CN110734451B - Semiconductor material, preparation method thereof and organic light-emitting diode - Google Patents

Abstract

The invention discloses a semiconductor material, a preparation method thereof and an organic light-emitting diode, wherein the general molecular structural formula of the semiconductor material is

Description

Semiconductor material and preparation method thereof, and organic light-emitting diode

technical field

The invention relates to the field of organic semiconductors, in particular to a semiconductor material and a preparation method thereof, and an organic light-emitting diode.

Background technique

Organic light-emitting diodes (OLEDs) have broad application prospects in the field of flexible display and lighting due to their advantages of low production cost and large-area fabrication. Therefore, the research on organic semiconductor materials for OLEDs has attracted the attention of researchers.

The development of organic semiconductor materials characterized by air stability, high hole mobility, and high luminous efficiency remains a challenge in this field. [1]Benzothiophene[3,2-b][1]benzothiophene (BTBT), as a classic semiconductor core, has aroused extensive interest of researchers due to its excellent device performance.

Furan derivatives have potential applications in the field of luminescence due to their unique properties. Furan is one of the simplest heterocyclic aromatic compounds with very similar chemical structure and electronic properties to thiophene. However, thiophenes contain relatively heavy sulfur atoms, which cause fluorescence quenching due to internal conversion of the heavy atoms due to spin-orbit coupling. However, furan semiconductors do not have the problem of fluorescence quenching caused by spin-orbit coupling. Compared with thiophene semiconductors, furan semiconductors have better fluorescence properties, so they can be used to prepare organic semiconductor light-emitting devices.

Thiophene derivatives have strong carrier mobility characteristics, while furan derivatives and have strong fluorescence properties, both of which have different characteristics due to their respective structures. However, the prior art lacks a semiconductor material with both high electron mobility and high fluorescence performance.

Therefore, the existing technology still needs to be improved and developed.

SUMMARY OF THE INVENTION

In view of the above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a semiconductor material, a preparation method thereof, and an organic light-emitting diode, aiming to solve the problem that the high electron mobility and high fluorescence efficiency of the existing organic semiconductor material cannot be achieved simultaneously.

The technical scheme of the present invention is as follows:

其中，Ar1和Ar2均为含N的芳香基团或缺电子基团取代的芳香基团。A semiconductor material, wherein the general formula of the molecular structure of the semiconductor material is

Among them, Ar1 and Ar2 are both aromatic groups substituted by N-containing aromatic groups or electron-deficient groups.

In the semiconductor material, the electron-deficient group includes a cyano group, a nitro group and a halogen group.

其中，R1，R2，R3，R4，R5，R6，R7，R8，R9，R10，R11，R12，R13，R14，R15、R16、R17，R18和R19独立地选自氰基、硝基、烷基、芳基或含氮杂环中的一种。The semiconductor material, wherein the N-containing aromatic group comprises:

wherein, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18 and R19 are independently selected from cyano, nitro, alkane one of a group, an aryl group or a nitrogen-containing heterocyclic ring.

The semiconductor material, wherein the semiconductor material comprises:

A method for preparing a semiconductor material, comprising the steps of:

Mixing benzothiophene with N-bromosuccinimide, the reaction generates 3-bromobenzothiophene;

Mixing the 3-bromobenzothiophene with hydrogen peroxide, the reaction generates benzothiophene oxide;

的第一中间体；The benzothiophene oxide is mixed with phenol, and the reaction generates the molecular structural formula as

the first intermediate;

的第二中间体；The first intermediate is mixed with diisobutylaluminum hydride, and the reaction generates the molecular structural formula as

the second intermediate;

的第三中间体；The second intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added, and the mixed reaction generates the molecular structural formula as

the third intermediate;

的第四中间体；The third intermediate is mixed with the catalyst PdCl ₂ (PPh ₃ ) ₂ , and the reaction generates the molecular structural formula as

the fourth intermediate;

的第五中间体；The fourth intermediate is mixed with liquid bromine, and the reaction generates molecular structural formula as

the fifth intermediate;

的半导体材料，其中，Ar1和Ar2均为含N的芳香基团或缺电子基团取代的芳香基团。The fifth intermediate is mixed with one of N-containing aryl boronic acid, N-containing aryl tin, aryl boronic acid substituted with an electron-deficient group, or aryl tin substituted with an electron-deficient group and passed through PdCl ₂ (PPh ₃ ) ₂ catalysts catalyze coupling, and the reaction obtains the molecular structural formula as

The semiconductor material, wherein Ar1 and Ar2 are both aromatic groups substituted by N-containing aromatic groups or electron-deficient groups.

An organic light-emitting diode, which includes an electronic functional layer, and the electronic functional layer is prepared by using the semiconductor material.

In the organic light emitting diode, the electronic functional layer is an electron injection layer and/or an electron transport layer.

其中，Ar1和Ar2均为含N的芳香基团或缺电子基团取代的芳香基团，由于所述Ar1和Ar2引入了缺电子官能团，能进一步[1]苯并噻吩[3,2-b][1]苯并呋喃的电子传递能力以及发光效率。本发明可有效解决现有半导体材料高电子迁移率与高荧光效率不兼得的问题。Beneficial effects: the present invention designs a semiconductor material containing both thiophene functional groups and furan functional groups in combination with the characteristics of high electron mobility of thiophene derivatives and high fluorescence properties of furan derivatives. The molecular structure of the semiconductor material The general formula is

Among them, Ar1 and Ar2 are both N-containing aromatic groups or aromatic groups substituted by electron-deficient groups. Since the Ar1 and Ar2 introduce electron-deficient functional groups, they can further [1]benzothiophene[3,2-b ][1] The electron transfer ability and luminous efficiency of benzofuran. The invention can effectively solve the problem that the high electron mobility and high fluorescence efficiency of the existing semiconductor materials cannot be achieved.

Detailed ways

The present invention provides a semiconductor material, a preparation method thereof, and an organic light-emitting diode. In order to make the purpose, technical solution and effect of the present invention clearer and clearer, the present invention is further described below in detail. It should be understood that the specific embodiments described herein are only used to explain the present invention, but not to limit the present invention.

其中，Ar1和Ar2均为含N的芳香基团或缺电子基团取代的芳香基团。In order to solve the problem that high electron mobility and high fluorescence efficiency of existing semiconductor materials cannot be achieved simultaneously, the present invention provides a semiconductor material, wherein the general formula of the molecular structure of the semiconductor material is:

Among them, Ar1 and Ar2 are both aromatic groups substituted by N-containing aromatic groups or electron-deficient groups.

Furan rings have been widely used to construct π-conjugated molecules, and furan derivatives have the following advantages: (1) Substituting sulfur atoms with oxygen reduces aromaticity on the one hand, and the molecules have more quinoid structural features, making π- The electrons are better delocalized; on the other hand, the oxidation potential can be reduced, so that the energy level of the HOMO orbital is increased, thus facilitating the injection and transport of holes. (2) Thiophene contains relatively heavy sulfur atoms. Due to the internal conversion of spin-orbit coupling of heavy atoms, fluorescence quenching occurs, while furan semiconductors do not have the problem of fluorescence quenching caused by spin-orbit coupling. Compared with thiophene Semiconductors have more excellent fluorescent properties, so they can be used to fabricate organic semiconductor light-emitting devices, including OLEDs and organic light-emitting transistors (OLETs). (3) Furan compounds have less aromaticity and less intermolecular π-π interaction, so the solubility is relatively large. (4) Furan is a biodegradable material that can be prepared from biorenewable raw materials, which makes it more suitable for large-scale applications.

In the present invention, a semiconductor material containing both a thiophene functional group and a furan functional group is designed in combination with the high electron mobility of the thiophene derivative and the high fluorescence performance of the furan derivative, and the name of the semiconductor material is [1] Benzothiophene[3,2-b][1]benzofuran derivatives, Ar1 and Ar2 bound to the [1]benzothiophene[3,2-b][1]benzofuran are both containing An aromatic group substituted with an N-containing aromatic group or an electron-deficient group, the N-containing aromatic group or an aromatic group substituted with an electron-deficient group can promote [1] benzothiophene due to the introduction of an electron-deficient functional group. [3,2-b][1]benzofuran has stronger electron mobility and luminous efficiency. Therefore, the semiconductor material provided by the present invention can be used as the electronic functional layer of the organic light emitting diode device. The semiconductor material is made into a semiconductor thin film by the method, and an organic light emitting diode device with high electron mobility and high fluorescence efficiency is further prepared.

其中，Ar1和Ar2均为含N的芳香基团或缺电子基团取代的芳香基团，所述Ar1和Ar2可以为相同的基团或不同的基团。Specifically, the semiconductor material provided by the present invention is a double-sided substituted [1]benzothiophene[3,2-b][1]benzofuran derivative, and the double-sidedly substituted [1]benzothiophene[3, The general molecular structure of 2-b][1]benzofuran derivatives is

Wherein, Ar1 and Ar2 are both N-containing aromatic groups or aromatic groups substituted by electron-deficient groups, and Ar1 and Ar2 may be the same group or different groups.

Preferably, the electron deficient group includes cyano, nitro and halo.

其中，R1，R2，R3，R4，R5，R6，R7，R8，R9，R10，R11，R12，R13，R14，R15、R16、R17，R18和R19独立地选自氰基、硝基、烷基、芳基或含氮杂环中的一种。More preferably, in the semiconductor material, the N-containing aromatic group includes:

wherein, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18 and R19 are independently selected from cyano, nitro, alkane one of a group, an aryl group or a nitrogen-containing heterocyclic ring.

As an example, the molecular structural formula of the semiconductor material provided by the present invention specifically includes:

半导体材料的制备方法，其中，包括步骤：Further, the present invention also provides a molecular structure with the general formula of

A preparation method of a semiconductor material, comprising the steps of:

Mixing benzothiophene with N-bromosuccinimide, the reaction generates 3-bromobenzothiophene;

Mixing the 3-bromobenzothiophene with hydrogen peroxide, the reaction generates benzothiophene oxide;

的第一中间体；The benzothiophene oxide is mixed with phenol, and the reaction generates the molecular structural formula as

the first intermediate;

的第二中间体；The first intermediate is mixed with diisobutylaluminum hydride, and the reaction generates the molecular structural formula as

the second intermediate;

的第三中间体；The second intermediate is dissolved in glacial acetic acid and N-bromosuccinimide is added, and the mixed reaction generates the molecular structural formula as

the third intermediate;

的第四中间体；The third intermediate is mixed with the catalyst PdCl ₂ (PPh ₃ ) ₂ , and the reaction generates the molecular structural formula as

the fourth intermediate;

的第五中间体；The fourth intermediate is mixed with liquid bromine, and the reaction generates molecular structural formula as

the fifth intermediate;

的半导体材料，其中，Ar1和Ar2均为Ar1和Ar2均为含N的芳香基团或缺电子基团取代的芳香基团。The fifth intermediate is mixed with one of N-containing aryl boronic acid, N-containing aryl tin, aryl boronic acid substituted with an electron-deficient group, or aryl tin substituted with an electron-deficient group and passed through PdCl ₂ (PPh ₃ ) ₂ catalysts catalyze coupling, and the reaction obtains the molecular structural formula as

The semiconductor material, wherein Ar1 and Ar2 are both Ar1 and Ar2 are aromatic groups substituted by N-containing aromatic groups or electron-deficient groups.

Further, the present invention also provides an organic light emitting diode, which includes an electronic functional layer, and the electronic functional layer is prepared by using the semiconductor material. Specifically, the electronic functional layer is an electron injection layer and/or an electron transport layer.

The preparation method of a semiconductor material of the present invention will be further explained below through specific embodiments:

Example 1

其具体制备步骤包括：The synthetic scheme of 2,7-bis(pyridin-2-yl)[1]benzothiophene[3,2-b][1]benzofuran is:

Its specific preparation steps include:

Dissolve 20 g (150 mmol) of benzothiophene in 150 mL of chloroform, add 33.2 g (186 mmol) of N-bromosuccinimide in batches at 0 °C, and react at 0 °C for 4 h, then warm to room temperature and continue to stir 24h. 60 mL of chloroform was added, washed with sodium thiosulfate aqueous solution, saturated sodium carbonate and water respectively, the organic phase was dried with anhydrous magnesium sulfate, concentrated, and 3-bromobenzothiophene was obtained by column chromatography.

Dissolve 10 g (46 mmol) of 3-bromobenzothiophene in 80 mL of dichloromethane and 80 mL of trifluoroacetic acid solution, stir at room temperature for 5 minutes, add 4 mL of 35% hydrogen peroxide, stir until the reaction of the raw materials is complete, add saturated carbonic acid The sodium solution was neutralized to neutral, the layers were separated, the organic phase was washed with saturated sodium bicarbonate and water, dried over anhydrous magnesium sulfate, concentrated, and the compound 3-bromobenzothiophene-1-oxygen was obtained by column chromatography.

2.3g (10mmol) of 3-bromobenzothiophene-1-oxygen, 3.4g (20mmol) of phenol, 2.76g (20mmol) of potassium carbonate and 30mL of anhydrous DMF were stirred and reacted at 70°C overnight, cooled to room temperature, and concentrated. , the residue was dissolved in 50 mL of dichloromethane, washed with saturated brine and water, the organic phase was dried over anhydrous magnesium sulfate, concentrated, and subjected to column chromatography to obtain 3-phenoxybenzothiophene-1-oxygen.

Dissolve 2.54 g (8 mmol) 3-phenoxybenzothiophene-1-oxygen in 50 mL of anhydrous toluene, and slowly add diisobutylaluminum hydride (16 mmol, 13 mL, 20% toluene solution) dropwise at 0 °C. ), the addition was completed, the reaction was stirred at 65°C until the raw materials disappeared, cooled to 0°C, neutralized with 2M aqueous sodium hydroxide solution, extracted with dichloromethane three times, combined with the organic phases, washed with water to the center, anhydrous sulfuric acid Dry over magnesium, concentrate and column chromatography to give 3-phenoxybenzothiophene.

Dissolve 1.82g.6 (6mmol) 3-phenoxybenzothiophene in 30mL glacial acetic acid, add 1.2g (6.6mmol) NBS, stir for 10 minutes, and continue to stir the reaction at 55°C for 2h. Cool to room temperature, add 80 mL of ice water, extract three times with ethyl acetate, combine the organic phases, wash the organic phases with saturated sodium carbonate, saturated brine and water, dry over anhydrous magnesium sulfate, and obtain 2-bromo-3- Phenoxybenzothiophene.

Dissolve 1.51g (4mmol) 2-bromo-3-phenoxybenzothiophene and 0.67g (8mmol) sodium acetate in 80mL N,N-dimethylacetamide, add 0.14g (0.2mmol) PdCl under nitrogen ₂ (PPh ₃ ) ₂ , stirred overnight at 140°C, cooled to room temperature, added 200 mL of 1 mol/L hydrochloric acid, extracted with 500 mL of ethyl acetate and n-hexane (volume ratio 1:1), and the organic phase was washed with saturated brine and Washed with water, dried over anhydrous magnesium sulfate, concentrated, and subjected to column chromatography to obtain the target compound [1]benzothiophene[3,2-b][1]benzofuran.

Dissolve 4.48g, 20mmol of [1]benzothiophene[3,2-b][1]benzofuran in 250mL of chloroform at 0°C and 100mL of chloroform solution containing 9.6g, 60mmol of liquid bromine, dropwise add liquid bromine in chloroform solution, until the reaction of the raw materials is complete, add a saturated aqueous solution of sodium thiosulfate to reduce the excess liquid bromine. The organic phase was washed with saturated aqueous sodium bicarbonate solution and water, and then dried, and column chromatography was performed using petroleum ether as the eluent to obtain 2,7-dibromo[1]benzothiophene[3,2-b][1]benzoyl. furan.

2.0 g (5 mmol) 2,7-dibromo[1]benzothiophene[3,2-b][1]benzofuran and 1.84 g (15 mmol, 3 equiv) pyridine-2-boronic acid were dissolved in 50 mL toluene , add 10 mL of 2M potassium carbonate aqueous solution, blow with nitrogen for 30 min, add Pd(PPh ₃ ) ₄ (2% equiv.), stir at 110°C for 24 h under nitrogen atmosphere, pour the reaction mixture into 100 mL of methanol, filter, and use hydrochloric acid for the solid. and water wash. 2,7-bis(pyridin-2-yl)[1]benzothiophene[3,2-b][1]benzofuran was obtained by high vacuum sublimation.

Example 2

其具体制备步骤包括：The synthetic scheme of 2,7-bis(pyridin-3-yl)[1]benzothiophene[3,2-b][1]benzofuran is:

Its specific preparation steps include:

2,7-Dibromo[1]benzothiophene[3,2-b][1]benzofuran was prepared by the same procedure as in Example 1;

2.0 g (5 mmol) 2,7-dibromo[1]benzothiophene[3,2-b][1]benzothiophene and 1.84 g (15 mmol, 3 equiv) pyridine-3-boronic acid were dissolved in 50 mL toluene , add 10 mL of 2M potassium carbonate aqueous solution, blow with nitrogen for 30 min, add Pd(PPh ₃ ) ₄ (2% equiv.), stir at 110°C for 24 h under nitrogen atmosphere, pour the reaction mixture into 100 mL of methanol, filter, and use hydrochloric acid for the solid. and water wash. 2,7-bis(pyridin-3-yl)[1]benzothiophene[3,2-b][1]benzofuran was obtained by high vacuum sublimation.

Example 3

其具体制备步骤包括：The synthetic scheme of 2,7-bis(pyridin-4-yl)[1]benzothiophene[3,2-b][1]benzofuran is:

Its specific preparation steps include:

2,7-Dibromo[1]benzothiophene[3,2-b][1]benzofuran was prepared by the same procedure as in Example 1;

2.0 g (5 mmol) 2,7-dibromo[1]benzothiophene[3,2-b][1]benzofuran and 1.84 g (15 mmol, 3 equiv) pyridine-4-boronic acid were dissolved in 50 mL toluene , add 10 mL of 2M potassium carbonate aqueous solution, blow with nitrogen for 30 min, add Pd(PPh ₃ ) ₄ (2% equiv.), stir at 110°C for 24 h under nitrogen atmosphere, pour the reaction mixture into 100 mL of methanol, filter, and use hydrochloric acid for the solid. and water wash. 2,7-bis(pyridin-4-yl)[1]benzothiophene[3,2-b][1]benzofuran was obtained by high vacuum sublimation.

Example 4

其具体制备步骤包括：The synthetic scheme of 2,7-bis(quinolin-3-yl)[1]benzothiophene[3,2-b][1]benzofuran is:

Its specific preparation steps include:

2,7-Dibromo[1]benzothiophene[3,2-b][1]benzofuran was prepared by the same procedure as in Example 1;

2.0 g (5 mmol) of 2,7-dibromo[1]benzothiophene[3,2-b][1]benzofuran and 2.60 g (15 mmol, 3 equiv.) of quinoline-3-boronic acid were dissolved in 50 mL of toluene , add 10 mL of 2M potassium carbonate aqueous solution, blow with nitrogen for 30 min, add Pd(PPh ₃ ) ₄ (2% equiv.), stir at 110 C for 24 h under nitrogen atmosphere, pour the reaction mixture into 100 mL of methanol, filter, and use Washed with hydrochloric acid and water. 2,7-bis(quinolin-3-yl)[1]benzothiophene[3,2-b][1]benzofuran was obtained by high vacuum sublimation.

Example 5

其具体制备步骤包括：The synthetic scheme of 2,7-bis(quinolin-8-yl)[1]benzothiophene[3,2-b][1]benzofuran is:

Its specific preparation steps include:

2,7-Dibromo[1]benzothiophene[3,2-b][1]benzofuran was prepared by the same procedure as in Example 1;

2.0 g (5 mmol) of 2,7-dibromo[1]benzothiophene[3,2-b][1]benzofuran and 2.60 g (15 mmol, 3 equiv.) of quinoline-8-boronic acid were dissolved in 50 mL of toluene , add 10 mL of 2M potassium carbonate aqueous solution, blow with nitrogen for 30 min, add Pd(PPh ₃ ) ₄ (2% equiv.), stir at 110 C for 24 h under nitrogen atmosphere, pour the reaction mixture into 100 mL of methanol, filter, and use Washed with hydrochloric acid and water. 2,7-bis(quinolin-8-yl)[1]benzothiophene[3,2-b][1]benzofuran was obtained by high vacuum sublimation.

Example 6

其具体制备步骤包括：The synthesis process of 2,7-bis(1,10-o-phenanthrolin-3-yl)-4-yl[1]benzothiophene[3,2-b][1]benzofuran is:

Its specific preparation steps include:

2,7-Dibromo[1]benzothiophene[3,2-b][1]benzofuran was prepared by the same procedure as in Example 1;

2.0 g (5 mmol) of 2,7-dibromo[1]benzothiophene[3,2-b][1]benzofuran and 3.36 g (15 mmol, 3 equiv.) of 1,10-o-phenanthroline-3 - Boric acid was dissolved in 50 mL of toluene, 10 mL of 2M potassium carbonate aqueous solution was added, blown with nitrogen for 30 min, Pd(PPh ₃ ) ₄ (2% equiv.) was added, stirred at 110 C for 24 h under nitrogen atmosphere, and the reaction mixture was poured into 100 mL of methanol , filtered, and the solid was washed with hydrochloric acid and water. 2,7-bis(1,10-o-phenanthrolin-3-yl)-4-yl[1]benzothiophene[3,2-b][1]benzofuran was obtained by high vacuum sublimation.

Example 7

The synthesis process of 2,7-di-benzothiazol-4-yl[1]benzothiophene[3,2-b][1]benzofuran is:

其具体制备步骤包括：

Its specific preparation steps include:

2,7-Dibromo[1]benzothiophene[3,2-b][1]benzofuran was prepared by the same procedure as in Example 1;

Under nitrogen protection, 2,7-dibromo[1]benzothiophene[3,2-b][1]benzofuran (3.8 g, 10 mmol), bispinacol boronate (7.62 g, 30 mmol) ), potassium acetate (3.92 g, 40 mmol) and [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) dichloromethane complex (0.3 mmol, 0.25 g) were dissolved in 100mL of dimethyl sulfoxide, purged with nitrogen for 15 minutes, heated at 80C for 10h, cooled to room temperature, poured into ice water, extracted three times with dichloromethane, combined the organic phases, washed with water three times, dried over magnesium sulfate, concentrated , and purified by column chromatography to obtain 2,7-dipinacol boronate[1]benzothiophene[3,2-b][1]benzofuran;

2.38 g (5 mmol) of 2,7-dipinacol boronate[1]benzothiophene[3,2-b][1]benzofuran and 3.23 g (15 mmol, 3 equiv.) of 4-bromobenzene The thiadiazole was dissolved in 50 mL of toluene, 10 mL of 2M potassium carbonate aqueous solution was added, blown with nitrogen for 30 min, added with Pd(PPh ₃ ) ₄ (2% equiv.), stirred at 110 C for 24 h under nitrogen atmosphere, and the reaction mixture was poured into 100 mL of methanol, filtered, and the solid was washed with hydrochloric acid and water. 2,7-Di-benzothiazol-4-yl[1]benzothiophene[3,2-b][1]benzofuran was obtained by high vacuum sublimation.

Example 8

其具体制备步骤包括：The synthesis process of 2,7-dibenzothiazol-5-yl[1]benzothiophene[3,2-b][1]benzofuran is as follows:

Its specific preparation steps include:

2,7-Dipinacol boronate[1]benzothiophene[3,2-b][1]benzofuran was prepared by the same procedure as in Example 7;

2.38 g (5 mmol) 2,7-dipinacol boronate[1]benzothiophene[3,2-b][1]benzofuran and 3.23 g (15 mmol, 3 equiv.) 5-bromobenzene The thiadiazole was dissolved in 50 mL of toluene, 10 mL of 2M potassium carbonate aqueous solution was added, blown with nitrogen for 30 min, added with Pd(PPh ₃ ) ₄ (2% equiv.), stirred at 110 C for 24 h under nitrogen atmosphere, and the reaction mixture was poured into 100 mL of methanol, filtered, and the solid was washed with hydrochloric acid and water. 2,7-Di-benzothiazol-5-yl[1]benzothiophene[3,2-b][1]benzofuran was obtained by high vacuum sublimation.

Example 9

其具体制备步骤包括：Synthesis scheme of 2,7-bis-(2,4-diphenyl-1,3,5-triazin-6-yl)[1]benzothiophene[3,2-b][1]benzofuran for:

Its specific preparation steps include:

2,7-Dipinacol boronate[1]benzothiophene[3,2-b][1]benzofuran was prepared by the same procedure as in Example 7;

2.38 g (5 mmol) of 2,7-dipinacol boronate[1]benzothiophene[3,2-b][1]benzofuran and 4.00 g (15 mmol, 3 equiv.) of 2,4- Diphenyl-6-chloro-1,3,5-triazine was dissolved in 50 mL of toluene, 10 mL of 2M potassium carbonate aqueous solution was added, nitrogen was purged for 30 min, Pd(PPh ₃ ) ₄ (2% equiv.) was added, and Stir at 110C for 24h under nitrogen atmosphere, pour the reaction mixture into 100mL methanol, filter, and wash the solid with hydrochloric acid and water. 2,7-Di-benzothiazol-5-yl[1]benzothiophene[3,2-b][1]benzofuran was obtained by high vacuum sublimation.

Example 10

Device preparation and performance testing:

The silicon wafer is masked with a semiconductor mask, an appropriate substrate temperature is selected, and the thin film is prepared under high vacuum. The evaporation rate of the semiconductor material is controlled, and the electrode mask is used for electrode evaporation after the film is prepared, and Au is used as the electrode material. The properties of the prepared organic light-emitting diode devices were tested by a semiconductor analyzer. The Id-Vg and Id-Vd curves were tested, and the mobility calculation was performed using the following formula: _Id =(W/2L) _{μTFT Ci ( Vg} - _Vth ) ² .

The existing material DPh-BTBT and the semiconductor materials prepared in Example 1, Example 4, Example 6 and Example 9 of the present invention were used to prepare the same organic thin film transistor device, and their electron mobility and fluorescence quantum efficiency were tested respectively. , the result looks like this:

(DPh-BTBT)材料均具有较高的电子迁移率，但是本发明提供的材料相较于现有DPh-BTBT材料具有更高的荧光效率。It can be seen from the above experimental results that the semiconductor material prepared by the present invention is comparable to the existing

(DPh-BTBT) materials all have higher electron mobility, but the materials provided by the present invention have higher fluorescence efficiency than existing DPh-BTBT materials.

其中，Ar1和Ar2均为含N的芳香基团或缺电子基团取代的芳香基团，所述Ar1和Ar2由于引入了缺电子官能团，能进一步[1]苯并噻吩[3,2-b][1]苯并呋喃的电子传递能力以及发光效率。本发明可有效解决现有半导体材料高电子迁移率与高荧光效率不兼得的问题。To sum up, the present invention designs a semiconductor material containing both thiophene functional groups and furan functional groups in combination with the high electron mobility of thiophene derivatives and the high fluorescence properties of furan derivatives. The general molecular structure is

Among them, Ar1 and Ar2 are both N-containing aromatic groups or aromatic groups substituted by electron-deficient groups. Due to the introduction of electron-deficient functional groups, Ar1 and Ar2 can further [1]benzothiophene[3,2-b ][1] The electron transport ability and luminous efficiency of benzofuran. The invention can effectively solve the problem that the high electron mobility and high fluorescence efficiency of the existing semiconductor materials cannot be achieved.

It should be understood that the application of the present invention is not limited to the above examples. For those skilled in the art, improvements or changes can be made according to the above description, and all such improvements and changes should belong to the appended claims of the present invention.

Claims (5)

1. The semiconductor material is characterized in that the general molecular structural formula of the semiconductor material is

Wherein Ar1 and Ar2 are both N-containing aromatic groups or aromatic groups substituted by electron-deficient groups; the electron-deficient group is one of cyano, nitro and halogen, and the N-containing aromatic group is

Wherein, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18 and R19 are independently selected from one of cyano-group, nitro-group, alkyl-group, aryl-group or nitrogen-containing heterocycle.

2. The semiconductor material of claim 1, wherein the semiconductor material is

One kind of (1).

3. A method for preparing a semiconductor material, comprising the steps of:

mixing benzothiophene and N-bromosuccinimide, and reacting to generate 3-bromobenzothiophene;

mixing the 3-bromobenzothiophene with hydrogen peroxide, and reacting to generate benzothiophene oxide;

mixing the benzothiophene oxide with phenol to react to generate a compound with a molecular structural formula of

The first intermediate of (a);

reacting the first intermediate with diisobutylhydrogenMixing aluminum oxide, reacting to generate a molecular structural formula

A second intermediate of (a);

dissolving the second intermediate in glacial acetic acid, adding N-bromosuccinimide, and mixing to obtain the final product with a molecular structural formula

A third intermediate of (4);

reacting the third intermediate with a catalyst PdCl₂(PPh₃)₂Mixing, reacting to obtain the compound with the molecular structural formula

The fourth intermediate of (1);

mixing the fourth intermediate with liquid bromine, and reacting to obtain a compound with a molecular structural formula

The fifth intermediate of (4);

mixing the fifth intermediate with one of N-aryl-containing boric acid, N-aryl-tin-containing aromatic boric acid substituted by electron-deficient group or aromatic tin substituted by electron-deficient group, and passing through PdCl₂(PPh₃)₂The catalyst is catalyzed, coupled and reacted to obtain the molecular structural formula

Wherein Ar1 and Ar2 are both N-containing aromatic groups or electron-deficient group-substituted aromatic groups.

4. An organic light emitting diode comprising an electronic functional layer, wherein the electronic functional layer is prepared from the semiconductor material according to any one of claims 1 to 2.

5. The OLED of claim 4, wherein the electron functional layer is an electron injection layer and/or an electron transport layer.