阅读说明：本技术 有机光电半导体材料及其制备方法与应用 (Organic photoelectric semiconductor material and preparation method and application thereof ) 是由 胡文平 李金峰 郑磊 张小涛 于 2018-06-22 设计创作，主要内容包括：本发明公开了一种有机光电半导体材料及其制备方法与应用,有机光电半导体材料为2,6-二蒽基萘、2,6-双(9,10-二三异丙基硅基乙炔基蒽基)萘或2,6-二蒽-1,5-双(三异丙基硅基乙炔基)萘。有机光电半导体材料的制备方法,包括以下步骤：在惰性气体环境下,将反应物A、反应物B、作为催化剂的四(三苯基磷)钯、甲苯和碳酸钾水溶液均匀混合,混合后升温至90～100℃反应24～96小时,过滤得到滤渣,用洗涤剂洗涤滤渣,得到有机光电半导体材料,本发明提供的制备反应路线具有简单高效、环境友好、原料价格廉价、合成成本低的优点；方法普适性高,重复性好；本发明为高性能有机光电材料提供了一个新的选择。(The invention discloses an organic photoelectric semiconductor material and a preparation method and application thereof, wherein the organic photoelectric semiconductor material is 2, 6-dianthracene naphthalene, 2, 6-bis (9, 10-triisopropylsilylethynyl anthracene group) naphthalene or 2, 6-dianthracene-1, 5-bis (triisopropylsilylethynyl group) naphthalene. The preparation method of the organic photoelectric semiconductor material comprises the following steps: in an inert gas environment, uniformly mixing a reactant A, a reactant B, palladium tetrakis (triphenylphosphine) as a catalyst, toluene and a potassium carbonate aqueous solution, heating to 90-100 ℃ after mixing, reacting for 24-96 hours, filtering to obtain filter residues, and washing the filter residues with a detergent to obtain the organic photoelectric semiconductor material, wherein the preparation reaction route provided by the invention has the advantages of simplicity, high efficiency, environmental friendliness, low raw material price and low synthesis cost; the method has high universality and good repeatability; the invention provides a new choice for high-performance organic photoelectric materials.)

1. An organic photoelectric semiconductor material has a structural formula as follows:

wherein R is₁Is hydrogen or triisopropylsilylacetylene, R₂The organic photoelectric semiconductor material is 2, 6-dianthracene naphthalene, 2, 6-bis (9, 10-triisopropylsilylethynyl anthracene) naphthalene or 2, 6-dianthracene-1, 5-bis (triisopropylsilylethynyl) naphthalene.

2. The method for producing an organic photoelectric semiconductor material according to claim 1, comprising the steps of:

uniformly mixing a reactant A, a reactant B, tetrakis (triphenylphosphine) palladium as a catalyst, toluene and a potassium carbonate aqueous solution in an inert gas environment, heating to 90-100 ℃ after mixing, reacting for 24-96 hours, filtering to obtain filter residue, and washing the filter residue with a detergent to obtain the organic photoelectric semiconductor material, wherein the mass ratio of the reactant A to the reactant B is (2.1-2.4): 1, the ratio of the volume parts of the toluene, the mass parts of the reactant B and the mass parts of the potassium carbonate in the potassium carbonate aqueous solution is (9-15): 1: (4-15);

when the organic photoelectric semiconductor material is 2, 6-dianthracene naphthalene, the reactant A is 2-anthracene borate, and the reactant B is 2, 6-dibromo naphthalene;

when the organic photoelectric semiconductor material is 2, 6-bis (9, 10-triisopropylsilylethynyl anthracene base) naphthalene, the reactant A is 2-bromo-9, 10-triisopropylsilylethynyl anthracene, and the reactant B is 2, 6-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) naphthalene;

when the organic photoelectric semiconductor material is 2, 6-dianthracene-1, 5-bis (triisopropylsilylethynyl) naphthalene, the reactant A is 2-anthracene borate, and the reactant B is 2, 6-dibromo-1, 5-bis (triisopropylsilylethynyl) naphthalene.

3. The method according to claim 2, wherein when the organic photoelectric semiconductor material is 2, 6-dianthracene naphthalene, the ratio of the amounts of the reactant A and the reactant B is (2.1-2.2): 1.

4. the method according to claim 2, wherein when the organic photoelectric semiconductor material is 2, 6-bis (9, 10-triisopropylsilylethynyl anthracenyl) naphthalene, the ratio of the amounts of the substances of the reactant A and the reactant B is (2.2-2.4): 1.

5. the production method according to claim 2, wherein when the organic photoelectric semiconductor material is 2, 6-dianthracene-1, 5-bis (triisopropylsilylethynyl) naphthalene, the ratio of the amounts of the substances of the reactant A and the reactant B is (2.1 to 2.2): 1.

6. the method of claim 3 or 4 or 5, wherein the ratio of the reactant B to the catalyst is 1: (0.05-0.1).

7. The preparation method according to claim 6, wherein the concentration of potassium carbonate in the aqueous potassium carbonate solution is 2M, the unit of volume fraction is mL, and the unit of mass fraction is mmol.

8. The method of claim 7, wherein the inert gas is argon or nitrogen.

9. The use of the preparation method according to claims 2 to 8 for preparing the organic optoelectronic semiconductor material.

10. The use according to claim 9, wherein the preparation process has a yield of 69 to 89%.

Technical Field

The invention belongs to the technical field of organic photoelectric semiconductor materials, and particularly relates to an organic photoelectric semiconductor material and a preparation method and application thereof.

Background

Organic semiconductor devices such as organic solar cells (OPVs), Organic Light Emitting Diodes (OLEDs), Organic Electrochromism (OECs), and Organic Thin Film Transistors (OTFTs) have been developed and applied in many fields. In all these organic photoelectric fields, organic photoelectric materials are key. The organic semiconductor material which is designed and synthesized and has simple process, lower cost, stable material performance and long service life so as to achieve the purpose of commercialization has wide application prospect.

The condensed ring acene material is an organic material with good photoelectric property. For example, the single crystal mobility of pentacene has reached 15-40cm²V^-1s^-1. Anthracene is the smallest member of the acene family with transistor properties and has better luminescence and device performance. In general, increasing conjugation can increase the combination of transfer integration and decreasing recombination energy resulting in higher charge carrier mobility. Therefore, naphthalene ring is added in the middle of the anthracene ring, so that conjugation is increased, and luminescence of anthracene is maintained.

Although a large number of organic semiconductor materials have been designed and synthesized, there are not many materials that have high fluorescence quantum efficiency and high mobility. However, such materials are critical in the preparation of OLETs and OLEDs. The preparation of such materials is of great importance.

Disclosure of Invention

In view of the defects of the prior art, the invention aims to provide an organic photoelectric semiconductor material, the invention also aims to provide a preparation method of the organic photoelectric semiconductor material, and the invention also aims to provide application of the preparation method in preparing the organic photoelectric semiconductor material.

The purpose of the invention is realized by the following technical scheme.

An organic photoelectric semiconductor material has a structural formula as follows:

wherein R is₁Is hydrogen or triisopropylsilylacetylene, R₂The organic photoelectric semiconductor material is 2, 6-dianthracene naphthalene, 2, 6-bis (9, 10-triisopropylsilylethynyl anthracene) naphthalene or 2, 6-dianthracene-1, 5-bis (triisopropylsilylethynyl) naphthalene.

The preparation method of the organic photoelectric semiconductor material comprises the following steps:

uniformly mixing a reactant A, a reactant B, tetrakis (triphenylphosphine) palladium as a catalyst, toluene and a potassium carbonate aqueous solution in an inert gas environment, heating to 90-100 ℃ after mixing, reacting for 24-96 hours, filtering to obtain filter residue, and washing the filter residue with a detergent to obtain the organic photoelectric semiconductor material, wherein the mass ratio of the reactant A to the reactant B is (2.1-2.4): 1, the ratio of the volume parts of the toluene, the mass parts of the reactant B and the mass parts of the potassium carbonate in the potassium carbonate aqueous solution is (9-15): 1: (4-15);

when the organic photoelectric semiconductor material is 2, 6-dianthracene naphthalene, the reactant A is 2-anthracene borate, and the reactant B is 2, 6-dibromo naphthalene;

when the organic photoelectric semiconductor material is 2, 6-bis (9, 10-triisopropylsilylethynyl anthracene base) naphthalene, the reactant A is 2-bromo-9, 10-triisopropylsilylethynyl anthracene, and the reactant B is 2, 6-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) naphthalene;

when the organic photoelectric semiconductor material is 2, 6-dianthracene-1, 5-bis (triisopropylsilylethynyl) naphthalene, the reactant A is 2-anthracene borate, and the reactant B is 2, 6-dibromo-1, 5-bis (triisopropylsilylethynyl) naphthalene.

In the above technical solution, when the organic photoelectric semiconductor material is 2, 6-dianthracene naphthalene, the ratio of the amounts of the reactant a and the reactant B is (2.1-2.2): 1.

when the organic photoelectric semiconductor material is 2, 6-bis (9, 10-triisopropylsilylethynyl anthracenyl) naphthalene, the ratio of the amounts of the reactant A and the reactant B is (2.2-2.4): 1.

when the organic photoelectric semiconductor material is 2, 6-dianthracene-1, 5-bis (triisopropylsilylethynyl) naphthalene, the ratio of the amounts of the reactant A and the reactant B is (2.1-2.2): 1.

in the above technical solution, the ratio of the reactant B to the catalyst is 1: (0.05-0.1).

In the above technical scheme, the concentration of potassium carbonate in the potassium carbonate aqueous solution is 2M.

In the above technical scheme, the inert gas is argon or nitrogen.

In the technical scheme, the unit of volume parts is mL, and the unit of mass parts is mmol.

The preparation method is applied to the preparation of the organic photoelectric semiconductor material.

In the technical scheme, the yield of the preparation method is 69-89%.

Compared with the prior art, the invention has the following beneficial effects:

the preparation reaction route provided by the invention has the advantages of simplicity, high efficiency, environmental friendliness, low raw material price and low synthesis cost; the method has high universality and good repeatability;

the invention provides a new choice for high-performance organic photoelectric materials.

Drawings

FIG. 1 is a UV-VIS absorption spectrum of 2, 6-dianthracene naphthalene in solid state prepared in example 1;

FIG. 2 is a UPS plot of 2, 6-dianthracene naphthalene prepared in example 1;

FIG. 3 is a TGA curve of 2, 6-dianthracene naphthalene prepared in example 1;

FIG. 4 is a schematic structural diagram of an organic field effect transistor;

FIG. 5(a) is a typical transfer curve for OFETs prepared from 2, 6-dianthracene naphthalene prepared in example 1;

FIG. 5(b) is a graph of the output of OFETs prepared from 2, 6-dianthracene naphthalene prepared in example 1;

FIG. 6 shows the single crystal structure of 2, 6-dianthracene naphthalene prepared in example 1.

Detailed Description

The technical scheme of the invention is further explained by combining specific examples.

The following examples relate to pharmaceutical products as purchasers and purities as follows:

the following examples relate to the apparatus and models for the test characterization as follows:

nuclear magnetism: BRUKER AVANCE III

Mass spectrum: APEX II type Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR-MS)

Elemental analysis: FLASH EA1112 element analyzer

Ultraviolet: UV2600 ultraviolet visible spectrophotometer

UPS test: ESCLAb 250Xi multifunctional X-ray photoelectron spectrometer

And (3) thermogravimetric testing: thermal Analysis Excellence TGA 2

And (3) testing a device: keithley 4200-scs

Crystal resolution: XtalaBmini, Inc. of society