Application of triarylamine compound as laser gain medium in laser device

Abstract

The invention discloses an application of a triarylamine compound as a laser gain medium in a laser device. The triarylamine compound is selected from a structure as shown in a formula (I). Researches show that the triarylamine compound shown in the formula (I) can be used as a laser gain material for preparing a laser device, and the triarylamine compound is mainly characterized in that the half-peak width of a laser emission spectrum is sharply narrowed, and the laser threshold value is low: diene triarylamine Eth is equal to 5.37 mu J cm <-2 >, and monoene triarylamine Eth is equal to 7.47 mu J cm <-2 >. Compared with monoene triarylamine, diene triarylamine has a lower gain threshold. The triarylamine compound shown in the formula (I) can be used as a laser gain medium to be applied to the field of organic laser devices.

Description

Technical Field

[0001] The invention relates to the technical field of organic laser gain media, and more specifically to the application of a triarylamine compound as a laser gain medium in a laser device. Background Art

[0002] Since the invention of lasers by humans more than 50 years ago, the application of lasers has entered all walks of life. At present, the emission wavelengths of different types of laser light sources have covered the ultraviolet, visible, and infrared bands, achieving controllable adjustment of different wavelengths, different energy levels, and different pulse line widths, which can meet the application requirements of different fields. Although the structures and characteristics of various types of lasers are different, lasers must have three basic components: gain medium, pump source, and resonant cavity. The gain medium can be gas, liquid or solid, and the light wave is amplified through stimulated emission. The pump source provides energy, and the gain medium absorbs energy to achieve a particle number inversion between the upper and lower energy levels. The function of the resonant cavity is to realize the feedback of light waves, thereby determining the spatial and spectral coherence of the output light spot.

[0003] The reason why lasers work is because they contain a gain medium that can amplify light waves. Unlike simple photon absorption, if the incident photon interacts with the excited gain material and an additional photon with the same frequency and direction as the incident photon is released from the excited state, this process is called stimulated emission. That is to say, when the light wave propagates through the gain medium, more photons are emitted, a stronger light intensity is generated, and it increases exponentially with the increase of distance.

[0004] Organic lasers have always attracted the attention of scientific researchers due to their advantages such as simple preparation, low price and easy integration. Compared with inorganic laser media, organic laser materials have a wide range of sources and have the characteristics of wide emission spectrum, large absorption and emission cross-sectional area, so they have great development potential. Among the many organic laser materials, π-conjugated small molecules or polymers are a very important category. After long-term development, a rich system of organic laser materials has been formed. In the mid-1960s, Schafer reported the first organic laser phenomenon with a solution of π-conjugated high fluorescence efficiency dye molecules as the gain medium. Since the luminescence spectrum of organic dye lasers has a very wide adjustable range, it has attracted widespread attention. At present, more and more organic laser gain medium materials have been reported.

[0005] Existing monoolefin and diene triarylamine compounds are mainly used as hole transport materials for organic photosensitive drums and light-emitting devices. For example, patent US2021 / 0124279A1 discloses the use of monoolefin triarylamine or diene triarylamine as hole transport materials for the preparation of photosensitive drum functional layers for copiers. However, the use of triarylamine compounds as laser gain media and their application in organic laser devices has not yet been reported. Summary of the invention

[0006] The first object of the present invention is to overcome the above-mentioned defects and shortcomings in the prior art and provide the application of triarylamine compounds as laser gain media.

[0007] The second object of the present invention is to provide the use of triarylamine compounds as laser gain media in the preparation of organic laser devices.

[0008] The third object of the present invention is to provide an organic photolaser device.

[0009] The fourth object of the present invention is to provide a method for preparing the organic photolaser device.

[0010] The above-mentioned object of the present invention is achieved through the following technical solutions:

[0011] The triarylamine compound is used as a laser gain medium, wherein the triarylamine compound has a structural formula as shown in the following formula (I):

[0012]

[0013] n is selected from 0 or 1. When n=0, it is a monoolefin triarylamine, and when n=1, it is a diene triarylamine.

[0014] In the application of photosensitive materials, the light emitted by the triarylamine compounds of formula (I) is spontaneous fluorescence, and the electrons are excited from the ground state to the excited state and then freely return to the ground state, and the half-peak width of the spectrum does not change; and the present invention finds that in the field of lasers, the triarylamine compounds of formula (I) can be used as gain media, and under the excitation of excitation light, stimulated radiation is emitted to emit laser, which can make the half-peak width of the laser emission spectrum sharply narrowed, and the laser threshold is low.

[0015] After measurement, the threshold value E of the diene triarylamine in the laser device made of the triarylamine compound of formula (I) is th =5.37 μJ cm -2 , the threshold E of monoolefin triarylamine th =7.47 μJ cm -2 , the laser threshold is low. Therefore, the triarylamine compound shown in formula (I) can be used as a laser gain medium in the field of organic laser devices.

[0016] Therefore, the present invention also provides the use of triarylamine compounds as laser gain media in the preparation of organic laser devices, wherein the triarylamine compounds have a structural formula as shown in the following formula (I):

[0017]

[0018] n is selected from 0 or 1.

[0019] Furthermore, the organic laser device is an organic photolaser device or an organic electrolaser device.

[0020] The present invention also provides an organic photolaser device, comprising a light-emitting layer, wherein the light-emitting layer contains a triarylamine compound as a laser gain medium; the triarylamine compound has a structural formula as shown in the following formula (I):

[0021]

[0022] n is selected from 0 or 1.

[0023] Furthermore, the light-emitting layer uses CBP as a host and the triarylamine compound represented by formula (I) as a guest.

[0024] The present invention also provides a method for preparing the organic photolaser device, which comprises first cleaning the base material, then coating the base material with a light-emitting layer solution to prepare a thin film, and then placing the film in a resonant cavity to form an organic laser device with an external pump source.

[0025] Furthermore, the substrate material is quartz glass.

[0026] Furthermore, the cleaning comprises the following steps:

[0027] a. Ultrasonicate the quartz glass in a vigorous detergent diluted with deionized water for 5 to 30 minutes;

[0028] b. Ultrasonication in deionized water for 5 to 30 minutes, repeated 2 to 5 times;

[0029] c. Ultrasonic washing with ethyl acetate for 5 to 30 minutes;

[0030] d. Ultrasonic washing with isopropanol for 5 to 30 minutes;

[0031] e. Heat isopropyl alcohol at 220-240℃ and boil for 3-7 minutes;

[0032] f. After the quartz glass is blown dry with nitrogen, it is dried at 60°C for later use.

[0033] Furthermore, the luminescent layer solution is prepared by mixing the triarylamine compound represented by formula (I) with CBP at a mass ratio of 0.5% to 2.5%, and then dissolving the mixture in CHCl3 at a mass ratio of 0.5% to 3%.

[0034] Furthermore, the coating method is spin coating at 500-6000 rpm for 10-60s.

[0035] As an embodiment, the preparation synthesis route of the triarylamine compound represented by the material formula (I) of the present invention is shown in the following equation:

[0036]

[0037] Specifically, triphenylamine reacts with phosphorus oxychloride (POCl3) in an organic solvent to generate a compound shown in Formula 1, and then the compound shown in Formula 1 reacts with diethyl diphenylmethyl phosphite or diethyl diphenylpropenyl phosphite in a potassium tert-butoxide and organic solvent environment to generate a triarylamine compound shown in Formula (I).

[0038] Compared with the prior art, the present invention has the following beneficial effects:

[0039] The present invention provides the use of triarylamine compounds represented by formula (I) as laser gain media in laser devices. The present invention shows that the triarylamine compounds represented by formula (I) can be used as a laser gain material for preparing laser devices, which is mainly manifested in that the half-peak width of its laser emission spectrum is sharply narrowed and the laser threshold is low: Diolefin triarylamine E th =5.37μJcm -2 , monoolefin triarylamine E th =7.47 μJ cm -2 Compared with monoolefin triarylamine, diolefin triarylamine has a lower gain threshold. The triarylamine compound represented by formula (I) can be used as a laser gain medium in the field of organic laser devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 For monoolefin triarylamine 1 H NMR (400 MHz, DMSO-d6).

[0041] Figure 2 For diene triarylamine 1 H NMR (400 MHz, CDCl3).

[0042] Figure 3 The laser spectra of the monoolefin triarylamine photolaser device under different pump energies.

[0043] Figure 4The laser characteristics of monoolefin triarylamine in CBP with a mass fraction of 2% are shown in Figure 2: the relationship between the emission fluorescence and the half-peak width and the pump energy (E th =7.47 μJ cm -2 ).

[0044] Figure 5 The laser spectra of the diarylamine photolaser device under different pump energies.

[0045] Figure 6 The laser characteristics of diene triarylamine in CBP with a mass fraction of 1% are shown in Figure 1: the relationship between the emission fluorescence and the half-peak width and the pump energy (E th =5.37 μJ cm -2 ). DETAILED DESCRIPTION

[0046] The present invention is further described below in conjunction with the accompanying drawings and specific examples, but the examples do not limit the present invention in any form. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0047] Unless otherwise specified, the raw materials in the examples of the present invention were purchased from commercial sources.

[0048] The room temperature in the specific embodiment of the present invention is 25°C.

[0049] Example 1 Preparation of triarylamine gain materials

[0050] (1) Preparation of trialdehyde intermediates

[0051] Ar protection, anhydrous and oxygen-free treatment. Add DMF (7.0 mL, 90.79 mmol, 22.30 eq) to a 50 mL two-necked bottle, stir in an ice-water bath for 20 min, slowly add POCl3 (5.7 mL, 61.15 mmol, 15.02 eq) dropwise in an ice-water bath, stir in an ice-water bath for 60 min, add triphenylamine (998.9 mg, 4.07 mmol, 1.00 eq). Stir in a 95 ° C oil bath and react for 21 h.

[0052] The reaction solution after the above reaction was added with water and ethyl acetate. At this time, there were a large number of insoluble particles. The solid-liquid separation was performed by suction filtration, and the filtrate was collected for extraction. Among them, the aqueous phase was extracted with ethyl acetate three times and ethyl acetate was extracted 3 times, each time using 30mL ethyl acetate, and the extraction was 5min. The organic layer was retained, and 8675.6mg anhydrous magnesium sulfate was added to the organic layer after extraction and stirred for 1h. After filtering, it was spin-dried to obtain 1718.4mg of brown oily liquid. After being fully dried with an oil pump and a hair dryer, the sample was mixed with an appropriate amount of silica gel, and column chromatography was performed for separation (eluent PE / EA = 50 / 1) to obtain 996.7mg of pure compound 1 (bright yellow solid), with a yield of 74%.

[0053] The specific reaction formula is as follows:

[0054]

[0055] (2) Preparation of monoolefin triarylamine

[0056] Ar protection, compound 1 (203.3 mg, 0.62 mmol, 1.00 eq), diethyl benzhydryl phosphite (1190.7 mg, 3.91 mmol, 6.34 eq), potassium tert-butoxide (823.9 mg, 7.34 mmol, 11.89 eq) were added to a 50 mL two-necked flask, 20 mL of redistilled tetrahydrofuran was added, the mixture was placed in an oil bath at 60 °C with stirring, and the reaction was carried out for 18 h.

[0057] After the reaction, the reaction liquid was added with water and ethyl acetate for extraction. The aqueous phase was extracted with ethyl acetate three times and ethyl acetate three times, each time using 30 mL of ethyl acetate for 5 min. The organic layer was retained. After the extraction, 8675.6 mg of anhydrous magnesium sulfate was added to the organic layer and stirred for 1 h. After filtering, the reaction liquid was poured into a 50 mL single-mouth bottle, spin-dried, and fully dried with an oil pump and a hair dryer. Then, the reaction liquid was filtered with silica gel and dichloromethane. After being spin-dried and fully dried with a 50 mL single-mouth bottle, the sample was mixed with an appropriate amount of silica gel, and column chromatography was performed for separation (eluent PE / EA=50 / 1). 363.7 mg of pure compound 2 (bright yellow solid) was obtained, and the yield was 75.21%. The hydrogen nuclear magnetic resonance spectrum of compound 2 is shown in Figure 1 As shown, it is consistent with the reported data (Chem. Commun. 2011, 47, 7770-7772).

[0058] The specific reaction formula is as follows:

[0059]

[0060] (3) Preparation of Diolefin Triarylamine

[0061] Ar protection, diphenyl propylene phosphite diethyl ester (4100mg, 2.4mmol, 1.00eq) was added to a 100mL round-bottom flask, compound 1 (1300mg, 4mmol, 1.67eq), DMF (30mL, 387.7mmol), cooled to 0°C and stirred for 5min in a light-proof environment. Potassium tert-butoxide (1400mg, 12.4mol) was slowly added to the reaction system, stirred at the same temperature for 30min and heated to room temperature, and reacted for 24h. After the reaction was completed, the reaction system was slowly poured into 100mL NH4Cl saturated solution, stirred for 10min, filtered, and the filter cake was washed 3 times with 30mL NH4Cl saturated solution, dried, and the water was removed to obtain 3670mg crude product, which was dissolved in 50mL DCM, 5.0g silica gel was added, and DCM was removed by rotary evaporator to make the crude product and silica gel uniformly mixed. Column chromatography was performed using an eluent (PE:DCM = 20:1 to 10:1; 0.5 mL of triethylamine was added for every 100 mL of eluent) to obtain 2750 mg (80.2%) of pure compound 3. The H NMR spectrum of compound 3 is as follows Figure 2 Shown: 1 H NMR (600MHz, CDCl3): δ (ppm) = 7.41 (t, J = 7.4Hz, 6H), 7.36 (d, J = 7.3Hz, 3H), 7.33-7.26 (m, 21H), 7.16 (d, J = 8.3Hz, 5H), 6.94 (d, J = 8.1Hz, 5H), 6.87 (d, J = 10.8Hz, 3H), 6.78 (t, J = 13.1Hz, 3H), 6.67 (d, J = 15.2Hz, 3H).

[0062] The specific reaction formula is as follows:

[0063]

[0064] Example 2 Monoolefin triarylamine gain material threshold test

[0065] The monoolefin triarylamine prepared in Example 1 was used to prepare a photolaser device to test its threshold, wherein CBP was used as the host and the monoolefin triarylamine was used as the guest.

[0066] The method for preparing the triarylamine compound photolaser device specifically comprises the following steps:

[0067] (1) Glass cleaning:

[0068] a. Ultrasonicate the quartz glass in a vigorous detergent diluted with deionized water for 10 minutes;

[0069] b. Ultrasonication in deionized water for 10 min, repeated 3 times;

[0070] c. Ultrasonic washing with ethyl acetate for 10 min;

[0071] d. Ultrasonic washing with isopropanol for 10 min;

[0072] e. Heat isopropanol at 230℃ and boil for 5 minutes;

[0073] f. After the quartz glass is dried with nitrogen, it is placed in an oven for drying;

[0074] (2) Preparation of monoolefin triarylamine light-emitting layer:

[0075] The monoolefin triarylamine organic gain medium was mixed with CBP at a mass ratio of 2.0%, and then dissolved in CHCl3 at a mass ratio of 2%, stirred evenly, and spin-coated at 1000 rpm for 60 seconds. After the film was prepared, it was placed in a nitrogen atmosphere for 12 hours.

[0076] The laser spectrum and ASE threshold of the monoolefin triarylamine laser device were tested in air atmosphere under the excitation light of 337nm laser using PMA-12 photon multi-channel analyzer (C10027-01). Figure 3 and Figure 4 As shown in the figure, the laser device made of monoolefin triarylamine has a pump energy of 1.95 to 33.97 μJ cm -2 In the range of 2.5 μJ cm-2, the half-peak width of the laser spectrum dropped sharply, showing its ASE effect, and 7.47 μJ cm-2 was obtained. -2 The lower gain threshold of

[0077] Example 3 Diolefin triarylamine gain material threshold test

[0078] Referring to Example 2, the bistriarylamine prepared in Example 1 was prepared into a photolaser device to test its threshold value.

[0079] The diene triarylamine organic gain medium was mixed with CBP at a mass ratio of 1.0%, and then dissolved in CHCl3 at a mass ratio of 2%, stirred evenly, and spin-coated at 1000 rpm for 60 seconds. After the film was prepared, it was placed in a nitrogen atmosphere for 12 hours.

[0080] The laser spectrum and ASE threshold of the diphenyltriarylamine laser device were tested in air atmosphere under the excitation light of 337nm laser using PMA-12 photon multi-channel analyzer (C10027-01). Figure 5 and Figure 6 As shown in the figure, the laser device made of diolefin triarylamine has a pump energy of 4.18 to 27.49 μJ cm -2 In the range of 2.5 μJ cm-2, the half-peak width of the laser spectrum dropped sharply, showing its good ASE effect, and 5.37 μJ cm-2 was obtained. -2That is, compared with mono-olefin triarylamine, the gain threshold of di-olefin triarylamine is lower.

Claims

1. Application of a triarylamine compound as a laser gain medium, It is characterized in that The triarylamine compound has a structural formula as shown in the following formula (I): n is selected from 0 or 1.

2. Application of a triarylamine compound as a laser gain medium in the preparation of an organic laser device, It is characterized in that The triarylamine compound has a structural formula as shown in the following formula (I): n is selected from 0 or 1.

3. The use according to claim 2, It is characterized in that The organic laser device is an organic photolaser device or an organic electrolaser device.

4. An organic photolaser device, It is characterized in that The invention comprises a light-emitting layer, wherein the light-emitting layer contains a triarylamine compound as a laser gain medium; the triarylamine compound has a structural formula shown in the following formula (I): n is selected from 0 or 1.

5. The organic photolaser device according to claim 4, It is characterized in that The light-emitting layer uses 4,4'-bis(N-carbazolyl)-1,1'-biphenyl as a main body and a triarylamine compound represented by formula (I) as a guest.

6. The method for preparing the organic photolaser device according to claim 4, It is characterized in that The substrate material is first cleaned, and then a light-emitting layer solution is coated on the substrate material to prepare a thin film, which is placed in a resonant cavity to form an organic laser device with an external pump source.

7. The preparation method according to claim 6, It is characterized in that The substrate material is quartz glass, and the quartz glass needs to be cleaned.

8. The preparation method according to claim 7, It is characterized in that The cleaning of the quartz glass comprises the following steps: a. Ultrasonicate the quartz glass in a vigorous detergent diluted with deionized water for 5 to 30 minutes; b. Ultrasonication in deionized water for 5 to 30 minutes, repeated 2 to 5 times; c. Ultrasonic washing with ethyl acetate for 5 to 30 minutes; d. Ultrasonic washing with isopropanol for 5 to 30 minutes; e. Heat isopropyl alcohol at 220-240℃ and boil for 3-7 minutes; f. After the quartz glass is blown dry with nitrogen, it is dried at 60°C for later use.

9. The preparation method according to claim 6, It is characterized in that The luminescent layer solution is prepared by mixing the triarylamine compound represented by formula (I) with CBP at a mass ratio of 0.5% to 2.5%, and then dissolving the mixture in CHCl at a mass ratio of 0.5% to 3%. 3 Prepared in.

10. The preparation method according to claim 6, It is characterized in that The coating is performed by spin coating at 500-6000 rpm for 10-60 seconds.

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