Organic semiconductor material based on organometallic sulfides of silver hexathiophenolate and use thereof

Abstract

The application discloses an organic semiconductor material based on a hexamer capto benzene silver organic metal sulfide and application thereof. The heterogeneous synthesis method of the hexamer capto benzene silver comprises the following steps: under the condition of heating, the hexamer capto benzene silver is reacted with silver chloride in an organic solvent under an inert atmosphere, and the reaction temperature is 45-65 DEG C, and the reaction time is 24-72 h. The hexamer capto benzene silver is prepared through a P-type organic semiconductor device, and the migration rate can be up to 50 cm 2 / (V.s)~200 cm 2 / (V.s). The raw material is cheap and easy to obtain, is low-toxicity and harmless, is an environment-friendly and sustainable development new method for preparing materials. The reaction process of the method is convenient and controllable, the utilization rate is high, and the method is more suitable for laboratory and commercial production, and has a good application prospect for the development of the organic metal sulfide material in the field of organic semiconductor materials.

Description

Technical Field

[0001] This invention relates to an organic semiconductor material based on hexamercaptophenylsilver organometallic sulfide and its applications, belonging to the field of organic semiconductor materials. Background Technology

[0002] Organic semiconductor materials have attracted great interest from the scientific community and have great application prospects due to their advantages such as low production cost, lightweight materials, convenient processing and synthesis, and easy design and control of their structure to obtain different electrical properties.

[0003] In the exploration of organic semiconductor materials, organometallic sulfides, especially hexamercaptobenzene metal coordination polymers, have been extensively studied due to their excellent electrical transport properties. However, current preparation methods for these coordination polymers rely on cumbersome interfacial reactions, and the fabrication of semiconductor devices is limited by the size of single-crystal materials, allowing only macroscopic device fabrication and testing methods at the bulk thin-film scale, which fails to capture the intrinsic properties of the material and the fabrication of the device. Furthermore, the mobility of organic semiconductor materials is significantly lower than that of traditional inorganic semiconductor materials. Therefore, finding new synthetic methods to obtain organic semiconductor materials with suitable size and high mobility is of great significance. Summary of the Invention

[0004] The purpose of this invention is to provide an organometallic sulfide based on hexamercaptophenylsilver (Ag5BHT), which is prepared by a heterogeneous synthesis method and can be used as a semiconductor material with high mobility.

[0005] The heterogeneous synthesis method of hexamercaptophenylsilver provided by this invention includes the following steps:

[0006] Hexamercaptobenzene is obtained by reacting with silver chloride in an organic solvent under an inert atmosphere and under heating conditions.

[0007] In the above heterogeneous synthesis method, the organic solvent can be methanol or isopropanol.

[0008] In the above heterogeneous synthesis method, the reaction temperature is 45–65°C and the reaction time is 24–72 h.

[0009] In the above heterogeneous synthesis method, the molar ratio of silver chloride to hexamercaptobenzene is 2-3:1, preferably 2.5:1.

[0010] In the above heterogeneous synthesis method, the following processing steps are further included after the reaction is completed:

[0011] The filtered product of the reaction system was washed sequentially with water, methanol, and anhydrous diethyl ether.

[0012] The single crystal length of the hexamercaptophenyl silver (Ag5BHT) provided by this invention is 10μm to 25μm, such as 15μm.

[0013] The hexamercaptophenylsilver (Ag5BHT) provided by this invention exhibits a p-type organic semiconductor mobility of 50 cm⁻¹ at room temperature. 2 / (V·s)~200cm 2 / (V·s).

[0014] The application of hexamercaptophenylsilver (Ag5BHT) provided by this invention as an organic semiconductor material, and its application in the preparation of organic semiconductor devices, are also within the scope of protection of this invention.

[0015] The present invention has the following advantages:

[0016] The heterogeneous synthesis method used for hexamerylbenzene silver (Ag5BHT) allows for a degree of control over the size of the product over time, resulting in higher crystallinity and phase purity. In this invention, hexamerylbenzene silver, when used in the fabrication of p-type organic semiconductor devices, achieves a mobility as high as 50 cm⁻¹. 2 / (V·s)~200cm 2 / (V·s). The raw materials are inexpensive, readily available, low in toxicity, and harmless, making this a novel, environmentally friendly, and sustainable method for preparing materials. The reaction process of this invention is convenient and controllable, with high utilization, making it more suitable for laboratory and commercial production. It shows great promise for the development of organometallic sulfide materials in the field of organic semiconductor materials. Attached Figure Description

[0017] Figure 1 A flowchart illustrating the steps involved in the preparation of hexamercaptophenylsilver (Ag5BHT) using a heterogeneous synthesis method.

[0018] Figure 2 The image shows the powder X-ray diffraction (XRD) pattern of hexamercaptophenylsilver (Ag5BHT) prepared in Example 1 of this invention and its comparison with the theoretical pattern.

[0019] Figure 3 The image shows the SEM pattern of the hexamercaptophenylsilver (Ag5BHT) powder prepared in Example 1 of this invention.

[0020] Figure 4 The TEM image is of the hexamercaptophenylsilver (Ag5BHT) powder prepared in Example 1 of this invention.

[0021] Figure 5 AFM spectrum of the hexamercaptophenylsilver (Ag5BHT) powder prepared in Example 1 of this invention.

[0022] Figure 6This is a schematic diagram of the bottom-gate top-contact organic semiconductor device prepared in Embodiment 1 of the present invention.

[0023] Figure 7 This is the transfer curve of the P-type organic semiconductor measured in Example 1 of the present invention.

[0024] Figure 8 This is the output curve of the P-type organic semiconductor measured in Example 1 of the present invention. Detailed Implementation

[0025] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0026] Unless otherwise specified, all materials and reagents used in the following examples are commercially available.

[0027] The following examples demonstrate the testing of the mobility performance of p-type organic semiconductor materials using the following methods:

[0028] Using a Keithley 4200 SCS semiconductor analyzer, the p-type transfer and output curves of bottom-gate top-contact organic semiconductor devices were tested using a fabrication and testing method to obtain their mobility.

[0029] (1) The SiO2 / Si wafer was immersed in a solution of concentrated sulfuric acid and hydrogen peroxide (7:3) for 30 minutes, followed by ultrasonic cleaning with deionized water, ethanol, and acetone for 5 minutes each. After cleaning, it was dried with nitrogen. The cleaned SiO2 / Si wafer was subjected to plasma surface cleaning treatment (Plasma) for 5 minutes (100% power). Then, the treated SiO2 / Si wafer was placed in a vacuum oven and modified with octadecyltrichlorosilane (OTS) at 120°C for 3 hours. The modified SiO2 / Si wafer was then ultrasonically cleaned with n-hexane, ethanol, and chloroform for 5 minutes each, and dried with nitrogen to obtain a SiO2 / Si silicon wafer ready for testing.

[0030] (2) Take a small amount of Ag5BHT powder and ultrasonically disperse it in ethanol or acetone, such as an ethanol solution. Then, use a dropper method to evenly drop the Ag5BHT ethanol solution onto the treated SiO2 / Si wafer.

[0031] (3) Under a microscope, through methods such as Figure 6 After obtaining a bottom-gate top-contact organic semiconductor device by applying a gold film, the mobility is tested.

[0032] Example 1: Hexamercaptophenylsilver (Ag5BHT) was produced using a heterogeneous reaction method.

[0033] (1) Solvent degassing: Add 50 ml of isopropanol to a 100 ml two-necked flask and use the Freeze-Thaw method to remove dissolved oxygen from the solvent using liquid nitrogen.

[0034] (2) Under an argon atmosphere, hexamethylenetetramine (27 mg, 0.1 mmol) and silver chloride (35 mg, 0.25 mmol) were added to a 100 mL two-necked flask containing 50 mL of degassed isopropanol. The mixture was ultrasonically dispersed for 5 minutes, and then the temperature of the reaction solution was raised to 50 °C and the reaction was carried out for 36 h. After the reaction was completed, the mixture was allowed to cool to room temperature naturally and then filtered. It was washed successively with water, methanol, and anhydrous diethyl ether, and dried at 60 °C for 24 h in a vacuum drying oven (absolute pressure of 0.05 Pa) to obtain hexamethylenetetramine silver organometallic sulfide, which was labeled as Ag5BHT.

[0035] Elemental analysis of Ag5BHT material revealed the following: theoretical elemental content: C, 8.97; S, 23.93; Ag, 67.10; experimental elemental content: C, 9.02; S, 23.43; Ag, 67.52, indicating that the obtained material has high phase purity.

[0036] Figure 1 A flowchart of the heterogeneous synthesis method for preparing hexamercaptophenylsilver (Ag5BHT).

[0037] Figure 2 The image shows the powder XRD pattern of the Ag5BHT material prepared in this embodiment. As can be seen from the image, the experimental XRD (top) and the simulated XRD (bottom) are highly consistent, and the material exhibits excellent crystallinity.

[0038] Figures 3-5 The SEM, TEM, and AFM spectra of the Ag5BHT material prepared in this embodiment show that the single crystal size of Ag5BHT material is between 10μm and 25μm, and the thickness is about 200nm.

[0039] Figure 7 and Figure 8 The image shows the characteristic curves of the Ag5BHT p-type organic semiconductor material prepared in this embodiment. It can be seen that the material of this invention exhibits excellent mobility performance, with a p-type organic semiconductor mobility of 50 cm⁻¹. 2 / (V·s)~200cm 2 / (V·s).

Claims

1. The application of hexamercaptophenylsilver as a material or in the preparation of organic semiconductor materials, characterized in that: The preparation method of the hexamercaptophenylsilver is as follows: 1) Solvent degassing: Add 50 mL of isopropanol to a 100 mL two-necked flask and use the Freeze-Thaw method to remove dissolved oxygen from the solvent using liquid nitrogen; (2) Under an argon atmosphere, 27 mg, 0.1 mmol hexamercaptobenzene and 35 mg, 0.25 mmol silver chloride were added to a 100 mL two-necked flask containing 50 mL of degassed isopropanol. The mixture was ultrasonically dispersed for 5 minutes, and the temperature of the reaction solution was raised to 50 °C. The reaction was carried out for 36 h. After the reaction was completed, the mixture was naturally cooled to room temperature and filtered. It was washed successively with water, methanol and anhydrous diethyl ether. It was dried at 60 °C for 24 h in a vacuum drying oven with an absolute pressure of 0.05 Pa to obtain silver hexamercaptobenzene organometallic sulfide, labeled as Ag5BHT.

2. An application of hexamercaptophenylsilver in the construction of organic semiconductor devices, characterized in that: The preparation method of the hexamercaptophenylsilver is as follows: 1) Solvent degassing: Add 50 mL of isopropanol to a 100 mL two-necked flask and use the Freeze-Thaw method to remove dissolved oxygen from the solvent using liquid nitrogen; (2) Under an argon atmosphere, 27 mg, 0.1 mmol hexamercaptobenzene and 35 mg, 0.25 mmol silver chloride were added to a 100 mL two-necked flask containing 50 mL of degassed isopropanol. The mixture was ultrasonically dispersed for 5 minutes, and the temperature of the reaction solution was raised to 50 °C. The reaction was carried out for 36 h. After the reaction was completed, the mixture was naturally cooled to room temperature and filtered. It was washed successively with water, methanol and anhydrous diethyl ether. It was dried at 60 °C for 24 h in a vacuum drying oven with an absolute pressure of 0.05 Pa to obtain silver hexamercaptobenzene organometallic sulfide, labeled as Ag5BHT.

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