Optical switch organic thin film laser device and preparation method and application thereof

Abstract

The application discloses a light-controlled switch organic thin film laser device and a preparation method and application thereof, and comprises a substrate and an organic thin film arranged in an up-down mode, wherein the organic thin film is prepared by mixing a photochromic compound and a ladder compound, and the photochromic compound is [1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)-3,3,4,4,5,5-hexafluoro-1-cyclopentene]. The light-controlled switch organic thin film laser device provided by the application has a low threshold and good light cycle stability, and can remain stable in multiple light cycles.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of organic laser materials and their applications, and particularly relates to a light-controlled switch organic thin film laser device and a preparation method and application thereof. BACKGROUND

[0002] Organic laser devices have become a research hotspot of new laser devices due to their low-cost production, soluble processing and tunable emission wavelength. For inorganic lasers, tuning the quality of the resonator is a long-established technique to obtain extremely short or time-precise laser pulses. However, this so-called q-switching, i.e. the resonator can be "turned on" and maintain lasing, and "turned off" and suppress lasing, is widely unknown for many organic lasers. One way to modulate the resonator and emission characteristics of a laser is by controlling the absorption (i.e. transmission loss) around the laser to change the quality of the resonator. The adjustment of the resonance condition can be achieved by mechanically stretching organic silicone elastomer DFB resonators, or by changing the refractive index of liquid crystal resonator materials through voltage driving.

[0003] Compared with these methods, light as a physical and chemical stimulus can provide excellent spatial, temporal and energy resolution, which makes light-addressed molecular switches an ideal candidate for controlling material properties.

[0004] At present, researchers have proposed the concept of reversible laser threshold modulation based on a mixed system of dithienylethene (DTE) and conjugated polymers. This method has the advantages of simplicity, rapidity, controllability, etc., and can realize high repetition rate and low conversion time, providing a new direction for the research of organic lasers. In addition, the mixed system of DTE and conjugated polymers has tunable optical properties, which can realize controllable laser output wavelength and provide a way to customize laser performance. DTE molecules can undergo reversible ring-closing and ring-opening reactions through photochemical reactions, thereby modulating the laser threshold of the mixed system. Therefore, the mixing of DTE molecules with other organic gain media (such as ladder compounds) still has great research space and application value in the field of organic laser devices. In addition, with the increasing demand for functions of optoelectronic devices, it is crucial to develop a multifunctional integrated organic laser device. SUMMARY

[0005] This section is intended to summarize some aspects of the embodiments of the present application and briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section and the abstract and title of the specification to avoid obscuring the purpose of this section, the abstract and the title, and such simplifications or omissions cannot be used to limit the scope of the present application.

[0006] In view of the above and / or problems existing in the prior art, the present application is proposed.

[0007] Therefore, the present application aims at overcoming the deficiencies in the prior art and providing a light-controlled switch organic thin film laser device.

[0008] To solve the above technical problems, the present application provides the following technical scheme: a light-controlled switch organic thin film laser device, comprising a substrate, wherein the substrate is provided with an organic thin film, the organic thin film is prepared by mixing a photochromic compound and a ladder compound, and the photochromic compound is [1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)-3,3,4,4,5,5-hexafluoro-1-cyclopentene].

[0009] As a preferred scheme of the light-controlled switch organic thin film laser device, the substrate is quartz.

[0010] As a preferred scheme of the light-controlled switch organic thin film laser device, the substrate is a quartz sheet or a distributed Bragg grating made of quartz.

[0011] Another object of the present application is to provide a preparation method of the light-controlled switch organic thin film laser device.

[0012] To solve the above technical problems, the present application provides the following technical scheme: a preparation method of a light-controlled switch organic thin film laser device, comprising the following steps:

[0013] The photochromic compound and the ladder compound are mixed in chloroform to prepare a doped solution;

[0014] The doped solution is used to prepare the organic thin film by using a spin coating method.

[0015] The preparation of the organic thin film is performed on a substrate, and after the preparation is completed, the organic thin film is naturally covered on the substrate to form the light-controlled switch organic thin film laser device.

[0016] As a preferred scheme of the preparation method of the light-controlled switch organic thin film laser device, the mass ratio of the photochromic compound to the ladder compound in the organic thin film is 1-4:6-9.

[0017] As a preferred scheme of the preparation method of the light-controlled switch organic thin film laser device, the mass ratio of the photochromic compound to the ladder compound in the organic thin film is 3:7.

[0018] As a preferred scheme of the preparation method of the light-controlled switch organic thin film laser device, the organic thin film is prepared by using a spin coating method or an evaporation method.

[0019] As a preferred scheme of the preparation method of the light-controlled switch organic thin film laser device, the organic thin film is a doped solution prepared by mixing a photochromic compound and a ladder compound, and the concentration of the doped solution is 20 mg / mL.

[0020] As a preferred scheme of the preparation method of the light-controlled switch organic thin film laser device, the spin coating is performed at a volume of 45 muL, a rotation speed of 2000 rpm, an acceleration of 2000 rpm, and a duration of 60 seconds.

[0021] Another object of the present application is to provide an application of the light-controlled switch organic thin film laser device, which comprises placing the thin film device in an ultraviolet light exposure environment.

[0022] The present application has the following beneficial effects:

[0023] The light-controlled switch organic thin film laser device based on light response realizes reversible modulation of the threshold value of amplified spontaneous emission in a blending system of an organic semiconductor laser gain medium and a photochromic molecule, and realizes switch control of light emission. The device has a low threshold value and good light cycle stability, and the lowest threshold value of light amplified spontaneous emission (ASE) is 23.7 muJ / cm 2 , and can remain stable in multiple light cycles. This work combines photochromism with the principle of Foster energy transfer, successfully applies this strategy to a light-controlled switch organic thin film laser device, realizes a multifunctional integrated organic thin film laser device with light response and controllable switch, and has potential application value in the fields of optical sensing and light-controlled optoelectronic devices. This provides a possibility for realizing light control in an environment full of green environmental light, and is suitable for maintaining normal operation of light-controlled switches in an environment full of such as Boston ivy in an uninhabited old house. Compared with other colors of environmental light, there is a stronger demand for use. BRIEF DESCRIPTION OF DRAWINGS

[0024] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed in the embodiment description will be briefly introduced. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor. Among them:

[0025] Figure 1 The structural formula and mass spectrum of the ladder compound with laser performance used in embodiment 1 of the present application;

[0026] Figure 2 The half peak width and emission intensity change diagram of the ASE emission of the ladder compound used in the embodiment;

[0027] Figure 3The ASE spectrum of the ladder compound used in the example is shown in the figure;

[0028] Figure 4 The device structure schematic diagram described in Example 2 of the application is shown in the figure;

[0029] In the figure, 101 is an organic thin film, and 201 is a substrate;

[0030] Figure 5 The amplified spontaneous emission performance characterization of the organic thin film laser device in Example 1 under ultraviolet and visible light conditions is shown in the figure;

[0031] Figure 6 The amplified spontaneous emission performance characterization of the organic thin film laser device in Example 4 under ultraviolet and visible light conditions is shown in the figure;

[0032] Figure 7 The amplified spontaneous emission performance characterization of the organic thin film laser device in Example 5 under ultraviolet and visible light conditions is shown in the figure. DETAILED DESCRIPTION

[0033] In order to make the above-mentioned purposes, features and advantages of the application more obvious and easy to understand, the specific embodiments of the application will be described in detail below in combination with the description of the embodiments.

[0034] In the following description, many specific details are set forth in order to provide a thorough understanding of the application, but the application can also be implemented in other ways different from those described herein, and those skilled in the art can make similar generalizations without departing from the scope of the application, therefore the application is not limited to the specific embodiments disclosed below.

[0035] Secondly, the "one embodiment" or "embodiment" referred to herein means that the specific features, structures or characteristics can be included in at least one implementation of the application. "In one embodiment" appearing in different places in this specification does not mean the same embodiment, nor is it an independent or alternative embodiment that excludes other embodiments.

[0036] Example 1

[0037] The ladder compound was prepared, and the preparation method referred to [1] Gao K. Design, synthesis and performance of different waveband luminescent materials[D]. Nanjing University of Posts and Telecommunications, 2020. DOI: 10.27251 / d.cnki.gnjdc.2020.000631. The structure of the prepared ladder compound is shown as follows:

[0038]

[0039] The mass spectrum of the prepared ladder compound is shown as follows: Figure 1 ​

[0040] Figure 2 and Figure 3 is a trapezoidal compound ASE data graph;

[0041] from Figure 2 It can be seen that the lowest threshold of the trapezoidal compound optical amplification spontaneous emission (ASE) is very low, and the performance is good, from Figure 3 It can be seen that the trapezoidal compound has a good radiation amplification effect, and the wavelength shift generated is the color shift within the green light, but the magnitude of the shift is large.

[0042] Example 2

[0043] This embodiment is used to illustrate the structure of the light-controlled switch organic thin film laser device:

[0044] The light-controlled switch organic thin film laser device includes a substrate 201, which is made of quartz, and has an organic thin film 101 provided thereon, as shown in the structure of Figure 4 .

[0045] When light enters the light-controlled switch organic thin film laser device, it passes through the organic thin film 101 to reach the substrate 201, forming a light path through the light-controlled switch organic thin film laser device.

[0046] Through the up-and-down arrangement of the organic thin film 101 and the substrate 201, the light path is deflected on the light-controlled switch organic thin film laser device, and the light emitted from the light-controlled switch organic thin film laser device is refracted with a large magnitude, even forming a 90° angle with the incident light path.

[0047] Example 3

[0048] This embodiment illustrates the preparation of the trapezoidal compound:

[0049] A quartz sheet is used as the substrate, and the trapezoidal compound prepared in Example 1 is selected as the gain medium; the photochromic compound is [1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)-3,3,4,4,5,5-hexafluoro-1-cyclopentene].

[0050] The mass ratio of the photochromic compound in the doped system is 30%, and the mass ratio of the trapezoidal compound is 70%. A doped solution with a concentration of 20 mg / mL is prepared using chloroform. The doped solution is used to prepare a thin film by spin coating, with a usage of 45 μL, a rotation speed of 2000 rpm, an acceleration of 2000 rpm, and a duration of 60 seconds, to obtain a thin film with a thickness of about 100 nm. The prepared organic thin film is used to prepare the light-controlled switch organic thin film laser device according to Example 2.

[0051] Figure 5Amplified spectrum of the organic thin film device of the light-controlled switch under different radiation light, Figure 5 It is shown that the device does not emit after ultraviolet light exposure, restores amplified spontaneous emission after visible light exposure, and still has the function of light-controlled switch emission state after multiple ultraviolet-visible light cycle exposure.

[0052] Example 4

[0053] This example is basically the same as Example 3, and the differences between Example 3 are as follows:

[0054] The mass ratio of the photochromic compound in the doped system is 10%, and the mass ratio of the ladder compound is 90%. The concentration of the doped solution is still 20 mg / mL.

[0055] The thickness of the prepared thin film is about 100 nm, and the prepared thin film device can realize the function of light-controlled switch emission state in the first few ultraviolet-visible light exposure processes. However, after multiple cycle exposure, the device cannot completely quench fluorescence, and does not have the function of inhibiting emission state, which is due to the low proportion of photochromic compounds, and the photoisomerization efficiency gradually decreases with the increase of exposure times.

[0056] Example 5

[0057] This example is basically the same as Example 3, and the differences between Example 3 are as follows:

[0058] The mass ratio of the photochromic compound in the doped system is 40%, and the mass ratio of the ladder compound is 60%. The concentration of the doped solution is still 20 mg / mL.

[0059] The thickness of the prepared thin film is about 100 nm, and the prepared thin film device can realize the function of light-controlled switch emission state in the first few ultraviolet-visible light exposure processes. However, after multiple cycle exposure, the device cannot completely quench fluorescence, and does not have the function of inhibiting emission state, which is due to the low proportion of photochromic compounds, and the photoisomerization efficiency gradually decreases with the increase of exposure times.

[0060] The prepared thin film device can realize the function of light-controlled switch emission state in the first few ultraviolet-visible light exposure processes. However, after multiple cycle exposure, the device no longer emits fluorescence, which is due to the high proportion of photochromic compounds, and the photo-reverse isomerization efficiency gradually decreases after visible light exposure, eventually completely inhibiting fluorescence emission.

[0061] Example 6

[0062] This example is basically the same as Example 3, and the only difference is that a quartz material distributed Bragg grating is selected as the substrate.

[0063] The thin-film device prepared according to the method in Example 2 is shown in the magnified spectra under different radiation light as follows. Figure 6 As shown, Figure 6 This indicates that the fabricated device does not emit after exposure to ultraviolet light, but resumes amplified spontaneous emission after exposure to visible light. It still retains the function of light-controlled switching emission after multiple ultraviolet-visible light cycle exposures, and has higher emission intensity and smaller emission peak position shift.

[0064] Example 7

[0065] Using a quartz sheet as a substrate, the ladder compound from Example 3 was selected as the gain medium. Its structural formula and mass spectrum are shown below. Figure 2 As shown, Figure 3 and Figure 4 The ASE data plot is shown; the selected photochromic compound is [1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)-3,3,4,4,5,5-hexafluoro-1-cyclopentene].

[0066] The photochromic compound comprised 30% by mass of the doping system, the ladder-like compound comprised 70% by mass, and the doping solution concentration was 20 mg / mL. Thin films were prepared by vacuum evaporation, with the vacuum level evaporated to 1 × 10⁻⁶. -4 Pa, temperature controlled at 250℃~300℃, organic source in The film was thermally evaporated and deposited on a quartz plate at a rate of approximately 100 nm thick, resulting in a thin film.

[0067] Figure 7 The purpose is to obtain the magnified spectrum of the thin film device under different radiation light. The device does not emit after exposure to ultraviolet light, but resumes amplified spontaneous emission after exposure to visible light. After multiple ultraviolet-visible light cycle exposures, it still has the function of light-controlled switch emission state, and the amplified spontaneous emission threshold is even lower.

[0068] Comparative Example 1

[0069] In [1] Liu Taiqi, Yang Liyan, Yu Jianxiang. Synthesis of 1,2-bis[2-methyl-5-(3,4-difluorophenyl)thiophen-3-yl]perfluorocyclopentene [J]. Organic Chemistry, 2007, 27(10):3. Among them, 1,2-bis[2-methyl-5-(3,4-difluorophenyl)thiophen-3-yl]perfluorocyclopentene is also a photochromic compound, but its maximum absorption wavelength is 575 nm. This is different from the absorption wavelength achieved by [1,2-bis(2,4-dimethyl-5-phenyl-3-thiophenyl)-3,3,4,4,5,5-hexafluoro-1-cyclopentene] in the example.

[0070] Comparative Example 2

[0071] The present embodiment is basically the same as that of Embodiment 3, and the difference from Embodiment 3 is that a spiro[l,3,3-trimethylindolinochromene] is used as the photochromic compound.

[0072] During the experiment, when the wavelength of the light used is 492-550 nm, the light intensity generated is negligible.

[0073] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present application but not limit the present application. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or equivalently replaced without departing from the spirit and scope of the present application, and all of them should be covered in the scope of the claims of the present application.

Claims

1. A light-controlled switch organic thin film laser device, characterized by: The application relates to a photo-controlled switch organic thin film laser device, which comprises a substrate (201) and an organic thin film (101) on the top surface of the substrate (201), wherein the organic thin film (101) is prepared by mixing a photochromic compound and a ladder compound, and the photochromic compound is [1,2-bis(2,4-dimethyl-5-phenyl-3-thiophenyl)-3,3,4,4,5,5-hexafluoro-1-cyclopentene].

2. The optically controlled switch organic thin film laser device of claim 1, wherein: The substrate (201) is made of quartz.

3. The optically controlled switch organic thin film laser device according to claim 1 or 2, characterized in that: The substrate (201) is a quartz sheet or a distributed Bragg grating made of quartz.

4. The method of claim 1, wherein the method further comprises: The application further discloses a preparation method of the photo-controlled switch organic thin film laser device. The photochromic compound and the ladder compound are mixed in chloroform to prepare a doped solution; The doped solution is used to prepare the organic thin film by using a spin coating method; The prepared organic thin film is naturally covered on the substrate to obtain the photo-controlled switch organic thin film laser device.

5. The method of claim 4, wherein the method further comprises: The mass ratio of the photochromic compound to the ladder compound in the organic thin film (101) is 1-4:6-9.

6. The method of claim 4, wherein the method further comprises: The mass ratio of the photochromic compound to the ladder compound in the organic thin film (101) is 3:

7.

7. The method of claim 4, wherein the method further comprises: The organic thin film (101) is prepared by using a spin coating method or an evaporation method.

8. The method of claim 4 or 7, wherein the method further comprises: The concentration of the doped solution is 20 mg / mL.

9. The method of claim 4 or 6, wherein the method further comprises: The spin coating is performed by using a dosage of 45 muL, a rotating speed of 2000 rpm, an acceleration of 2000 rpm and a duration of 60 seconds.

10. The use of a photo-switching organic thin-film laser device according to claim 1, characterized in that: The thin film laser device is placed in an ultraviolet light exposure environment.

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