CN109456327B - High-mobility light-emitting semiconductor, and preparation method, application and application method thereof - Google Patents
High-mobility light-emitting semiconductor, and preparation method, application and application method thereof Download PDFInfo
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Abstract
The invention discloses a high-mobility light-emitting semiconductor and a preparation method, application and application method thereof, wherein the preparation method of the high-mobility light-emitting semiconductor comprises Suzuki coupling chemical reaction between aryl bromide or iodide and aryl boric acid or boric acid ester, and a method for applying the high-mobility light-emitting semiconductor to a device, wherein the device adopts a bottom gate top contact device structure, a grid adopts n-type doped silicon, and a layer of 300nm SiO thermally grows2As an insulating layer, before depositing an organic semiconductor layer, modifying the gate insulating layer by OTS at 120 ℃ in a vacuum furnace to form a single-layer OTS modification layer; the modification layer is sequentially cleaned by chloroform, normal hexane, isopropanol and acetone, and the high-mobility light-emitting semiconductor is coated by adopting a spin coating mode. The material synthesized by the invention shows the property of aggregation-induced luminescence, and the traditional fluorescent dye has the phenomenon of aggregation-induced fluorescence quenching under the condition of high concentration, so that the defects of the traditional fluorescent dye are effectively overcome.
Description
Technical Field
The invention belongs to the technical field of organic photoelectric materials, and particularly relates to a high-mobility light-emitting semiconductor, and a preparation method, application and application method thereof.
Background
Organic semiconductors are also used in a variety of flexible optoelectronic devices such as organic light emitting diodes, organic field effect transistors, organic photovoltaics, and the like. Although high mobility organic semiconductors and high luminous efficiency organic light emitting diodes have been well developed, organic semiconductor materials having both high mobility and high luminous brightness are still a challenge. The high-mobility organic light-emitting semiconductor can be used for preparing a mailing light-emitting transistor, pumping laser and the like, and in addition, the near-infrared organic light-emitting semiconductor has application in night vision, encrypted display, fluorescent probes and the like.
Disclosure of Invention
The invention aims to provide a high-mobility light-emitting semiconductor and a preparation method, application and an application method thereof, and solves the technical problems that most of the existing AIE light-emitting materials are low in mobility, and most of the high-mobility semiconductor materials are quenched in fluorescence in a solid state. The invention aims to apply the idea of aggregation-induced emission to the design of high-mobility semiconductors, and hopefully combines the advantages of the two to obtain a semiconductor material with high mobility and high luminous efficiency.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a high mobility aggregation-induced emission material, characterized by: comprises the following chemical formula:
r1, R2 and R3 are H or various imide acceptors, wherein the acceptors specifically comprise the following structural formula:
r5 is alkyl chain or glycol chain CnOmH2n+1O，n＝1～24，m＝0～10。
Further preferably, the specific structures of R1, R2, R3 and R4 are as follows,
wherein the receptor is the receptor.
Furthermore, the number of C in R5 is 1-24, and the number of O is 0-10.
The preparation method of the high-mobility light-emitting semiconductor is characterized by comprising the following steps of: the preparation method of the high-mobility light-emitting semiconductor comprises Suzuki coupling chemical reaction between aryl bromide or iodide and aryl boric acid or boric acid ester, and specifically comprises the following chemical formula:
wherein the receptor is the receptor.
More preferably, the high mobility light emitting semiconductor comprises a TriPE-nPDI series compound, wherein n ═ 1, 2, or 3.
Use of a high mobility light emitting semiconductor characterized in that: the high mobility light emitting semiconductors are useful in OLEDs, OFETs and OLETs.
A method of applying a high mobility light emitting semiconductor to a device, characterized by: the device adopts a bottom-gate top-contact device structure, the gate adopts n-type doped silicon, and a layer of SiO with the thickness of 300nm is thermally grown2As an insulating layer, before depositing an organic semiconductor layer, modifying the gate insulating layer by OTS at 120 ℃ in a vacuum furnace to form a single-layer OTS modification layer; the modification layer is sequentially cleaned by chloroform, normal hexane, isopropanol and acetone, and the high-mobility light-emitting semiconductor is coated by adopting a spin coating mode.
Further preferably, the specific method for performing the film coating by using the high-mobility light-emitting semiconductor in a spin coating manner is as follows:
dissolving TriPE-1PDI in chloroform with the concentration of 7mg/mL, coating the solution on a device at the spin-coating speed of 3000rpm for 30s, dissolving TriPE-2PDI in chloroform with the concentration of 5mg/mL, coating the solution on the device at the spin-coating speed of 3000rpm for 30s, finally dissolving TriPE-3PDI in m-xylene with the concentration of 2mg/mL, filtering the solution at 100 ℃ by using a 0.22-micron filter head, dripping the filtered solution on the device, and standing the filtered solution at room temperature overnight; dissolving a compound TriPE-3PDIL in a chloroform solution with the concentration of 8mg/ml, coating the solution on a device, coating the solution at the rotating speed of 3000rpm for 30s, performing vacuum evaporation on the surface of an organic layer through a mask to form 50nm gold as a source-drain motor, annealing the device in a nitrogen atmosphere at the temperature of 140 ℃ for 40min, and finishing coating the film by using a high-mobility light-emitting semiconductor in a spin coating manner.
Further preferably, the application of the high-mobility light-emitting semiconductor to the device needs to perform source-drain current testing, and the specific steps include testing in nitrogen at room temperature by adopting Keithley4200, and testing the mobility and the threshold voltage VTHThe calculation is that linear fitting is carried out after a curve saturation region of source-drain current relative to grid voltage is developed, and the formula is IDS＝(W/2L)μeCi(VG-VTH)2；
IDSIs the source-drain current, μ is the mobility, W is the channel width, L is the channel length, CiCapacitance per unit area of gate insulating layer, VTHIs the threshold voltage.
More preferably, the capacitance of the insulating layer is 10nFCm-2。
The implementation of the invention can achieve the following beneficial effects:
the invention provides a new strategy for designing and synthesizing high-mobility luminous semiconductor molecules, realizes perfect balance between charge transmission and luminescence of the molecules, and can be widely applied to OLED, OFET and OLET;
the aggregate-state luminescent efficiency of the material synthesized by the method is high, and the yield of fluorescence quantum is as high as 30%;
the material synthesized by the invention shows the property of aggregation-induced luminescence, and the traditional fluorescent dye has the phenomenon of aggregation-induced fluorescence quenching under the condition of high concentration, so that the defects of the traditional fluorescent dye are effectively overcome;
the material synthesized by the invention shows the characteristics of red light and near infrared luminescence;
the synthesized material of the invention has higher electron mobility which is as high as 0.04cm2V-1s-1。
Drawings
FIG. 1 is a NMR hydrogen spectrum of Compound 2;
FIG. 2 is a NMR carbon spectrum of Compound 2;
FIG. 3 is a high resolution mass spectrum of Compound 2;
FIG. 4 is a NMR hydrogen spectrum of Compound 3;
FIG. 5 is a NMR carbon spectrum of Compound 3;
FIG. 6 is a high resolution mass spectrum of Compound 3;
FIG. 7 shows the NMR spectrum of TriPE-1 PDI;
FIG. 8 shows a TriPE-1PDI NMR carbon spectrum of a compound;
FIG. 9 is a high resolution mass spectrum of TriPE-1 PDI;
FIG. 10 is a NMR spectrum of TriPE-2 PDI;
FIG. 11 is a high resolution mass spectrum of TriPE-2 PDI;
FIG. 12 is a NMR spectrum of TriPE-3 PDI;
FIG. 13 is a high resolution mass spectrum of TriPE-3 PDI;
FIG. 14 is a NMR spectrum of TriPE-3 PDIL;
FIG. 15 is a high resolution mass spectrum of TriPE-3 PDIL;
FIG. 16 is a NMR carbon spectrum of TriPE-3 NDI;
FIG. 17 is a high resolution mass spectrum of TriPE-3 NDI;
FIG. 18 is a molar extinction coefficient of the compound TriPE-nPDIs (A) in chloroform solution, (B) normalized fluorescence spectra in chloroform solution, (C) normalized ultraviolet absorbance spectra and (D) film normalized absorbance spectra at a concentration of 10. mu.M;
FIG. 19 is the emission spectra of TriPE-1PDI (A), TriPE-2PDI (B), TriPE-3PDI (C) in chloroform/hexane with different hexane ratios compound concentrations (10 μ M); lambda ex:572nm (D-F) compounds TriPE-1PDI (D), TriPE-2PDI (E), photographs of TriPE-2PDI (F) in chloroform/n-hexane with different n-hexane ratios, excitation wavelength 365 nm;
FIG. 20 is a thermogravimetric analysis curve of a series of compounds TriPE-nPDI, test conditions: heating in nitrogen atmosphere at a heating rate of 10 ℃/min;
FIG. 21 is a differential scanning calorimetry curve of a series of compounds TriPE-nPDI, under the following test conditions: heating in nitrogen atmosphere at a heating rate of 10 ℃/min;
FIG. 22 is a cyclic voltammogram of compound (A) TriPE-1PDI, (B) TriPE-2 PDIDTdScriptE-3 PDI; and (3) testing conditions are as follows: 0.1MBu4+ NPF 6-chloroform solution, scanning speed: 100 mV/s;
FIG. 23 is a plot of organic field effect transistor output and transfer at 140 ℃ annealing for compound TriPE-3PDI (AandB) andDredge-3 PDIL (CandD);
FIG. 24 is a transfer curve at room temperature for compound (A) TriPE-1PDI (B, C) output and transfer curve at 140 ℃ annealing temperature for compound TriPE-2 PDI;
FIG. 25 shows AFM and XRD images of thin films of compounds TriPE-1PDI, TriPE-2PDI, TriPE-3PDI and TriPE-3PDIL at room temperature and 140 ℃ annealing temperature;
FIG. 26 shows absorption and emission spectra of TriPE-3PDIL in chloroform solution and thin film.
Detailed Description
For a more clear understanding of the technical features, objects and effects of the present invention, embodiments of the present invention will now be described in detail with reference to the accompanying drawings. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A high mobility aggregation-induced emission material, characterized by: comprises the following chemical formula:
r1, R2 and R3 are H or various imide acceptors, wherein the acceptors specifically include the following structural formula:
r5 is alkyl chain or glycol chain CnOmH2n+1OWherein n is 1 to 24 and m is 0 to 10, the number of C in R5 is 1 to 24, the number of O is 0 to 10, R1, R2, R3 and R4 have the following specific structures,
wherein the receptor is the receptor.
The preparation method of the high-mobility light-emitting semiconductor comprises Suzuki coupling chemical reaction between aryl bromide or iodide and aryl boric acid or boric acid ester, and specifically comprises the following chemical formula:
wherein the acceptor is the above acceptor, and the high mobility light-emitting semiconductor comprises TriPE-nPDI (perylene imide substituted triphenylethylene) series compounds, wherein n is 1, 2 or 3.
Taking an example of synthesis of a TriPE-nPDI (n ═ 1, 2, 3) series of compounds:
synthesis of arylboronic acids or boronic esters:
the specific synthesis steps of the compound 2 (the chemical reaction formula 2 is the compound 2) are as follows:
benzyl chloride (3g, 23.7mmol) dissolved in phosphorous acid trisEthyl ester (4.92g, 29.6mmol) was stirred at room temperature for 2h then reacted at 170 ℃ for 5h, after cooling to room temperature, 4, 4' -dibromobenzophenone (7.3g, 21.3mmol), tetrahydrofuran (40mL), potassium tert-butoxide (5.8g, 52.1mmol) were added successively and stirred at room temperature for 20 h. Cooling to room temperature, washing the reaction system twice with water, extracting the organic phase with dichloromethane, performing column chromatography with n-hexane as eluent to obtain compound 4 (the chemical reaction formula indicates 4 is compound 4), with a yield of 90%, and reacting compound 4(500mg, 1.21mmol), PdCl under the protection of nitrogen2[P(cy)3]2(99mg, 10% mmol), pinacolborate (767mg, 3.02mmol), potassium acetate (949mg, 9.66mmol) were dissolved in dioxane and refluxed for 24 h. After water quenching reaction, washing an organic phase twice by using saturated ammonium chloride, drying by using anhydrous sodium sulfate, distilling under reduced pressure to remove a solvent, purifying a crude product by using a flash column chromatography, wherein an eluent is n-hexane: 1-dichloromethane: 1, compound 2 was obtained in 70% yield,
characterizing the chemical structure of the compound 2 to obtain nuclear magnetic resonance hydrogen spectrum data:1HNMR(400MHz，CDCl3，δ)：7.78-7.74(t，J＝8Hz，4H，ArH)，7.32-7.30(d，J＝8Hz，2H；ArH)，7.23-7.21(d，J＝8Hz，2H；ArH)，7.14-7.11(m，3H；ArH)，7.06-7.02(m，3H；ArH)，1.38-1.27(br，24H，CH3) As in fig. 1; nuclear magnetic resonance carbon spectrum (fig. 2) data for compound 2:13CNMR(100MHz，CDCl3δ): 146.1, 143.3, 142.4, 137.1, 135.0, 134.7, 129.8, 129.6, 129.1, 128.0, 127.0, 126.9, 83.9, 83.8, 83.5, 25.0, 24.9; high resolution mass spectrometry (fig. 3) data for compound 2: HRMS (MALDI-TOF) m/z: [ M ] A]+Theoretical value C32H38B2O4508.2956; actual value, 508.3000.
The synthetic route of compound 3 (the above chemical reaction formula 3 is compound 3) is the same as compound 2. yield: 89 percent.
Characterizing the chemical structure of compound 3 to obtain nmr hydrogen spectrum data:1HNMR(400MHz，CDCl3，δ)：7.76-7.74(d，4H，J＝8Hz)，7.57-7.55(d，2H；J＝8Hz)，7.33-7.31(d，2H，J＝8Hz)，7.20-7.18(d，J＝8Hz，2H)，7.03-7.01(d，J＝8Hz，2H)，1.38-1.32(br，36H，CH3) As in fig. 4; nuclear magnetic resonance carbon spectrum (figure five) data for compound 3:13CNMR(100MHz，CDCl3δ): 145.9, 143.4, 143.1, 140.0, 135.0, 134.7, 134.4, 129.8, 129.1, 128.9, 127.1, 83.9, 83.80, 83.7, 25.0, 24.9; high resolution mass spectrometry (fig. 6) data for compound 3: HRMS (MALDI-TOF) m/z: [ M ] A]+Theoretical value C38H49B3O6634.3808; actual value 634.3775.
Synthesizing a compound TriPE-1PDI (perylene imide monosubstituted triphenylethylene):
under the protection of nitrogen, the compound 1(40mg, 0.13mmol) and 1Br-PDI-2EH (102mg, 0.15mmol) are shown in the chemical reaction formula 1, namely the compound 1, Pd (PPh)3)4(49mg, 28%) and potassium carbonate (21mg, 1.5mmol) were dissolved in freshly distilled tetrahydrofuran (10mL) and deoxygenated water (4mL) and reacted at 80 ℃ for 48 h. After cooling to room temperature, the mixture is washed twice by water and then extracted by dichloromethane, and after column chromatography purification, recrystallization is carried out to obtain 65mgTriPE-1PDI, wherein the yield is as follows: 58 percent.
The chemical structure of the compound TriPE-1PDI is characterized, and nuclear magnetic resonance hydrogen spectrum data shown in figure 7 is obtained:1HNMR(400MHz，CDCl3δ): 8.64-8.59(m, 2H), 8.52-8.50(m, 2H), 8.13-8.11(d, J ═ 8Hz, 2H), 7.81-7.79(d, J ═ 8Hz, 2H), 7.40-7.34(m, 8H), 7.29-7.28(m, 2H), 7.26-7.16(m, 4H), 7.06(s, 1H), 4.16-4.11(m, 4H), 1.58(m, 2H), 1.40-1.32(m, 16H), 0.97-0.89(m, 12H), nuclear magnetic resonance carbon spectrum (fig. 8) data of compound TriPE-1 PDI:13CNMR(100MHz，CDCl3δ): 163.7, 163.6, 144.3, 143.1, 141.4, 140.3, 140.1, 138.2, 135.7, 134.4, 134.1, 131.5, 130.8, 130.6, 130.4, 129.9, 129.8, 128.8, 128.7, 128.3, 128.0, 127.9, 127.78, 127.2, 127.1, 123.3, 123.1, 123.0, 122.4, 122.1, 122.0, 44.3, 44.2, 38.0, 30.8, 28.8, 28.7, 24.1, 24.0, 23.1, 14.1, 10.7; high resolution mass spectrometry (FIG. 9) data for compound TriPE-1 PDI: HRMS (MALDI-TOF) m/z: [ M ] A]+Theoretical value C60H56N2O4868.4240; actual value, 868.4231.
Synthesizing a compound TriPE-2PDI (perylene bisimide disubstituted triphenylethylene):
compound 2(30mg, 0.059mmol), 1Br-PDI-2EH (90mg, 0.13mmol), Pd (PPh) under nitrogen protection3)4(19mg, 28%) and potassium carbonate (81mg, 0.59mmol) were dissolved in tetrahydrofuran (10mL) and deoxygenated water (4mL) and reacted at 80 ℃ for 48h, after cooling to room temperature, the mixture was washed twice with water and extracted with dichloromethane, purified by column chromatography and recrystallized to give 55mg of TriPE-2PDI, yield: and 63 percent.
Characterizing the chemical structure of the TriPE-2PDI compound to obtain nuclear magnetic resonance hydrogen spectrum data:1HNMR(400MHz，CDCl3δ): 8.68-8.56(m, 10H), 8.19-8.17(d, J ═ 8Hz, 2H), 8.04-8.02(d, J ═ 8Hz, 1H), 7.97-7.95(d, J ═ 8Hz, 1H), 7.55-7.54(m, 8H), 7.49-7.34(m, 5H), 7.16(s, 1H), 4.12-4.02(m, 8H), 1.95-1.88(m, 4H), 1.34-1.31(m, 32H), 0.89-0.87(m, 24H), as in fig. 10; high resolution mass spectrometry (FIG. 11) data for compound TriPE-2 PDI: HRMS (MALDI-TOF) m/z: [ M + H ]]+Theoretical value C100H96N4O81481.7301; actual value, 1481.7263.
Synthesizing a compound TriPE-3PDI (triphenylethylene trisubstituted by perylene imide):
compound 3(30mg, 0.047mmol), 1Br-PDI-2EH (105mg, 0.15mmol), Pd (PPh) under nitrogen protection3)4(15mg, 28%) and potassium carbonate (52mg, 0.38mmol) were dissolved in tetrahydrofuran (8mL) and deoxygenated water (2mL) and reacted at 80 ℃ for 48 h. After cooling to room temperature, the mixture was washed twice with water, extracted with dichloromethane, purified by column chromatography and recrystallized to give 76mg TriPE-3PDI, yield: 77 percent.
Characterizing the chemical structure of the TriPE-3PDI compound to obtain nuclear magnetic resonance hydrogen spectrum data:1HNMR(400MHz，CDCl3，δ)：8.79-8.62(m，12H)，8.56-8.53(dd，J＝4Hz，2H)，8.41-8.33(m，2H)，8.15-8.13(br，1H)，7.92-7.88(m，2H)，7.81-7.69(m，14H)，4.24(br，8H)，3.37(br，2H)，3.24(br，2H)，2.09-2.06(m，4H)，1.49-1.41(m，36H) 1.04-0.97(m, 38H), 0.81-0.70(m, 12H), as in fig. 12; high resolution mass spectrometry (FIG. 13) data for compound TriPE-3 PDI: HRMS (MALDI-TOF) m/z: [ M + H ]]+Theoretical value C100H96N4O81481.7301; actual value, 1481.7263.
Synthesizing a compound TriPE-3PDIL (long-chain perylene imide trisubstituted triphenylethylene):
compound 3(30mg, 0.047mmol), 1Br-PDI (105mg, 0.15mmol), Pd (PPh) under nitrogen protection3)4(15mg, 28%) and potassium carbonate (52mg, 0.38mmol) were dissolved in tetrahydrofuran (8mL) and deoxygenated water (2mL) and reacted at 80 ℃ for 48 h. After cooling to room temperature, the mixture is washed twice by water and then extracted by dichloromethane, and after column chromatography purification, recrystallization is carried out to obtain 76mg TriPE-3PDIL, yield: 77 percent.
Characterizing the chemical structure of the TriPE-3PDIL compound to obtain nuclear magnetic resonance hydrogen spectrum data:1HNMR(400MHz，CDCl3δ): 8.71-8.49(m, 14H), 8.31-8.28(m, 2H), 8.01(br, 1H), 7.75-7.61(m, 16H), 7.37(s, 1H), 4.15-4.09(br, 8H), 3.23(s, 2H), 3.05(s, 2H), 2.01(br, 4H), 1.75(m, 2H), 1.24-1.06(m, 138H), 0.84-0.79(br, 42H), as shown in FIG. 14; high resolution mass spectrometry (FIG. 15) data for compound TriPE-3 PDIL: HRMS (MALDI-TOF) m/z: [ M + H ]]+Theoretical value C188H232N6O122766.7801; actual value, 2766.7813.
Synthesis of the compound TriPE-3 NDI:
the synthetic route of the compound TriPE-3NDI is the same as that of TriPE-3 PDI. Yield: 90 percent.
The chemical structure of the compound TriPE-3NDI was characterized to obtain NMR carbon spectrum data, as shown in FIG. 16:13CNMR(100MHz，CDCl3δ): 164.2, 164.0, 146.2, 142.3, 138.5, 137.7, 137.3, 131.2, 130.8, 130.6, 130.1, 130.0, 129.8, 128.7, 128.0, 127.9127.8, 126.9, 126.8, 123.0, 40.5, 31.6, 28.0, 26.8, 22.6, 14.0. high resolution mass spectrometry (fig. 17) data for compound TriPE-3 NDI: HRMS (MALDI-TOF) m/z: [ M + H ]]+Theoretical value C74H67N3O6，1094.5103; actual value, 1094.5134.
Use of a high mobility light emitting semiconductor for OLEDs, OFETs and OLETs.
The method for applying high-mobility light-emitting semiconductor to device adopts a bottom-gate top-contact device structure, a gate electrode adopts n-type doped silicon, and a layer of SiO with the thickness of 300nm is thermally grown2As an insulating layer, the insulating layer has a capacitance of 10 nCm-2Before depositing an organic semiconductor layer, modifying a grid insulating layer by OTS at 120 ℃ in a vacuum furnace to form a single-layer OTS modification layer; the modification layer is sequentially cleaned by chloroform, normal hexane, isopropanol and acetone, and the high-mobility light-emitting semiconductor is coated by adopting a spin coating mode
Chemical structure characterization of TriPE-1PDI and some key intermediates:
the chemical structures of the TriPE-nPDI and the TriPE-NDI obtained by synthesis are subjected to nuclear magnetic characterization (figures 1-17).
Photophysical property characterization:
photophysical properties of the series of compounds, TriPE-nPDIs, were studied using UV-visible absorption and fluorescence spectroscopy (FIGS. 18 and 19, respectively). In a dilute chloroform solution, the absorption spectra of the compounds TriPE-1PDI, TriPE-2PDI and TriPE-3PDI are almost the same, and mainly show two absorption peaks of 500 nm and 536 nm. The molar absorption value of the compound increases linearly with the number of perylene bisimides. The compounds TriPE-1PDI, TriPE-2PDI and TriPE-3PDI showed red and near infrared emission (650-900nm) in both solution and solid state. From solution to solid, the emission of the compound showed a red shift, with the emission wavelength red-shifted to 680nm for the compound TriPE-3 PDI. The aggregation-induced emission properties of a series of compounds TriPE-nPDIs were studied. The three compounds all show luminescence behaviors in solution, the fluorescence quantum yield of TriPE-1PDI is 2.5%, the fluorescence quantum yield of TriPE-2PDI is 17%, and the fluorescence quantum yield of TriPE-3PDI is 8%. The three compounds in chloroform solution with n-hexane added, its fluorescence intensity gradually increased. The fluorescence quantum yields of the three compounds in the solid state were (TriPE-1 PDI: 11%, TriPE-2 PDI: 4% and TriPE-3 PDI: 30%).
Thermodynamic and electrochemical properties are key parameters required for device fabrication. Thermogravimetric analysis showed that the three compounds, TriPE-1PDI, TriPE-2PDI and TriPE-3PDI, all showed good thermal stability with 5% thermogravimetric temperatures of 435, 447 and 453 deg.C (FIG. 20). Differential scanning calorimetry showed that the glass transition temperatures of the compounds TriPE-1PDI, TriPE-2PDI and TriPE-3PDI were 107, 203 and 239 ℃ in this order. The melting points of the three compounds were 210 ℃, 315 ℃ and 382 ℃ in this order. Thermal analysis indicated that the three compounds had good thermodynamic and morphological stability (fig. 21). Electrochemical tests show that the HOMO/LUMO energy levels of the three compounds of TriPE-nPDIs are respectively-5.43/-3.79 eV, -5.52/-3.82eV and-5.50/-3.84 eV. The lower LUMO energy level is suitable for electron transport (fig. 22).
Three compound organic field effect transistor devices were prepared. The device structure is a bottom gate top contact device. The device performance test was performed under a nitrogen atmosphere. In general, the compounds TriPE-1PDI, TriPE-2PDI and TriPE-3PDI all exhibited electron transport properties, with the mobility of the compounds increasing with increasing PDI units (FIGS. 23 and 24). The electron mobility of the compound TriPE-1PDI film is 10-4cm2V-1s-1Threshold voltage 22V, switching ratio 102. The performance is reduced after the annealing treatment at 140 ℃. The electron mobility, threshold voltage and on-off ratio of the compound TriPE-2PDI are all improved. The compound TriPE-3PDI shows much higher electron mobility than TriPE-1PDI and TriPE-2PDI, and is about 0.01cm2V-1s-1. After the side chain of the compound TriPE-3PDI is lengthened, the film forming property is greatly improved, and the mobility is further improved to 0.04cm2V-1s-1We investigated the thin film morphology and crystallinity of the compounds using thin film X-ray diffraction (XRD) and Atomic Force Microscopy (AFM) (fig. 25). The results show that the amorphous film of the compound TriPE-1PDI shows lower mobility, and the crystalline film has no performance. The compound TriPE-2PDI also exhibits an amorphous film, and the film morphology is not affected by annealing temperature. The compound TriPE-3PDI film shows poor crystallinity and poor film continuity. When long chains are introduced, the film morphology is significantly improved, thus showing higher mobility, and in addition,the compound TriPE-3PDI still keeps good luminescence property after long chain introduction (FIG. 26). The photophysical properties of the compounds, as well as the device properties, are summarized in tables (tables 1 and 2) in which HOMO represents the highest occupied empty orbital; LUMO denotes the lowest unoccupied orbital; Td/Tg represents the thermal decomposition temperature/glass transition temperature, Ion/IoffDenotes the on-off ratio, VT denotes the threshold voltage, and μ e denotes the electron mobility.
Table 1 summarizes the photophysical properties of the compounds TriPE-nPDI, TriPE-2PDI and TriPE-3 PDI.
Table 2, summary of the field Effect properties of the compounds TriPE-nPDI and TriPE-3 PDIL.
Use of a high mobility light emitting semiconductor for OLEDs (organic light emitting diodes), OFETs (organic thin film transistors) and OLETs (organic light emitting transistors).
The method for applying high-mobility light-emitting semiconductor to device adopts a bottom-gate top-contact device structure, a gate electrode adopts n-type doped silicon, and a layer of SiO with the thickness of 300nm is thermally grown2As an insulating layer, before depositing an organic semiconductor layer, modifying the gate insulating layer by OTS at 120 ℃ in a vacuum furnace to form a single-layer OTS modification layer; the modification layer is sequentially cleaned by chloroform, normal hexane, isopropanol and acetone, and the high-mobility light-emitting semiconductor is coated by adopting a spin coating mode.
The specific method for coating by using the high-mobility light-emitting semiconductor in a spin coating mode comprises the following steps:
TriPE-1PDI was dissolved at a concentration of 7mg/mL chloroform, then coating on a device, wherein the spin-coating speed is 3000rpm for 30s, dissolving TriPE-2PDI in chloroform with the concentration of 5mg/mL, then coating on the device, the spin-coating speed is 3000rpm for 30s, finally dissolving TriPE-3PDI in m-xylene with the concentration of 2mg/mL, then filtering with a 0.22 mu m filter head at 100 ℃, then dripping on the device, and standing overnight at room temperature; dissolving a compound TriPE-3PDIL in a chloroform solution with the concentration of 8mg/ml, coating the solution on a device, coating the solution at the rotating speed of 3000rpm for 30s, performing vacuum evaporation on the surface of an organic layer through a mask to form 50nm gold as a source-drain motor, annealing the device in a nitrogen atmosphere at the temperature of 140 ℃ for 40min, and finishing coating the film by using a high-mobility light-emitting semiconductor in a spin coating manner. The application of the high-mobility light-emitting semiconductor to a device needs source-drain current test, and the specific steps are that Keithley4200 is adopted for testing in nitrogen at room temperature, and the mobility and the threshold voltage V areTHThe calculation is that linear fitting is carried out after a curve saturation region of the source-drain current relative to the grid voltage is developed, and the formula is
IDS＝(W/2L)μeCi(VG-VTH)2
IDSIs the source-drain current, μ is the mobility, W is the channel width, L is the channel length, CiCapacitance per unit area of gate insulating layer, VTHIs the threshold voltage.
While the present invention has been described with reference to the embodiments shown in the drawings, the present invention is not limited to the embodiments, which are illustrative and not restrictive, and it will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (8)
1. A high mobility aggregation-induced emission material, characterized by: comprises the following chemical formula:
the specific structures of R1, R2, R3 and R4 are as follows,
R1＝H，
r3 ═ R4 ═ acceptor or
R1＝R4＝H，
R3 ═ acceptor or
R1＝H，
R3 ═ H, R4 ═ acceptor or
Wherein the receptor is the receptor, and the receptor specifically comprises the following structural formula:
r5 is alkyl chain or glycol chain CnOmH2n+10N is 1-24, m is 0-10, and the high mobility aggregation-induced emission material does not include TPE-PDI 4.
2. The method for producing a high-mobility light-emitting semiconductor according to claim 1, wherein: the preparation method of the high-mobility light-emitting semiconductor comprises Suzuki coupling chemical reaction between aryl bromide or iodide and aryl boric acid or boric acid ester, and specifically comprises the following chemical formula:
3. The method for producing a high-mobility light-emitting semiconductor according to claim 2, wherein: the high-mobility light-emitting semiconductor comprises a TriPE-nPDI series compound, wherein n is 1, 2 or 3, and the structure of the TriPE-nPDI series compound is as follows:
4. use of a high mobility light emitting semiconductor according to any of claims 1 to 2, wherein: the high mobility light emitting semiconductors are useful in OLEDs, OFETs and OLETs.
5. A method of applying a high mobility light emitting semiconductor to a device according to any one of claims 1 to 2, wherein: the device adopts a bottom-gate top-contact device structure, the gate adopts n-type doped silicon, and a layer of SiO with the thickness of 300nm is thermally grown2As an insulating layer, before depositing an organic semiconductor layer, modifying the gate insulating layer by OTS at 120 ℃ in a vacuum furnace to form a single-layer OTS modification layer; the modification layer is sequentially cleaned by chloroform, normal hexane, isopropanol and acetone, and the high-mobility light-emitting semiconductor is coated by adopting a spin coating mode.
6. The method for applying the high-mobility light-emitting semiconductor to the device according to claim 5, wherein the specific method for coating by using the high-mobility light-emitting semiconductor by means of spin coating comprises the following steps:
dissolving TriPE-1PDI in chloroform with the concentration of 7mg/mL, coating the solution on a device at the spin-coating speed of 3000rpm for 30s, dissolving TriPE-2PDI in chloroform with the concentration of 5mg/mL, coating the solution on the device at the spin-coating speed of 3000rpm for 30s, finally dissolving TriPE-3PDI in m-xylene with the concentration of 2mg/mL, filtering the solution at 100 ℃ by using a 0.22-micron filter head, dripping the filtered solution on the device, and standing the filtered solution at room temperature overnight; dissolving a compound TriPE-3PDIL in a chloroform solution with the concentration of 8mg/ml, coating the solution on a device, coating the solution for 30s at the rotating speed of 3000rpm, performing vacuum evaporation on 50nm gold on the surface of an organic layer through a mask to serve as a source-drain motor, annealing the device for 40min in a nitrogen atmosphere at the temperature of 140 ℃, and finishing coating by using a high-mobility light-emitting semiconductor in a spin coating manner, wherein the TriPE-nPDI series compound has the following structure:
7. the method of claim 6, wherein the applying of the high mobility light emitting semiconductor to the device further comprises performing a source drain current test by using Keithley4200 under nitrogen at room temperature, mobility and a threshold voltage VTHThe calculation is that linear fitting is carried out after a curve saturation region of source-drain current relative to grid voltage is developed, and the formula is IDS＝(W/2L)μeCi(VG-VTH)2；
IDSIs the source-drain current, μ is the mobility, W is the channel width, L is the channel length, CiCapacitance per unit area of gate insulating layer, VTHIs the threshold voltage.
8. The method of applying a high mobility light emitting semiconductor to a device as claimed in claim 6, wherein the capacitance of the insulating layer is 10nFcm-2。
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