阅读说明：本技术 联苯乙烯基衍生物分子及合成方法、单晶及基于其的有机发光场效应晶体管器件 (Bistyryl derivative molecule, synthetic method, single crystal and organic light-emitting field effect transistor device based on single crystal ) 是由 廖清 黄涵 付红兵 于 2020-05-31 设计创作，主要内容包括：本发明公开了一种联苯乙烯基衍生物分子及其合成方法、联苯乙烯基衍生物单晶及基于联苯乙烯基衍生物单晶的有机发光场效应晶体管器件。设计合成了一种联苯乙烯基衍生物分子BPVAn,利用微距升华法可制得薄厚均匀,尺寸在50μm以上的薄片单晶,该晶体在400nm飞秒激光泵浦下,在较低的阈值(≤10μJ/cm～(2))即可实现激光发射,并且以该单晶材料制成的场效应晶体管只需在用Ag对称电极作为源漏极时即可实现双极性,且有很高的空穴迁移率(5.24cm～(2)V～(-1)s～(-1))和电子迁移率(0.16cm～(2)V～(-1)s～(-1)),同时可以观测到很强的电致发光。BPVAn单晶同时具备低的激光阈值与高的载流子迁移率,将成为实现有机电泵浦激光器可选材料中十分有竞争力的一种。(The invention discloses a distyryl derivative molecule and a synthetic method thereof, a distyryl derivative single crystal and an organic light-emitting field effect transistor device based on the distyryl derivative single crystal. Designed and synthesized a bisstyryl derivative molecule BPVAn, can prepare thin sheet single crystal with uniform thickness and over 50 mu m size by using a microspur sublimation method, and the crystal is pumped by a 400nm femtosecond laser at a lower threshold value (less than or equal to 10 mu J/cm) 2 ) The laser emission can be realized, and the field effect transistor made of the single crystal material can realize bipolarity only by using the Ag symmetrical electrode as a source electrode and a drain electrode, and has high hole mobility (5.24 cm) 2 V ‑1 s ‑1 ) And electron mobility (0.16 cm) 2 V ‑1 s ‑1 ) And strong electroluminescence can be observed at the same time. The BPVAn single crystal has low laser threshold and high carrier mobility, and becomes a very competitive material for realizing the organic electric pump laser.)

1. A method for synthesizing a bisstyryl derivative molecule is characterized in that a bisstyryl derivative 4,4 '-bis ((E) -2- (anthracene-2-yl) vinyl) -1,1' -biphenyl, namely BPVAn, is designed and synthesized, and the method comprises the following specific steps:

s1, loading 2-bromoanthracene powder into a branch pipe reactor tube, adding butyl lithium at-70 ℃ by taking ultra-dry tetrahydrofuran as a solvent, stirring for 1-2 h, then dropwise adding ultra-dry nitrogen dimethyl formamide (DMF), stirring overnight to obtain a primary product, adding deionized water for quenching reaction, extracting, purifying by a silica gel column chromatography, and drying to obtain an anthracene 2-formaldehyde solid;

s2, putting 4,4' -bis (diethoxyphosphonomethyl) biphenyl powder and dry NaH powder into the same one-leg reactor, taking ultra-dry tetrahydrofuran as a solvent, stirring for 1h under the condition of ice-water bath, then dissolving the anthracene 2-formaldehyde solid powder obtained in the step S1 in the ultra-dry tetrahydrofuran, adding the mixture into a reaction by using a syringe, stirring overnight at room temperature, adding deionized water to quench the reaction, carrying out suction filtration on the generated suspension under negative pressure, repeatedly washing the solid product by using ethanol and dichloromethane, and drying to obtain the final product BPVAn powder.

2. The method for synthesizing distyryl derivative molecules according to claim 1, wherein the reaction is carried out without water and oxygen.

3. The method for synthesizing distyryl derivative molecules according to claim 1, wherein the mass ratio of the substances of each drug in step S1 is 2-bromoanthracene: butyl lithium: nitrogen dimethylformamide ═ 2:5.3: 5.4; the amount ratio of the substances of each drug in step S2 was 4,4' -bis (diethoxyphosphonomethyl) biphenyl: NaH: anthracene 2-carbaldehyde 0.5: 3.3: 1.1.

4. the method for synthesizing distyryl derivative molecules according to claim 1, wherein a chromatography liquid used in the silica gel column chromatography in step S1 is a mixed liquid of dichloromethane and petroleum ether, and the volume ratio is 1: 3.

5. A bisstyryl derivative molecule BPVAn, prepared according to the synthetic method of claim 1, having the structure:

6. the distyryl derivative molecule according to claim 5, wherein absorption peak wavelengths of a tetrahydroxyfuran dilute solution are at 326nm, 338nm, 376nm and 395nm, luminescence peak wavelengths are at 430nm and 447nm, and a fluorescence quantum yield is 0.56; the solid single crystal has absorption peaks at 424nm and 460nm, luminescence peaks at 502nm and 536nm, and fluorescence quantum yield of 0.35.

7. A distyryl derivative single crystal, wherein the distyryl derivative molecule according to claim 5 or 6 is subjected to a microspur sublimation method to obtain a BPVAn thin sheet single crystal grown perpendicular to a substrate.

8. The distyryl derivative single crystal according to claim 7, wherein laser emission can be achieved at the crystal edge under excitation of 400nm femtosecond laser having a wavelength of 503nm and a threshold of 10 μ J/cm or less²。

9. An organic light-emitting field effect transistor device based on the distyryl derivative single crystal as claimed in claim 7 or 8, characterized in that a BPVAn thin sheet single crystal is transfer-tiled to Si/SiO coated with 20nm thick polymethyl methacrylate (PMMA)₂On the substrate, a silver electrode with the thickness of 100nm is evaporated after the transistor is masked, and the mask is removed to obtain the organic light-emitting field effect transistor device.

Technical Field

The invention relates to the technical field of organic lasers and organic light-emitting field effect transistors, in particular to a biphenyl vinyl derivative molecule which is designed and synthesized, has good optical property and electrical property, and can realize low-threshold photoluminescence and a high-mobility light-emitting field effect transistor.

Background

An organic light-emitting field effect transistor (OLEFET) is a new type of functional device that combines the light-emitting characteristics of an OLED with the switching characteristics of an OFET. Theoretically, a novel device structure is provided for researching the transmission characteristics of carriers and the light emitting theory of excitons, and the device structure has important scientific research significance. Meanwhile, the OLEFET has the characteristics of high current density, low metal electrode absorption loss and the like, and is an ideal structure for constructing an electrically pumped organic laser. The biphenyl ethylene compounds are a kind of multifunctional materials with excellent performance: can be used as a luminescent material to be applied to an electroluminescent device; the organic light-emitting diode can be used as a green light additive to improve the light-emitting efficiency and stability of the organic light-emitting diode; can be applied to a device as a hole transport layer. The invention will be described in its application to organic lasers and organic light emitting field effect transistors.

Disclosure of Invention

The invention relates to the technical field of biophotonics, in particular to a designed and synthesized biphenyl vinyl derivative molecule, and a crystal of the biphenyl vinyl derivative molecule has good optical properties and electrical properties. The invention aims to prepare a field effect transistor which realizes low threshold organic photoluminescence and high mobility luminous field effect. The development of organic solid-state lasers in recent years is relatively mature, and many low-threshold organic solid-state lasers are developed through the design of materials. Compared with an inorganic laser, the organic solid-state laser is convenient to prepare, low in cost and suitable for wider application fields. However, in organic single crystals, good emission properties and high carrier mobility are always difficult to achieve, which is a great obstacle to the realization of an electric injection laser.

The invention discloses a method for synthesizing a bisstyryl derivative molecule, which designs and synthesizes a bisstyryl derivative 4,4 '-bis ((E) -2- (anthracene-2-yl) vinyl) -1,1' -biphenyl, namely BPVAn, and comprises the following specific steps:

s1, loading 2-bromoanthracene powder into a branch pipe reactor tube, adding butyl lithium at-70 ℃ by taking ultra-dry tetrahydrofuran as a solvent, stirring for 1-2 h, then dropwise adding ultra-dry nitrogen dimethyl formamide (DMF), stirring overnight to obtain a primary product, adding deionized water for quenching reaction, extracting, purifying by a silica gel column chromatography, and drying to obtain an anthracene 2-formaldehyde solid;

s2, putting 4,4' -bis (diethoxyphosphonomethyl) biphenyl powder and dry NaH powder into the same one-leg reactor, taking ultra-dry tetrahydrofuran as a solvent, stirring for 1h under the condition of ice-water bath, then dissolving the anthracene 2-formaldehyde solid powder obtained in the step S1 in the ultra-dry tetrahydrofuran, adding the mixture into a reaction by using a syringe, stirring overnight at room temperature, adding deionized water to quench the reaction, carrying out suction filtration on the generated suspension under negative pressure, repeatedly washing the solid product by using ethanol and dichloromethane, and drying to obtain the final product BPVAn powder.

The invention designs and synthesizes a bisstyryl derivative molecule BPVAn, can prepare a thin single crystal with uniform thickness and over 50 mu m size by a microspur sublimation method, and the crystal is pumped by a 400nm femtosecond laser at a lower threshold value (less than or equal to 10 mu J/cm)²) That is, laser emission can be realized, and a field effect transistor made of the single crystal can realize high hole mobility (5.24 cm)²V^-1s^-1) And electron mobility (0.16 cm)²V^-1s^-1) And strong electroluminescence can be observed.

It is to be understood that the advantages of the invention will be set forth in the description which follows and that the following detailed description is illustrative and explanatory thereof. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.

Drawings

In order to more clearly illustrate the technical solution in the embodiment of the present invention, the drawings required in the description of the embodiment will be briefly introduced as follows:

FIG. 1 shows the specific steps of synthesizing a bisstyryl derivative BPVAn according to an embodiment of the present invention.

FIG. 2 shows the growth of BPVA by the micro-space sublimation method according to the second embodiment of the present inventionn single crystal and transferred to Si/SiO²Brief procedure on PMMA substrate.

FIG. 3 is a photograph of the morphology and luminescence of a single crystal of tri-BPVAn of the example of the present invention under a fluorescence microscope, and also the absorption emission spectra of molecules in a tetrahydrofuran dilute solution and the crystal.

FIG. 4 shows the laser behavior of a four BPVAn single crystal according to an embodiment of the present invention under 400nm femtosecond light.

Fig. 5 is a schematic structural diagram and a top view of an organic light emitting diode (OLET) device fabricated from a single crystal of five BPVAn in accordance with an embodiment of the present invention.

Fig. 6 is a transfer curve and an output curve of a six BPVAn single crystal OLET device according to an embodiment of the present invention.

Fig. 7 is a photograph of light emission at different gate voltages and spectra of light emission at different source-drain voltages and different gate voltages of a seven BPVAn single crystal OLET device according to an embodiment of the present invention.

Detailed Description

The following detailed description of the embodiments of the present invention will be provided with reference to the drawings and examples, so that how to apply the technical means to solve the technical problems and achieve the technical effects can be fully understood and implemented. It should be noted that, as long as there is no conflict, the features in the embodiments of the present invention may be combined with each other, and the formed technical solutions are within the scope of the present invention.

The first embodiment is as follows:

a method for synthesizing a bisstyryl derivative molecule designs and synthesizes a bisstyryl derivative 4,4 '-bis ((E) -2- (anthracene-2-yl) vinyl) -1,1' -biphenyl, namely BPVAn, and comprises the following specific steps:

1. weighing 520mg (2mMol) of 2-bromoanthracene powder in a branch tube reactor, repeatedly exhausting Ar gas and a vacuum pump for 3-4 times by using a double-exhaust tube, discharging water and oxygen in the branch tube reactor, protecting with Ar, adding 10mL of ultra-dry tetrahydrofuran by using an injector, and stirring for 5min at the rotating speed of 500r/min at the temperature of-70 ℃. 0.5mL (5.3mmol) of butyllithium was slowly added dropwise to the reaction using a syringe, and the reaction was stirred for 1h without changing the conditions. Then, 0.5mL of ultra-dry N-Dimethylformamide (DMF) was slowly added dropwise using a syringe(6.4mmol) in the reaction, conditions were unchanged overnight. And adding deionized water to quench the reaction, extracting the reaction product by using dichloromethane and water, collecting lower solution, removing water by using anhydrous sodium sulfate, and then spin-drying by using a rotary evaporator. The resulting yellow powder was purified by silica gel column chromatography (CHCl)₂: petroleum ether 1:3) to obtain 396mg (yield 95.6%) of anthracene 2-carbaldehyde for later use.

2. Weighing 227mg (0.5mmol) of 4,4' -bis (diethoxyphosphonomethyl) biphenyl powder and 80mg (3.3mmol) of NaH powder in a branch tube reactor, repeatedly exhausting Ar gas and a vacuum pump for 3-4 times by using a double-exhaust tube, discharging water and oxygen in the branch tube reactor, protecting with Ar, adding 10mL of ultra-dry tetrahydrofuran by using an injector, and stirring for 1h at the rotating speed of 500r/min under the condition of ice-water bath. 230mg (1.1mmol) of anthracene 2-formaldehyde powder was weighed, dissolved in 10mL of ultra-dry tetrahydrofuran, and the solution was added to the reaction by syringe, and stirred at 500r/min at room temperature overnight. Adding deionized water and adding deionized water to quench the reaction. And extracting the obtained suspension by using dichloromethane, collecting the lower suspension, performing suction filtration at negative pressure, repeatedly washing the lower suspension for 3-4 times by using deionized water, ethanol and dichloromethane, and drying to obtain a final product, namely BPVAn powder of 250mg (yield of 89%).

For example, the amount ratio of the substances of the respective medicines in the above step S1 is 2-bromoanthracene: butyl lithium: nitrogen dimethylformamide ═ 2:5.3: 5.4; the amount ratio of the substances of each drug in step S2 was 4,4' -bis (diethoxyphosphonomethyl) biphenyl: NaH: anthracene 2-carbaldehyde 0.5: 3.3: 1.1.

the chromatography liquid used in the silica gel column chromatography in the step S1 is a mixed liquid of dichloromethane and petroleum ether, and the volume ratio of the mixture is 1: 3.

The biphenyl vinyl derivative molecule BPVAn is prepared according to the synthesis method, and has the structure as follows:

example two:

uniformly smearing BPVAn powder 0.5mg on a pre-cleaned common glass cover glass, placing on a hot bench,adding a gasket with the thickness of 0.34mm, taking a clean glass slide as an upper substrate, placing the glass slide right above the upper substrate, heating to 440 ℃, stopping heating after 5min, taking down the upper substrate when the temperature is reduced to room temperature, observing a shining BPVAn crystal, and observing most of single crystals in the glass slide to grow vertical to the surface of the substrate under a microscope. An upper substrate with BPVAb single crystal was spin-coated with Si/SiO with PMMA 20nm thick₂And (4) attaching the plates, namely transferring and flatly paving the BPVAn crystal on the surface of the PMMA.

Example three:

the transferred BPAVn crystal is observed under a fluorescence microscope, and the crystal is good, the surface is flat, and the edge is smooth and sharp when the crystal is observed under a white field; the fluorescent photograph shows that the crystal has good optical waveguide and optical confinement effects, and the edge emits bright green light. The absorption peak wavelength of the tetrahydrofuran dilute solution obtained from the absorption emission spectrum is 326nm, 338nm, 376nm and 395nm, and the luminescence peak wavelength is 430nm and 447 nm; the solid single crystal has absorption peaks at 424nm and 460nm and luminescence peaks at 502nm and 536 nm.

Example four:

characterization of the laser behavior of the crystal: and (3) placing the transferred BPVAn crystal under 400nm femtosecond laser, and observing and collecting the laser behavior. The left graph shows the change of the luminescence spectrum of the crystal along with the increase of the pumping energy, and the half-peak width of the luminescence can be seen to reach 10 mu J/cm²Then, the pumping energy is sharply reduced along with the rise of the pumping energy, the obvious stimulated emission behavior is shown, and the inset is a crystal luminescence photo above the threshold value. The right graph is a graph of the change of the luminous intensity along with the increase of the pumping energy and shows an obvious S-shaped nonlinear relation, and the threshold value of the laser is 10.2 mu J/cm²。

Example five:

and transferring and flatly spreading the BPVAn sheet single crystal on a Si/SiO2 substrate coated with polymethyl methacrylate (PMMA) with the thickness of 20nm, then performing vapor deposition on a silver electrode with the thickness of 100nm after masking the crystal, and removing a mask plate to obtain the organic light-emitting field effect transistor device.

For example, in a flat-laid manner on PMMA/SiO₂Covering a layer of mask plate on BPVAn crystal on a/Si substrate, and then placing the BPVAn crystal in a vacuum metal evaporation machine for evaporation 100After the sample of the silver after nm was removed, the mask was removed, and an OLET device having a source/drain electrode of Ag symmetrical electrode and a channel width of 25 μm was fabricated, and its field effect was measured using a Keithley 4200SCS semiconductor electrical test system as shown in fig. 5.

Example six:

testing of migration and output curves of OLET devices: respectively testing the hole migration signals of the device by using source and drain voltages of-60V, -90V and-120V and a gate voltage range of 20V to-100V, wherein the hole migration rate is 5.24cm when the source and drain voltages are-60V²V^-1s^-1The output curve of the measured hole signal is shown in the middle graph. And then testing the electron migration signal of the device by using source-drain voltages of 60V, 90V and 120V and a gate voltage range of 0-200V, and measuring the electron migration rate of 0.16cm when the source-drain voltage is 60V²V^-1s^-1Then, the output curve of the measured electronic signal is shown in the right graph. Experimental data prove that the BPVAn crystal can realize double injection of hole electrons and high mobility under a symmetrical electrode.

Example seven:

collecting the light emission spectrum of the OLET device: for a BPVAn organic light-emitting field effect transistor device, the source-drain voltage of the BPVAn organic light-emitting field effect transistor device is kept to be 120V, the gate voltage of the BPVAn organic light-emitting field effect transistor device is changed from 100V to 140V, the luminance of light emission of the BPVAn organic light-emitting field effect transistor device can be seen to be position change through a pre-established observation light path, as shown in the figure, the light emission of the BPVAn organic light-emitting field effect transistor device moves from a source electrode to a drain electrode along with the increase of the gate voltage, the light emission is weakened and then strengthened, and the electron migration curve corresponds to 120V. The fixed grid voltage is not changed at 110V, the source-drain voltage is changed from 100V to 140V, the pre-established spectrum acquisition system is used for acquiring the luminescence of the light, and spectrum data with the intensity increasing along with the rising of the source-drain voltage can be measured. With the gate voltage changed from 110V to 130V with the fixed source-drain voltage 120V unchanged, a spectrum data decreasing with increasing gate voltage can be measured. Thus, the regulation and control of the voltage on the luminous intensity and the luminous position are proved to be realized.