阅读说明：本技术 一种有机半导体单晶及其制备方法和应用 (Organic semiconductor single crystal and preparation method and application thereof ) 是由 刘城芳 王嘉波 李爽 赖文勇 于 2021-06-23 设计创作，主要内容包括：本发明公开了一种有机半导体单晶及其制备方法和应用,属于有机电子器件技术领域。所述制备方法包括步骤如下：选取两种具有苯环共轭结构的有机半导体材料,混入有机溶剂后制成混合溶液,再将上述混合溶液滴加在基底上,待有机溶剂完全挥发后即得到所述有机半导体单晶,所述具有苯环共轭结构的有机半导体材料选自TrNa、TIPS、C8-BTBT或C6-DBTDT。本发明实现了高质量的有机半导体单晶制备及其优化,从而实现了场效应晶体管器件的低成本、高迁移率的制备。(The invention discloses an organic semiconductor single crystal and a preparation method and application thereof, belonging to the technical field of organic electronic devices. The preparation method comprises the following steps: selecting two organic semiconductor materials with a benzene ring conjugated structure, mixing the two organic semiconductor materials with an organic solvent to prepare a mixed solution, then dropwise adding the mixed solution on a substrate, and obtaining the organic semiconductor single crystal after the organic solvent is completely volatilized, wherein the organic semiconductor material with the benzene ring conjugated structure is selected from TrNa, TIPS, C8-BTBT or C6-DBTDT. The invention realizes the preparation and optimization of high-quality organic semiconductor single crystals, thereby realizing the preparation of field effect transistor devices with low cost and high mobility.)

1. A method for producing an organic semiconductor single crystal, characterized by comprising the steps of: selecting two organic semiconductor materials with a benzene ring conjugated structure, mixing the two organic semiconductor materials with an organic solvent to prepare a mixed solution, then dropwise adding the mixed solution on a substrate, and obtaining the organic semiconductor single crystal after the organic solvent is completely volatilized, wherein the organic semiconductor materials with the benzene ring conjugated structure are selected from TrNa, TIPS, C8-BTBT or C6-DBTDT;

the structural formula of the TrNa is shown as the following formula:

2. a method for preparing an organic semiconductor single crystal according to claim 1, wherein the mass ratio of the two organic semiconductor materials having a benzene ring conjugated structure is 1: 1.

3. A method for producing an organic semiconductor single crystal according to claim 1, wherein the organic solvent is a mixture of dichloromethane and methanol.

4. A method for preparing an organic semiconductor single crystal according to claim 3, wherein the volume ratio of dichloromethane to methanol is 1 (1-4).

5. A method for producing an organic semiconductor single crystal according to claim 1, wherein the substrate is a silicon wafer treated with an organic silane, and the organic silane is OTS or PMMA.

6. A method for producing an organic semiconductor single crystal according to claim 1, wherein the temperature at which the organic solvent is volatilized is 10 ℃ to 40 ℃.

7. A method for preparing an organic semiconductor single crystal according to claim 1, wherein the concentration of the mixed solution is 0.05mg/mL to 10 mg/mL.

8. An organic semiconductor single crystal produced by the method for producing an organic semiconductor single crystal according to any one of claims 1 to 7.

9. Use of the organic semiconductor single crystal according to claim 8 for producing an organic single crystal field effect transistor.

10. An organic single crystal field effect transistor comprising the organic semiconductor single crystal according to claim 8.

Technical Field

The invention belongs to the technical field of organic electronic devices, and particularly relates to an organic semiconductor single crystal and a preparation method and application thereof.

Background

Single crystals of organic semiconductors are the result of regular close packing between adjacent molecules, with relatively weak non-covalent bonds, such as hydrogen bonds, van der waals forces, charge transfer interactions, and the like. The organic single crystal can reflect the most basic characteristics of materials, is beneficial to the research of a carrier transmission channel, provides an ideal model system for exploring the influence of basic acting force between molecules, the accumulation mode of the molecules and the like on the device performance, and is considered as an optimal carrier for revealing the inherent property of an organic semiconductor and analyzing the structure-performance relationship. However, there remains a major challenge to accurately control the molecular packing arrangement in organic single crystals to achieve specific properties. On the one hand, molecular conformation and packing have a significant impact on the internal structure and symmetry of organic crystallites. On the other hand, the organic crystallites are bound together by weak intermolecular interactions, which makes the crystallization process of the organic crystallites strongly dependent on external environmental conditions including the kind of solvent, temperature, solution concentration and surfactant. To date, kinetic control of the growth of different organic semiconductor single crystals to optimize photovoltaic performance remains a formidable task. Therefore, it is important to develop a simple, convenient and low-cost method for preparing a high-quality single crystal for improving the performance of a field effect transistor device.

Disclosure of Invention

The technical problem to be solved is as follows: aiming at the technical problems, the invention provides an organic semiconductor single crystal, a preparation method and application thereof, which realize the preparation and optimization of the high-quality organic semiconductor single crystal and further realize the preparation of a field effect transistor device with low cost and high mobility.

The technical scheme is as follows: a method for producing an organic semiconductor single crystal, comprising the steps of: selecting two organic semiconductor materials with a benzene ring conjugated structure, mixing the two organic semiconductor materials with an organic solvent to prepare a mixed solution, then dropwise adding the mixed solution on a substrate, and obtaining the organic semiconductor single crystal after the organic solvent is completely volatilized, wherein the organic semiconductor materials with the benzene ring conjugated structure are selected from TrNa, TIPS, C8-BTBT or C6-DBTDT;

the structural formula of the TrNa is shown as the following formula:

preferably, the mass ratio of the two organic semiconductor materials with the benzene ring conjugated structure is 1: 1.

Preferably, the organic solvent is a mixture of dichloromethane and methanol.

Preferably, the volume ratio of the dichloromethane to the methanol is 1 (1-4).

Preferably, the substrate is a silicon wafer treated with organic silane, and the organic silane is OTS or PMMA.

Preferably, the temperature for volatilizing the organic solvent is 10-40 ℃.

Preferably, the concentration of the mixed solution is 0.05mg/mL to 10 mg/mL.

An organic semiconductor single crystal produced by the above production method.

The organic semiconductor single crystal is applied to the preparation of an organic single crystal field effect transistor.

An organic single crystal field effect transistor comprising the organic semiconductor single crystal.

Has the advantages that: the invention blends two organic semiconductor materials with pi-pi interaction according to a specific proportion, screens a proper organic solvent to prepare a solution, and adopts a solvent slow volatilization method to further optimize the two organic semiconductor materials on the basis of keeping the original crystal form, thereby obtaining high-quality organic single crystals and finally obtaining the high-performance organic single crystal field effect transistor.

The operation steps of the invention can be carried out in the atmospheric environment, the preparation method is simple and convenient, the raw materials are easy to obtain, and the cost is low.

The two organic semiconductor materials can be crystallized respectively, and the crystallization of each component can be promoted due to pi-pi interaction, so that single crystals with higher quality than the single crystallization of the two organic semiconductor materials are obtained, and the mobility of the device reaches about 1.

Drawings

FIG. 1 is a single crystal image of TrNa and TIPS, wherein TrNa is a rod-shaped crystal and TIPS is a rhombohedral crystal;

FIG. 2 is a graph showing the transfer and output of the TrNa single crystal.

Detailed Description

The invention is further described below with reference to the accompanying drawings and specific embodiments. Reagents, materials and the like used in the following examples are commercially available unless otherwise specified.

EXAMPLE 1 preparation of TrNa

Hexanaphthalenyltriacendene (TrNa) was synthesized according to the synthetic route shown below:

hexabromotris-indene (TrBr) white solid (100mg,0.075mmol), 2-naphthylboronic acid white solid (116.7mg,0.675mmol), tetrabutylammonium bromide (TBAB) white solid (14.5mg,0.045mmol) and potassium hydroxide (KOH) white solid (38.2mg,0.68mmol) were dissolved in 3mL Tetrahydrofuran (THF) with exclusion of light, and after complete dissolution, palladium tetratriphenylphosphine (Pd (PPh) was added under nitrogen protection₃)₄) (52.5mg,0.045mmol), placed in a CEM Discover microwave reactor. The reaction temperature was set at 150 ℃ and the power 200W. The temperature of the reaction was monitored by a calibrated infrared temperature control device in the reactor, which was connected to the vessel by a diaphragm, controlling the pressure. The reaction was maintained at 150 ℃ for 30min and the temperature was lowered to room temperature. The reaction mixture was extracted with DCM and water to give an organic layer, which was washed with water several times, the organic layers were combined, dried over anhydrous magnesium sulfate, filtered under suction, and the solvent was concentrated and then subjected to column chromatography to give 54mg of a white solid with a yield of 45%. The formula for obtaining TrNa is shown as the following formula, wherein R represents an alkane chain:

EXAMPLE 2 preparation of organic semiconductor Single Crystal

The first step is as follows: p-type heavily doped SiO₂Pretreatment of silicon wafer substrate

SiO used₂the/Si silicon wafer is a heavily doped p-type silicon wafer with SiO 300nm thick₂Layer and 10.5nF cm^-2The capacitance of (c). SiO is deposited on a single surface₂The silicon chip is sequentially placed into deionized water, ethanol and acetone for ultrasonic treatment for 15 minutes, then the deionized water is used for ultrasonic treatment for 10 minutes to clean the surface of the substrate, and after the substrate is rapidly dried by nitrogen, the substrate is subjected to ultraviolet UV treatment for 10 minutes. And finally, OTS treatment is carried out: dripping Octadecylsilane (Octadecylsilane-OTS, molecular formula C) into capillary₁₈H₄₀Si) solution is put in a culture dish, a silicon wafer is put in the culture dish, is put in an oven and is vacuumized, and is dried for 3 hours at the temperature of 120 ℃;

the second step is that: preparation of organic semiconductor single crystals

Preparing a mixed solution of dichloromethane and methanol with a mass ratio of TrNa to TIPS (namely 6, 13-bis (triisopropylsilylethynyl) pentacene) of 1:1, wherein the total concentration is 0.5mg/mL, the volume ratio of dichloromethane to methanol is 1:2, dripping the mixed solution onto a silicon wafer treated in the first step after ultrasonic dissolution, standing the silicon wafer in a closed container for one day at room temperature, and obtaining an organic semiconductor single crystal structure on the silicon wafer after the solvent is completely volatilized; wherein, the addition of TIPS can regulate the interaction between molecules and improve the crystal form of TrNa. As shown in FIG. 1, the organic semiconductor single crystal was composed of a TrNa rod-like crystal and a TIPS rhombohedral crystal, wherein TrNa was the rod-like crystal and TIPS was the rhombohedral crystal, and the TrNa rod-like crystal had a diameter of about 1 μm and a length of about 40 μm. The transfer and output curves of the organic semiconductor single crystal are shown in FIG. 2.

EXAMPLE 3 organic Single Crystal field Effect transistor preparation

A TrNa organic single crystal field effect transistor was produced by depositing a gold electrode having a thickness of 30 to 50nm on the organic semiconductor single crystal obtained in example 2 by vacuum evaporation. The transistor sequentially comprises from bottom to top: a substrate (including a gate electrode), an organic semiconductor single crystal, a source electrode and a drain electrode over the organic semiconductor single crystal perpendicularly.

Device performance testing

The samples were analyzed using a Keithley 4200 SCS semiconductor parameter analyzer (Tektronix, Johnston, USA) under atmospheric conditionsThe electrical characteristics of the TrNa organic single crystal field effect transistor were measured, and the mobility thereof was measured in the saturation region. The measured field-effect carrier mobility of the TrNa single crystal was 0.96cm²V.s, on-off ratio of 10⁵The threshold voltage is-4.71V, and the performance is high.

EXAMPLE 4 preparation of organic semiconductor Single Crystal

The first step is as follows: p-type heavily doped SiO₂Pretreatment of silicon wafer substrate

SiO used₂the/Si silicon wafer is a heavily doped p-type silicon wafer with SiO 300nm thick₂Layer and 10.5nF cm^-2The capacitance of (c). SiO is deposited on a single surface₂The silicon chip is sequentially placed into deionized water, ethanol and acetone for ultrasonic treatment for 15 minutes, then the deionized water is used for ultrasonic treatment for 10 minutes to clean the surface of the substrate, and after the substrate is rapidly dried by nitrogen, the substrate is subjected to ultraviolet UV treatment for 10 minutes. And finally, PMMA treatment: dripping PMMA solution into a culture dish by using a capillary tube, placing a silicon wafer into the culture dish, placing the culture dish into a drying oven, vacuumizing, and drying for 3 hours at 120 ℃;

the second step is that: preparation of organic semiconductor single crystals

Preparing a mixed solution of dichloromethane and methanol with the mass ratio of C8-BTBT to C6-DBTDT being 1:1, wherein the total concentration is 10mg/mL, the volume ratio of dichloromethane to methanol is 1:4, dripping the mixed solution onto the silicon wafer treated in the first step after ultrasonic dissolution, placing the silicon wafer into a closed container at room temperature for standing for one day, and obtaining an organic semiconductor single crystal structure on the silicon wafer after the solvent is completely volatilized.

The above are embodiments of the present invention, it should be noted that the present invention is not limited to these examples, and these examples are only for better understanding of the present invention, and any equivalent changes made according to the technical solution of the present invention are within the protection scope of the present invention.