Figure 1 . Figure 1 Figures A, B, C, E, and F are the photoluminescence spectra of the compounds TPNS-H, TPNS-F, TPNS-M, TPA-NA-H, and CZ-NA-H, respectively, tested in tetrahydrofuran / water solutions with different proportions, where f w is the proportion of water. Figures D and G are the fluorescence intensity change diagrams of the compounds TPNS-H, TPNS-F, TPNS-M, TPA-NA-H, and CZ-NA-H in tetrahydrofuran / water solutions with different water contents.
[0093] As can be seen from the figures, the blue light organic semiconductor materials of TPNS-H, TPNS-F, TPNS-M, TPA-NA-H, and CZ-NA-H all have certain AIE properties.
[0094] Example 9
[0095] Electrochemical energy level test based on the compounds TPNS-H, TPNS-F, TPNS-M, TPA-NA-H, and CZ-NA-H
[0096] The 1.9372 g of tetrabutylammonium hexafluorophosphate electrolyte was dissolved in 50 mL of spectral pure dichloromethane, 4 mL of the prepared solution was taken and 3 mg of TPNS-H sample was added, the polished glassy carbon working electrode, Ag / AgNO3 reference electrode and platinum auxiliary electrode were added, and the positive oxidation potential was tested. After the oxidation potential test, a small amount of ferrocene was added for calibration. Then 1.9372 g of tetrabutylammonium hexafluorophosphate electrolyte was dissolved in 50 mL of spectral pure N, N-dimethylformamide, 4 mL of the prepared solution was taken and 3 mg of TPNS-H sample was added, the polished glassy carbon working electrode, Ag / AgNO3 reference electrode and platinum auxiliary electrode were added, and the negative reduction potential was tested. After the reduction potential test, a small amount of ferrocene was added for calibration.
[0097] The electrochemical energy level test of TPNS-F, TPNS-M, TPA-NA-H and CZ-NA-H materials is the same as that of TPNS-H.
[0098] The electrochemical test results of the above compounds are shown in Figure 2 . After processing the test data, the highest occupied orbital (HOMO) and the lowest unoccupied orbital (LUMO) of the compound TPNS-H can be obtained, and the results are -5.85 eV and -2.55 eV, respectively, and the band gap is 3.30 eV. The results show that the compounds TPNS-H, TPNS-F and PNS-M are wide band gap deep blue molecules, which are very helpful for the injection of electrons and holes in electroluminescent devices, and are conducive to improving the luminous efficiency of the devices. Although TPA-NA-H and CZ-NA-H do not reach the range of deep blue light, they are in the category of positive blue light, and their lower LUMO is also very helpful for the injection of electrons and holes in electroluminescent devices, and is conducive to improving the luminous efficiency of the devices.
[0099] Example 10
[0100] Preparation of electroluminescent devices based on small molecule light-emitting materials
[0101] The ITO glass was cleaned by ultrasonic cleaning with acetone, detergent, deionized water and isopropanol in sequence, and then was treated by plasma for 10 minutes. The PEDOT:PSS aqueous solution doped with polystyrene sulfonic acid was spin-coated on the ITO to form a film with a thickness of 50 nm, and the PEDOT:PSS film was dried in a vacuum oven at 120°C for 20 minutes. Then, the TFB film was spin-coated on the surface of the PEDOT:PSS film to form a film with a thickness of 40 nm, and the TFB film was dried in a vacuum oven at 120°C for 20 minutes. The EML was spin-coated on the surface of the TFB film using the N,N-dimethylformamide solution of the compound TPNS-H, TPNS-F, TPNS-M, TPA-NA-H or CZ-NA-H, and the concentration was 20 mg / mL and the thickness was 30 nm. Then, the sample was annealed at 110°C for 30 minutes. Finally, the hole blocking layer Tm3PyPB with a thickness of 30 nm, the lithium fluoride (LiF) with a thickness of 1 nm and the aluminum (Al) thin layer with a thickness of 120 nm were sequentially evaporated on the light-emitting layer.
[0102] The results of the test of the photoelectric performance index of the electroluminescent device based on the compounds TPNS-H, TPNS-F, TPNS-M, TPA-NA-H and CZ-NA-H are shown in Table 1. Figures 3 to 5 .
[0103] The device structure was ITO / PEDOT:PSS (50 nm) / TFB (40 nm) / Active layer (30 nm) / TmPyPB (30 nm) / LiF (1 nm) / Al.
[0104] Figure 3 The J-V-L curve diagram of the electroluminescent device prepared based on the light-emitting layer of TPNS-H, TPNS-F, TPNS-M, TPA-NA-H and CZ-NA-H is shown in FIG. 1. As can be seen from the diagram, the maximum brightness of the electroluminescent device based on TPNS-H, TPNS-F, TPNS-M, TPA-NA-H and CZ-NA-H is 362 cd / m 2 , 751 cd / m 2 , 363 cd / m 2 , 24230 cd / m 2 and 10890 cd / m 2 , respectively, and the starting voltage is close to 2.8 V. Figure 4The graph of the efficiency of the device prepared based on TPNS-H, TPNS-F, TPNS-M, TPA-NA-H and CZ-NA-H materials versus luminance, from the graph, it can be seen that the electroluminescent devices based on TPNS-H, TPNS-F, TPNS-M, TPA-NA-H and CZ-NA-H all have good efficiency, and the maximum current efficiency and external quantum efficiency are 2.1 cd / A, 3.5%, 2.3 cd / A, 3.1%, 1.5 cd / A, 2.0%, 9.43 cd / A, 7.44%, 3.76 cd / A, 3.4%, respectively. Figure 5 The electroluminescent spectrum of the light-emitting device based on TPNS-H, TPNS-F, TPNS-M, TPA-NA-H and CZ-NA-H, from the graph, it can be seen that the color coordinates of the light-emitting device based on TPNS-H, TPNS-F, TPNS-M, TPA-NA-H and CZ-NA-H are (0.162, 0.062), (0.166, 0.079), (0.168, 0.084), (0.148, 0.161) and (0.164, 0.149), respectively, three compounds are in the blue light region, and good blue light emission is achieved.
[0105] The above examples are only preferred embodiments of the present application, and are used to explain the present application, but not to limit the present application, and the changes, replacements, modifications and the like made by those skilled in the art without departing from the spirit and essence of the present application should all belong to the protection scope of the present application.
Claims
1. A class of blue light organic semiconducting materials of aromatic and sila- polyheterocycles characterized in that, The chemical structural formula is shown as follows: Among them, Ar1, Ar2are one of the following structural formulae: ; Ar3 is one of the following structural formulas: 。 2. The method of producing a blue light organic semiconductor material of an aromatic sila- polycycle according to claim 1, characterized in that, The method comprises the following steps: Under the catalysis of tris(triphenylphosphine)carbonyl dihydrogen ruthenium (II), a blue light organic semiconductor material of aromatic and sila-hetero multi-ring is obtained by cyclization of a diphenyl-mononaphthyl silane derivative and a diaryl acetylene derivative in an organic solvent to form a naphtho-sila-hexacyclic ring; The structural formula of the diaryl acetylene derivative is shown as follows: The structural formula of the diphenyl-mononaphthyl silane derivative is shown as follows:
3. The preparation method according to claim 2, characterized in that, The molar ratio of the diphenyl-mononaphthyl silane derivative and the diaryl acetylene derivative is 1.5:1-1:1.
5.
4. The preparation method according to claim 2, characterized in that, The organic solvent is toluene; the molar volume ratio of the diphenyl-mononaphthyl silane derivative and the organic solvent is 1:1.5-1:3 mmol / mL.
5. The preparation method according to claim 2, characterized in that, The molar ratio of the diphenyl-mononaphthyl silane derivative and tris(triphenylphosphine)carbonyl dihydrogen ruthenium (II) is 1:0.05-1:0.
10.
6. Application of the blue light organic semiconductor material of aromatic and sila-hetero multi-ring in claim 1 in the preparation of an electroluminescent device.
7. Use according to claim 6, characterized in that, The blue light organic semiconductor material of aromatic and sila-hetero multi-ring is used as a light-emitting layer material, and the preparation of the light-emitting layer comprises the following steps: the blue light organic semiconductor material of aromatic and sila-hetero multi-ring is dissolved with an organic solvent, a film is formed by spin coating, and the light-emitting layer is obtained.