CN106431806B

CN106431806B - Compound of white light high mobility semiconductor material 2-fluorene anthracene derivative, preparation method and application

Info

Publication number: CN106431806B
Application number: CN201610828308.4A
Authority: CN
Inventors: 孟鸿; 陈梦芸; 赵阳; 闫丽佳; 黄维
Original assignee: Nanjing Tech University
Current assignee: Nanjing Tech University
Priority date: 2016-09-12
Filing date: 2016-09-12
Publication date: 2020-08-25
Anticipated expiration: 2036-09-12
Also published as: CN106431806A

Abstract

The invention relates to a compound of a white light high mobility material 2-fluorene anthracene derivative, a preparation method and application of the compound as a p-type organic semiconductor material and a luminescent material in an organic photoelectric device. The compound structure of the 2-fluorene anthracene derivative is shown as follows:

in the formula R₁‑R₉Can be the same or different and is independently selected from hydrogen, deuterium or a long alkyl chain of C1-C20, X is C, S or O, R₁₀‑R₁₁Can be the same or different and is independently selected from hydrogen, deuterium, long alkyl chains of C1-C20, doubly bound oxygen, or R₁₀、R₁₁And then jointly connected with fluorene to form 9, 9' -spirobifluorene. The material has better thermal stability and air stability, can be manufactured by a one-pot method, and is suitable for industrial production; the material has strong luminescence, can emit nearly pure white light in OLED, has excellent charge transmission property, can be applied to organic white light emitting transistor devices, and is used for realizing self-driven OLED illumination or display.

Description

Compound of white light high mobility semiconductor material 2-fluorene anthracene derivative, preparation method and application

Technical Field

The present invention relates to a 2-fluorenylanthracene derivative compound. In particular to a compound of 2-fluorene anthracene derivative, a preparation method and application of the compound as a p-type organic semiconductor and a luminescent material in an organic photoelectric device.

Background

White Organic Light Emitting Diodes (WOLEDs) have achieved significant results in many years of research due to their role in white lighting and OLED display. At present, white OLEDs are realized mainly by mixing monochromatic lights, one is by integrating three (red, green, blue) or two (blue, orange) light emitting layers in an OLED structure, and the other is by doping three (red, green, blue) or two (blue-orange) materials emitting lights of different colors into the same layer of host material. In both of these ways, the color stability of an OLED device must be affected by adverse charge transfer, phase separation, energy level mismatch, and doping concentration. Only when white light is from the same material, the problems of color stability and repeatability can be solved, and there have been some reports on the application of this kind of white light material in a single light-emitting substance OLED.

On the other hand, the white OLED also needs to be driven by a field effect transistor, and is structurally complicated. The Organic Light Emitting Transistor (OLET) integrates the functions of an Organic Light Emitting Diode (OLED) and an organic field effect transistor (OTFT), drives and emits light to operate on the same device, greatly simplifies the structure of the device and saves energy. In 2012, Dmitrii F. Perepichka et al reported the application of the material 2- (4-hexyl-phenylvinyl) anthracene (HPVAnt) to an OLET device (Angewandte chemical International Edition, ISSN: 1433-. However, to date, no material has been able to emit white light while having high mobility, and the lack of material has greatly hindered the implementation of white-light OLET devices and the development of self-driven OLED lighting and display applications.

Disclosure of Invention

Object of the Invention

The invention aims to provide a compound of 2-fluorene anthracene derivative.

Another object of the present invention is to provide three simple synthetic methods for the above-mentioned 2-fluorenylanthracene derivative compound.

It is still another object of the present patent to provide use of the above-mentioned compound of 2-fluorenylanthracene derivative for producing an organic light emitting diode device.

Still another object of the present invention is to provide the use of the above-mentioned 2-fluorenylanthracene derivative compound for the preparation of organic field effect transistor devices.

Detailed description of the invention

The invention designs and synthesizes the material 2-fluorene anthracene derivative, the molecular structure general formula of the 2-fluorene anthracene derivative provided by the invention is shown as the following formula,

in the formula R₁-R₉Can be the same or different and is independently selected from hydrogen, deuterium or a long alkyl chain of C1-C20, X is C, S or O, R₁₀-R₁₁Can be the same or different and is independently selected from hydrogen, deuterium, long alkyl chains of C1-C20, doubly bound oxygen, or R₁₀、R₁₁Co-linking with fluorene to form 9, 9' -spirobifluorene, preferably R₁-R₁₁Is hydrogen and X is C.

The molecular formula is shown in the specification, wherein in the molecular formula 1-molecular formula 6, R₁-R₁₁Which may be the same or different, are independently selected from hydrogen, deuterium, or a long alkyl chain of C1-C20:

the preparation method of the 2-fluorene anthracene derivative has the following reaction general formula:

in the formula R₁-R₉Can be the same or different and is independently selected from hydrogen, deuterium or a long alkyl chain of C1-C20, X is C, S or O, R₁₀-R₁₁Can be the same or different and is independently selected from hydrogen, deuterium, long alkyl chains of C1-C20, doubly bound oxygen, or R₁₀、R₁₁Co-linking with fluorene to form 9, 9' -spirobifluorene, preferably R₁-R₁₁Is hydrogen and X is C. The specific reaction steps of the invention are as follows:

the specific reaction steps of the invention are as follows:

the first method comprises the following steps: suzuki coupling (see formula (a) above): dissolving a 2-bromoanthracene derivative and boric acid ester of a fluorene derivative in a toluene solution according to a certain proportion, simultaneously adding a potassium carbonate aqueous solution and trioctylmethylammonium chloride, simultaneously adding a catalyst of tetratriphenylphosphine palladium, heating to 60-110 ℃ in a nitrogen environment, and reacting for 3-48 hours. Then cooled to room temperature, poured into methanol and filtered after the product precipitates. And finally purifying by a sublimation method. Wherein the proportion of the 2-bromoanthracene derivative, the fluorene derivative borate, the potassium carbonate and the tetratriphenyl phosphorus palladium is 1 to (1.0-1.5) to (2.0-3.0) to (0.005-0.05).

The second method comprises the following steps: still coupling reaction (see formula (b) above): dissolving a 2-bromoanthracene derivative and a tin reagent of a fluorene derivative in a toluene solution according to a certain proportion, simultaneously adding a catalyst of tetratriphenylphosphine palladium, heating to reflux in a nitrogen environment, and reacting for 3-24 hours. Then cooling to room temperature, pouring into methanol, precipitating the product and filtering. And finally purifying by a sublimation method. Wherein the ratio of the 2-bromoanthracene derivative, the fluorene derivative tin reagent and the tetratriphenyl phosphorus palladium is 1: 1.0-1.5: 0.01-0.1.

The third method comprises the following steps: negishi coupling reaction (see formula (c) above): dissolving zinc chloride salt of a fluorene derivative and a 2-bromoanthracene derivative in a tetrahydrofuran solution according to a certain proportion, simultaneously adding a catalyst of tetratriphenyl phosphine palladium, heating to 30-70 ℃, tracing the reaction process at a point plate in the process, cooling to normal temperature after the reaction is completed, and adding 1mol/L hydrochloric acid solution and dichloromethane to quench the reaction. Separating the oil layer by using a separating funnel, washing the oil layer to be neutral by using deionized water, drying and spin-drying. And finally purifying by a sublimation method. Wherein the ratio of the 2-bromoanthracene derivative, the zinc chloride salt of the fluorene derivative and the tetratriphenyl phosphorus palladium is 1: 1.0-1.5: 0.01-0.05.

The 2-fluorene anthracene derivative is prepared into a light emitting layer of the electroluminescent device by adopting an evaporation method. Specifically, the preparation method for preparing the electroluminescent device by taking the 2-fluorene anthracene derivative as the fluorescent luminescent material comprises the following steps:

the structure of the electroluminescent device is shown in figure 1, the electroluminescent device comprises ITO glass 1, and a hole injection layer 2, a hole transport layer 3, a luminescent layer 4, an electron transport layer 5, an electron injection layer 6 and an aluminum electrode 7 are sequentially attached to the ITO glass 1 from inside to outside. The ITO glass is sequentially cleaned in deionized water, acetone and isopropanol for 30 minutes by ultrasonic waves; preparing an organic film and a metal electrode in a vacuum chamber, and preparing the 2-fluorene anthracene derivative as a white fluorescent luminescent material into a luminescent layer of an electroluminescent device by an evaporation method. The current-voltage-luminance curve and the electroluminescence spectrum of the device are measured by corrected Keithley 2400 and Topcon BM-7A systems, the applied voltage is direct current voltage or alternating current voltage, and all the measurements are completed in room-temperature atmosphere.

The 2-fluorene anthracene derivative is used for preparing a functional layer of the organic field effect transistor device in an evaporation mode. Specifically, the preparation method for preparing the organic field effect transistor device by using the 2-fluorene anthracene derivative as the hole transport material comprises the following steps:

the structure is shown in figure 2, (a) is a horizontal structure, the device comprises a gate electrode 1, SiO₂The organic light-emitting diode comprises an insulating layer 2, an OTS modification layer 3, a functional layer 4, a source electrode 5 and a drain electrode 6. (b) For vertical structure, the device comprises a substrate 1, a gate electrode 2, SiO₂An insulating layer 3, a source electrode 4, a functional layer 5, and a drain electrode 6. Cleaning a silicon wafer with silicon dioxide in deionized water, acetone and isopropanol sequentially for 30 minutes by ultrasonic waves; drying by using nitrogen, treating for 15 minutes under ultraviolet illumination, preparing an organic film and a metal electrode in a vacuum chamber after OTS treatment, and taking the 2-fluorene-removed anthracene derivative as a functional layer by using an evaporation method. Wherein the transfer and transfer curves of the device were measured by a Keysight B1500A parametric analyzer, all measurements being performed in ambient temperature atmosphere.

Has the advantages that:

the invention combines simple anthracene derivative and fluorene derivative units to synthesize the new compound 2-fluorene anthracene derivative. The synthesis method has the advantages of simple steps, high yield, simple reaction device and convenient post-treatment. The cost of the synthetic material is greatly reduced, and the synthetic material has great commercial value. The derivatives have high thermal stability and air stability, and provide guarantee for the application of the derivatives in devices. The material adopts intermolecularlyJ-type aggregation, which has lower energy than H-type aggregation in common organic charge transport materials, inhibits quenching of fluorescence. The preferred molecule 2-fluorenylanthracene (R)₁-R₁₁Hydrogen, X is C) in chloroform solution with a fluorescence quantum yield of up to 51.4%. Meanwhile, due to special intermolecular force, an aggregation state formed by excited molecules and intrinsic molecules is promoted, and yellow green light emitted by the aggregation state is combined with blue light of the intrinsic molecules to form white light. Based on 2-fluorenylanthracene (R)₁-R₁₁Hydrogen, X is C) emits nearly pure white light with a CIE of (0.33, 0.34) at a voltage of 10V. When the substrate temperature is different in the device preparation process, the crystallinity and the stacking mode are changed, the mobility is changed, and when the substrate temperature is 60 ℃, the 2-fluorene anthracene (R) is based₁-R₁₁Hydrogen, X is C) has an OTFT mobility of at most 2.36cm²/(Vs). The property of white light high mobility enables the material to open a road for realizing white light OLET devices, and further preparing self-driven OLED display and illumination. Meanwhile, the method also provides a new idea for designing multifunctional materials in the subsequent research.

Drawings

FIG. 1 is a structural diagram of an OLED device based on a 2-fluorenylanthracene derivative according to the present invention.

FIG. 2 is a structural view of an OTFT device based on a 2-fluorenylanthracene derivative according to the present invention, wherein (a) and (b) correspond to field effect transistors of a horizontal structure and a vertical structure, respectively.

FIG. 3 shows that the present invention is based on 2-fluorenylanthracene (R)₁-R₁₁Hydrogen, X is C).

FIG. 4 shows that the present invention is based on 2-fluorenylanthracene (R)₁-R₁₁Hydrogen, X is C) is adopted as the light brightness diagram of the OLED device.

FIG. 5 shows that the present invention is based on 2-fluorenylanthracene (R)₁-R₁₁Current efficiency plot for OLED devices with X being C) for hydrogen.

FIG. 6 shows that the present invention is based on 2-fluorenylanthracene (R)₁-R₁₁Hydrogen, X is C) external quantum efficiency diagram of OLED device.

FIG. 7 shows that the present invention is based on 2-fluorenylanthracene (R)₁-R₁₁Hydrogen, X is C) at a substrate temperature of 60 degrees.

FIG. 8 shows that the present invention is based on 2-fluorenylanthracene (R)₁-R₁₁Hydrogen, X is C) at a substrate temperature of 60 degrees.

Detailed Description

Example 1:

the present invention provides the 2-fluorenylanthracene (R)₁-R₁₁Is hydrogen, X is C), the synthetic route is shown as the following formula,

the method specifically comprises the following steps:

suzuki reaction: dissolving 2-bromoanthracene and fluorene borate ester in a toluene solution according to a certain proportion, simultaneously adding a potassium carbonate aqueous solution and trioctylmethylammonium chloride, simultaneously adding a catalyst of tetratriphenylphosphamine, heating to 110 ℃ in a nitrogen environment, and reacting for 48 hours. Then cooled to room temperature, poured into methanol and filtered after the product precipitates. And finally purifying by a sublimation method. Wherein the ratio of the 2-bromoanthracene to the fluorene borate to the potassium carbonate to the tetratriphenylphosphamide is 1: 1.2: 2.4: 0.01.

Example 2:

the invention also provides an electroluminescent device, as shown in figure 1, the electroluminescent device comprises ITO glass 1, and a hole injection layer 2, a hole transport layer 3, a luminescent layer 4, an electron transport layer 5, an electron injection layer 6 and an aluminum electrode 7 are sequentially attached to the ITO glass 1 from inside to outside. Wherein the light-emitting layer 4 is composed of the 2-fluorenylanthracene (R)₁-R₁₁Is hydrogen, X is C), the hole injection layer 2 is MoO₃The electron injection layer 6 is LiF (lithium fluoride). The hole transport layer 3 is composed of NPB (N, N ' -di (naphthyl) -N, N ' -di (phenyl) biphenyl-4, 4 ' -diamine), and the electron transport layer 5 may be composed of TPBi (1, 3, 5-tris ((N-phenyl) benzimidazolyl) benzene). The thickness of the hole injection layers 2 and 6 can be 1nm, the thickness of the luminescent layer 4 can be 20nm, the thickness of the hole transport layer 3 can be 60nm, and the thickness of the electron transport layer5 a thickness of 40 nm. :

the 2-fluorenylanthracene (R)₁-R₁₁Hydrogen, X is C) is used for preparing the luminous layer of the electroluminescent device by adopting an evaporation mode. Specifically, the 2-fluorene anthracene (R)₁-R₁₁Is hydrogen, X is C) as a fluorescent luminescent material, and the preparation method of the electroluminescent device comprises the following steps:

the ITO glass is sequentially cleaned in deionized water, acetone and isopropanol for 30 minutes by ultrasonic waves; preparing an organic film and a metal electrode in a vacuum chamber, and preparing the 2-fluorene anthracene serving as a white fluorescent luminescent material into a luminescent layer of an electroluminescent device by an evaporation method. The current-voltage-luminance curve and the electroluminescence spectrum of the device were measured by Keithley 2400 with overcorrection and by Topcon BM-7A system, all measurements being carried out in a room temperature atmosphere.

FIG. 3 shows the emission spectrum of the OLED device of the present invention at a voltage of 4V, with a maximum brightness of 2610cd/m²The maximum current efficiency reaches 0.38cd/A, the color coordinate of the electroluminescence spectrum reaches nearly pure white (0.33, 0.34), and the maximum external quantum efficiency is 0.17%, as shown in figures 4-6.

Example 3:

the present invention also provides an organic field effect transistor device, as shown in fig. 2(a), comprising a gate electrode 1, SiO₂The organic light-emitting diode comprises an insulating layer 2, an OTS modification layer 3, a functional layer 4, a source electrode 5 and a drain electrode 6. Wherein the functional layer 3 is formed of the 2-fluorenylanthracene (R)₁-R₁₁Hydrogen, X is C), the gate electrode 1 is highly doped silicon, and the source electrode 5 and the drain electrode 6 are gold. The thickness of the functional layer 4 may be 30nm, SiO₂ The insulating layer 2 may have a thickness of 250nm and the source and

drain electrodes

5 and 6 may have a thickness of 40 nm.

The 2-fluorenylanthracene (R)₁-R₁₁Hydrogen, X is C) is a functional layer of the organic field effect transistor device manufactured by adopting an evaporation mode. Specifically, the 2-fluorene anthracene (R)₁-R₁₁For hydrogen, X being C) as hole-transporting material for making organic field-effect transistor devicesThe preparation method comprises the following steps:

cleaning a silicon wafer with silicon dioxide in deionized water, acetone and isopropanol sequentially for 30 minutes by ultrasonic waves; drying by using nitrogen, treating for 15 minutes under ultraviolet illumination, preparing an organic film and a metal electrode in a vacuum chamber after OTS treatment, and taking the 2-fluorene-removed anthracene as a functional layer 4 by an evaporation method. Wherein the transfer and transfer curves of the device were measured by a Keysight B1500A parametric analyzer, all measurements being performed in ambient temperature atmosphere.

When the temperature of the evaporated substrate is 60 ℃, the maximum mobility of the organic field effect transistor device reaches 2.36cm²/(Vs), the on-off ratio is 3.47 × 10⁶The threshold voltage was-44.2V, and the transfer curve and the transmission curve are shown in FIGS. 7 and 8.

Summarizing the above results, the organic semiconductor material 2-fluorenylanthracene (R)₁-R₁₁X is C) emits near-pure white light in a single-light-emitting-substance OLED and the mobility of OTFTs based on this material is up to 2.36cm²/(Vs), such white light high mobility materials provide material support for the fabrication of white light OLET devices, opening the way for self-driven OLED displays or lighting.

The 2-fluorene anthracene organic semiconductor material provided by the embodiments of the present invention, the preparation method and the application thereof are described in detail above, the principle and the embodiment of the present invention are illustrated herein by using specific examples, the description of the above embodiments is only used to help understanding the method of the present invention and the core concept thereof, and the content of the present specification should not be construed as limiting the present invention.

Claims

1. A compound of a 2-fluorenylanthracene derivative:

in the formula R₁-R₉Can be the same or different and is independently selected from C₁-C₂₀X is C, S or O, R₁₀-R₁₁Can be the same or different and are independently selected from hydrogen, doubly-bound oxygen, or R₁₀、R₁₁And then jointly connected with fluorene to form 9, 9' -spirobifluorene.

2. A process for producing a 2-fluorenylanthracene derivative according to claim 1, comprising the steps of:

(1) the first method comprises the following steps: suzuki coupling reaction: dissolving a 2-bromoanthracene derivative and boric acid ester of a fluorene derivative in a toluene solution, simultaneously adding a potassium carbonate aqueous solution and trioctylmethylammonium chloride, simultaneously adding a catalyst of tetratriphenylphosphonium palladium, heating to 60-110 ℃ in a nitrogen environment, reacting for 3-48 hours, then cooling to room temperature, pouring into methanol, separating out a product, filtering, and finally purifying by using a sublimation method, wherein the ratio of the 2-bromoanthracene derivative, the boric acid ester of the fluorene derivative, the potassium carbonate and the tetratriphenylphosphonium palladium is 1: 1.0-1.5: 2.0-3.0: 0.005-0.05);

(2) the second method comprises the following steps: still coupling reaction: dissolving a 2-bromoanthracene derivative and a tin reagent of a fluorene derivative in a toluene solution, adding a catalyst of tetratriphenyl phosphorus palladium, heating to reflux in a nitrogen environment, reacting for 3-24 hours, cooling to room temperature, pouring into methanol, separating out a product, filtering, and purifying by a sublimation method, wherein the ratio of the 2-bromoanthracene derivative, the tin reagent of the fluorene derivative and the tetratriphenyl phosphorus palladium is 1: 1.0-1.5: 0.01-0.1;

(3) the third method comprises the following steps: negishi coupling reaction: dissolving zinc chloride salt of a fluorene derivative and a 2-bromoanthracene derivative in a tetrahydrofuran solution, adding a catalyst of tetratriphenylphosphoropadium, heating to 30-70 ℃, tracking the reaction process by a point plate in the process until the reaction is completed, cooling to normal temperature, adding 1mol/L hydrochloric acid solution and dichloromethane to quench the reaction, separating an oil layer by using a separating funnel, washing to be neutral by using deionized water, drying, spin-drying, and purifying by using a sublimation method, wherein the ratio of the 2-bromoanthracene derivative to the zinc chloride salt of the fluorene derivative to the tetratriphenylphosphoropadium is 1: 1.0-1.5: 0.01-0.05.

3. The production method according to claim 2, wherein in the first method, the ratio of the 2-bromoanthracene derivative to the fluorene derivative borate is less than 1: 1; in a second method, the 2-bromoanthracene derivative and fluorene derivative tin reagent ratio is less than 1: 1; in a third method, the zinc chloride salt ratio of the 2-bromoanthracene derivative and the fluorene derivative is less than 1: 1.

4. The process according to claim 2, wherein in the first process and in the second process, the organic solvent is selected from toluene; in the third method, tetrahydrofuran is selected as the organic solvent in the reaction.

5. The method according to claim 2, wherein in the first and second methods, the reaction is carried out under an inert gas atmosphere, and the product is precipitated in methanol; in all three methods, the crude product is purified by sublimation.

6. Use of compounds of 2-fluorenylanthracene derivatives according to claim 1 for the production of organic electronic devices.

7. Use according to claim 6 as a light-emitting layer of an organic light-emitting diode.

8. The use according to claim 7, wherein the driving voltage in the organic light emitting diode is a direct current voltage or an alternating current voltage.

9. Use according to claim 6 as a semiconducting active layer of an organic field effect transistor.