CN111952827A - Bottle-shaped polymer microcavity laser based on aggregation-induced emission dye gain and preparation method thereof - Google Patents

Bottle-shaped polymer microcavity laser based on aggregation-induced emission dye gain and preparation method thereof Download PDF

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CN111952827A
CN111952827A CN202010747608.6A CN202010747608A CN111952827A CN 111952827 A CN111952827 A CN 111952827A CN 202010747608 A CN202010747608 A CN 202010747608A CN 111952827 A CN111952827 A CN 111952827A
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bottle
aggregation
dye
microcavity
polymer
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CN111952827B (en
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董国平
郭晓萍
甄士杰
欧阳天昶
杨丹丹
赵祖金
杨中民
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South China University of Technology SCUT
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
    • H01S3/05—Construction or shape of optical resonators; Accommodation of active medium therein; Shape of active medium
    • H01S3/06—Construction or shape of active medium
    • H01S3/063—Waveguide lasers, i.e. whereby the dimensions of the waveguide are of the order of the light wavelength
    • H01S3/067—Fibre lasers
    • H01S3/06708—Constructional details of the fibre, e.g. compositions, cross-section, shape or tapering
    • H01S3/06729—Peculiar transverse fibre profile
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
    • H01S3/10—Controlling the intensity, frequency, phase, polarisation or direction of the emitted radiation, e.g. switching, gating, modulating or demodulating
    • H01S3/102—Controlling the intensity, frequency, phase, polarisation or direction of the emitted radiation, e.g. switching, gating, modulating or demodulating by controlling the active medium, e.g. by controlling the processes or apparatus for excitation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
    • H01S3/14—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range characterised by the material used as the active medium
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    • H01S3/168—Solid materials using an organic dye dispersed in a solid matrix

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Abstract

The invention discloses a bottle-shaped polymer microcavity laser based on aggregation-induced emission dye gain and a preparation method thereof. The method comprises the following steps: dripping the dye solution into polymer fluid to obtain precursor solution; adding a precursor solution into the finest part of the bidirectional tapered optical fiber, self-assembling a polymer microcavity to obtain a bottle-shaped microcavity, and curing; and coupling the other bidirectional tapered optical fiber with the equatorial plane at the position with the maximum diameter of the bottle-shaped microcavity, and packaging to obtain the microcavity laser. The micro-cavity laser takes aggregation-induced luminescent dye as a laser gain medium and polymer as a matrix material, and is self-assembled to form the bottle-shaped micro-cavity laser, so that the aggregation-induced quenching phenomenon of the dye in the traditional polymer micro-cavity laser is overcome, and the laser output with low threshold and high efficiency can be obtained. The invention has simple process, low cost and universal method, and the obtained bottle-shaped polymer microcavity laser based on the gain of the aggregation-induced emission dye has important application prospect in the fields of sensing, communication and the like.

Description

Bottle-shaped polymer microcavity laser based on aggregation-induced emission dye gain and preparation method thereof
Technical Field
The invention relates to the field of optical devices, in particular to a bottle-shaped polymer microcavity laser based on aggregation-induced emission dye gain and a preparation method thereof.
Background
The microcavity laser introduces light into a specific microscale track, has the characteristics of small mode size, high quality factor, fast dynamic response, high sensitivity and the like, and shows great application potential in the aspects of optical communication, microsensors, three-dimensional imaging and data storage. For example, in document I (Baiske M D, Foreman M R, Vollmer F. Single-molecule nucleic acids detected on a label-free microcavity biosensor platform [ J ]. Nature Nanotechnology, 2014, 9(11): 933-9.), a glass microcavity is perturbed in a biological environment to achieve biomolecular detection. The polymer micro-cavity laser has the advantages of high mechanical flexibility, high optical quality and low manufacturing cost, and provides a strong driving force for the development of the micro-cavity laser. However, as an important gain medium in an active microcavity, a conventional organic dye generally has an aggregation quenching (ACQ) phenomenon, and only weak emission is generated due to strong interaction between molecules at a high concentration or in an aggregated state, which seriously affects the gain property of the dye. For example, document two (Luo J., Xie Z., et al. Aggregation-induced emission of 1-Methyl-1,2,3,4, 5-phenylphyllole [ J ]. Chem. Commun., 2001, 1740-. The aggregation-induced emission dye has the advantages of high luminous efficiency and high doping concentration, and has no self-quenching phenomenon of fluorescent dye under the conditions of high concentration or aggregation state, so that higher fluorescence emission intensity is obtained by increasing the concentration of the aggregation-induced emission dye, or the effective concentration of the application is reduced by high-efficiency luminescence of the aggregation state, so that the application prospect in the fields of biological detection, optical devices and the like can be widened, and the prepared material is an ideal dye capable of solving the problems.
Disclosure of Invention
In view of the above-mentioned problems and shortcomings of the prior art, it is a primary object of the present invention to provide a bottle-shaped polymer microcavity laser based on the gain of aggregation-induced emission dye. The invention overcomes the aggregation induced quenching phenomenon of dye in the traditional polymer micro-cavity laser and can obtain the micro-cavity laser with low laser output threshold.
Another objective of the present invention is to provide a method for preparing the above laser, which has a simple preparation process and can obtain a bottle-shaped polymer microcavity laser with high efficiency and low cost.
The purpose of the invention is realized by at least one of the following technical solutions.
The invention provides a preparation method of a bottle-shaped polymer microcavity laser based on aggregation-induced emission dye gain, which comprises the following steps:
(1) preparation of the polymer fluid: dissolving raw materials for preparing the polymer microcavity in a solvent, and uniformly dissolving to obtain a polymer fluid;
(2) preparing a precursor solution: dissolving a solid dye with aggregation-induced emission properties in a tetrahydrofuran solvent, and uniformly mixing (ultrasonically oscillating until the dye is completely dissolved) to obtain a dye solution; dripping the dye solution into the polymer fluid obtained in the step (1), and stirring until the dye solution is completely and uniformly mixed (stirring by magnetic force until the dye solution is completely and uniformly mixed) to obtain a precursor solution for preparing the polymer microcavity;
(3) drawing a tapered optical fiber: heating and softening the middle part of a commercial quartz fiber by a melt wire drawing method, and drawing to obtain a bidirectional tapered optical fiber;
(4) preparing a polymer micro-cavity: adding the precursor solution obtained in the step (2) into the thinnest part of the bidirectional tapered optical fiber obtained in the step (3), self-assembling a polymer microcavity, obtaining a bottle-shaped microcavity under the action of surface tension, and curing to obtain the polymer microcavity with the gain of the aggregation-induced emission dye;
(5) and (4) numbering another bidirectional tapered optical fiber B, coupling the bidirectional tapered optical fiber B with the equatorial plane at the position with the largest diameter of the bottle-shaped microcavity obtained in the step (4), and packaging to obtain the bottle-shaped polymer microcavity laser based on the gain of the aggregation-induced emission dye.
Further, the raw material for preparing the polymer microcavity in the step (1) is more than one of polymethyl methacrylate (PMMA), epoxy resin (AB glue), Polystyrene (PS) and the like; the solvent is more than one of acetone, toluene, ethyl acetate, tetrahydrofuran, N-dimethylformamide and the like. Such solvents are all capable of dissolving PMMA or PS.
Further, the mass of the raw material for preparing the polymer microcavity in the step (1) is 30-40% of the mass of the solvent.
Further, the solid dye with aggregation-induced emission property in the step (2) is 2, 6-bis (4- (3, 6-di-tert-butyl-9H-aminooxazol-9-yl) phenyl) -4, 8-bis ((2-ethylhexyl) oxy) benzo [1,2-b:4,5-b']Dithiophene 1,1,5,5-tetraoxide (TCzP-BDTO) and triphenylamine-benzo [1,2-b:4,5-b']-one or more of dithiophene 1,1,5,5-tetraoxide (TPA-BDTO).
Said 2, 6-bis (4- (3, 6-di-tert-butyl-9H-aminooxazol-9-yl) phenyl) -4, 8-bis ((2-ethylhexyl) oxy) benzo [1,2-b:4,5-b']Dithiophene 1,1,5,5-tetraoxide (TCzP-BDTO) and triphenylamine-benzo [1,2-b:4,5-b']Preparation of (TPA-BDTO) 1,1,5,5-tetraoxide is described in the literature (Zhen, Shijie, et al, "Efficient Red/Near-extracted fluorine Based on Benzo [1,2-b:4,5-b']dithiophene 1,1,5,5-Tetraoxide for Targeted Photodynamic Therapy and In Vivo Two-Photon Fluorescence bioimaging, "Advanced Functional Materials 28.13(2018): 1706945.1-1706945.15.).
Further, the mass of the solid dye with the aggregation-induced emission property in the step (2) is 0.1-1.0% of the mass of the solvent.
Preferably, the mass of the solid dye with aggregation-induced emission property in the step (2) is 0.2-1.0% of the mass of the solvent.
Further, the volume ratio of the dye solution to the polymer fluid in the step (2) is 1:10-1: 1.
further, the melting and drawing method in the step (3) is to melt the middle part of the optical fiber by a heating source and uniformly draw the two ends of the optical fiber along the axial direction to obtain the bidirectional tapered fiber with the diameter of 1-50 μm at the thinnest part.
Preferably, the melt-drawing method in step (3) is to melt the middle part of the optical fiber with oxyhydrogen flame, carbon dioxide laser, or other heating source, and clamp the two ends of the optical fiber with a clamp, and uniformly draw the optical fiber along the axial direction to obtain the bidirectional tapered fiber with the diameter of the narrowest part of 1 μm to 50 μm.
Preferably, the optical fiber of the present invention is a commercial optical fiber.
Preferably, the bidirectional tapered optical fiber in the step (3) is cut from the thinnest part, so that a single tapered fiber can be obtained.
Further, the preparation of the polymer microcavity in the step (4) comprises: the precursor solution in the step (2) is transferred to the thinnest part of the bidirectional tapered optical fiber in the step (3) (dipping can be carried out by using the tip of a single tapered fiber), and liquid drops of the precursor automatically form a bottle-shaped microcavity under the action of surface tension, and the size of the liquid drops determines the size of the cavity; the size of the cavity of the bottle-shaped micro-cavity is 10-200 μm.
Further, the packaging of step (5) comprises: connecting a pump light source with one end of the coupled bidirectional tapered optical fiber B, and connecting a light wavelength division multiplexer with the other end of the coupled bidirectional tapered optical fiber B; when the packaged laser works, the pump light source excites one point on the equator of the polymer microcavity laser through the coupled bidirectional tapered optical fiber B, and laser output by the polymer microcavity laser is output through the output port of the optical wavelength division multiplexer.
The invention provides a bottle-shaped polymer microcavity laser based on the gain of a aggregation-induced emission dye prepared by the preparation method.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention effectively improves the luminous intensity of the dye in the microcavity by introducing the aggregation-induced luminescent dye as the gain medium of the laser, fundamentally breaks the limit action of aggregation-induced quenching phenomenon, and is beneficial to reducing the threshold of the laser output by the laser.
(2) The invention adopts a self-assembly method to prepare the micro-cavity laser, and has simple preparation process and flexible operation.
(3) The microcavity laser obtained by the invention has high integration level, high quality factor and controllable size, and the bottle-shaped structure is highly differentiated in space and is beneficial to the field of non-contact sensing.
Drawings
Fig. 1 is a schematic structural diagram of an operating device of a bottle-shaped polymer microcavity laser based on the gain of a aggregation-induced emission dye according to an embodiment of the present invention.
FIG. 2 is a laser spectrum of a bottle-shaped PS microcavity laser based on the gain of the aggregation-induced emission dye TCzP-BDTO obtained in embodiment 1 of the invention, which is output under different power pumps.
FIG. 3 is the laser spectra of the bottle-shaped PMMA microcavity laser based on the gain of the aggregation-induced emission dye TCzP-BDTO obtained in the invention example 2 under different power pumps.
FIG. 4 is the laser spectra of the bottle-shaped epoxy microcavity laser based on the gain of the aggregation-induced emission dye TPA-BDTO obtained in example 3 of the invention under different power pumps.
FIG. 5 is the laser spectra of the bottle-shaped PMMA microcavity laser based on the gain of the aggregation-induced emission dye TPA-BDTO obtained in example 4 of the present invention under different power pumps.
FIG. 6 is a schematic line width diagram of the output laser of the bottle-shaped PMMA microcavity laser based on the gain of the aggregation-induced emission dye TPA-BDTO obtained in example 4 of the present invention.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
The following example describes 2, 6-bis (4- (3, 6-di-tert-butyl-9H-aminooxazol-9-yl) phenyl) -4, 8-bis ((2-ethylhexyl) oxy) benzo [1,2-b:4,5-b']Dithiophene 1,1,5,5-tetraoxide (TCzP-BDTO) and triphenylamine-benzo [1,2-b:4,5-b']Preparation of (TPA-BDTO) 1,1,5,5-tetraoxide is described in the literature (Zhen, Shijie, et al, "Efficient Red/Near-extracted fluorine Based on Benzo [1,2-b:4,5-b']dithiophene 1,1,5, 5-tetroxide for Targeted Photodynamic Therapy and In Vivo Two-Photon Fluorescence bioimaging, "Advanced Functional Materials 28.13(2018): 1706945.1-1706945.15.).
Example 1
(1) The precursor material for preparing the bottle-shaped Polystyrene (PS) micro-cavity laser based on the gain of the aggregation-induced emission dye comprises the following raw materials: PS polymer solid particles, aggregation-induced emission dye 2, 6-bis (4- (3, 6-di-tert-butyl-9H-aminooxazol-9-yl) phenyl) -4, 8-bis ((2-ethylhexyl) oxy) benzo [1,2-b:4,5-b']Dithiophene 1,1,5,5-tetraoxide (i.e., TCzP-BDTO) and tetrahydrofuran solvent.
(2) Weighing 0.4 g of PS solid particles according to the mass percentage of the solute to the solvent being 40%, placing the PS solid particles into a 2ml serum bottle, injecting 1g of tetrahydrofuran solvent, covering the bottle cap, and heating in a water bath until the PS solid particles are completely dissolved to obtain the polymer fluid.
(3) Weighing 1 mg of dye TCzP-BDTO according to the mass percentage of the solute to the solvent of 0.1 percent, placing the dye TCzP-BDTO in a 1.5 ml serum bottle, injecting 1g of tetrahydrofuran solvent, covering the bottle cap, and carrying out ultrasonic oscillation until the dye is completely dissolved to obtain a dye solution.
(4) And (3) dropwise adding 1ml of the dye solution obtained in the step (3) into 1ml of the polymer fluid obtained in the step (2) according to the volume ratio of the dye solution to the polymer fluid of 1:1, and magnetically stirring until the dye solution and the polymer fluid are completely and uniformly mixed to obtain a precursor solution for preparing the polymer microcavity.
(5) Cutting a section of commercial optical fiber with the length of 5cm, clamping two ends of the commercial optical fiber by using a clamp, heating and melting the middle part by using a carbon dioxide laser, and uniformly stretching the two ends by using a stepping motor to obtain a bidirectional tapered fiber with the diameter of 1-50 mu m; and taking one of the two-way tapered fibers, and cutting the two-way tapered fiber from the finest part by using a tungsten steel knife to obtain the single tapered fiber.
(6) Selecting a single-cone fiber with the diameter of 20 mu m at the thinnest part, dipping one drop of the precursor solution obtained in the step (4), transferring the drop to the middle part of a bidirectional cone fiber with the diameter of 10 mu m at the thinnest part, and forming a bottle-shaped microcavity under the action of surface tension; the diameter of the bottle-shaped micro-cavity is 10-200 μm.
(7) And selecting a bottle-shaped microcavity with the diameter of 60 mu m as a polymer microcavity laser, coupling another bidirectional tapered optical fiber with an equatorial plane at the position with the largest diameter, and packaging to obtain the bottle-shaped PS microcavity laser based on the gain of the aggregation-induced emission dye.
The schematic structural diagram of the working device of the polymer microcavity laser obtained in this embodiment is shown in fig. 1, and includes five parts, namely a pump laser, a Wavelength Division Multiplexer (WDM), a holder, a polymer microcavity, and an output port. In this embodiment, the pump laser is an optical parametric oscillation laser (model: Opolette, the same applies below), the excitation wavelength is 520 nm, the pulse width is less than 7 ns, and the output power is tunable. The pump light source excites one point on the equator of the polymer micro-cavity laser through the coupled tapered optical fiber, and the laser output by the polymer micro-cavity laser is output through the output port of the optical wavelength division multiplexer.
The laser spectrum of the bottle-shaped polymer PS microcavity laser based on TCzP-BDTO dye gain obtained in this example is shown in FIG. 2. As can be seen from fig. 2, the center wavelength of the output laser light of the polymer microcavity laser in this embodiment is about 624 nm, and when the pump power is increased, the output intensity of the microcavity laser is also increased.
Example 2
(1) The raw materials required for preparing the precursor material of the bottle-shaped polymethyl methacrylate (PMMA) microcavity laser based on the gain of the aggregation-induced emission dye comprise: PMMA polymer solid particles, an aggregation-induced emission dye TCzP-BDTO and a tetrahydrofuran solvent.
(2) Weighing 0.3g of PMMA solid particles according to the mass percentage of the solute to the solvent being 30%, placing the PMMA solid particles into a 2ml serum bottle, injecting 1g of tetrahydrofuran solvent, covering the bottle cap, and heating in a water bath until the PMMA solid particles are completely dissolved to obtain the polymer fluid.
(3) Weighing 10 mg of dye TCzP-BDTO according to the mass percentage of the solute to the solvent of 1.0 percent, placing the dye TCzP-BDTO into a 1.5 ml serum bottle, injecting 1g of tetrahydrofuran solvent, covering the bottle cap, and carrying out ultrasonic oscillation until the dye is completely dissolved to obtain a dye solution.
(4) According to the volume ratio of the dye solution to the polymer fluid of 1:10, 0.1ml of completely dissolved dye solution is dropwise added into a serum bottle filled with 1ml of polymer fluid, and the mixture is magnetically stirred until the mixture is completely and uniformly mixed, so that the precursor solution for preparing the polymer microcavity is obtained.
(5) Cutting a section of commercial optical fiber with the length of 5cm, clamping two ends of the commercial optical fiber by using a clamp, heating and melting the middle part by using a carbon dioxide laser, and uniformly stretching the two ends by using a stepping motor to obtain a bidirectional tapered fiber with the diameter of 1-50 mu m; and taking one of the two-way tapered fibers, and cutting the two-way tapered fiber from the finest part by using a tungsten steel knife to obtain the single tapered fiber.
(6) And (3) selecting a single-cone fiber with the diameter of 20 microns at the narrowest part, dipping one drop of the precursor solution obtained in the step (4), transferring the drop to the middle part of a bidirectional cone fiber with the diameter of 10 microns at the narrowest part, and forming a bottle-shaped microcavity under the action of surface tension. The diameter of the bottle-shaped micro-cavity is 10-200 μm.
(7) And selecting a bottle-shaped microcavity with the diameter of about 60 mu m as a polymer microcavity laser, coupling another bidirectional tapered optical fiber with an equatorial plane at the position with the largest diameter, and packaging to obtain the bottle-shaped polymer microcavity laser based on the gain of the aggregation-induced emission dye.
The schematic structural diagram of the working device of the polymer microcavity laser obtained in this embodiment is shown in fig. 1, and includes five parts, namely a pump laser, a Wavelength Division Multiplexer (WDM), a holder, a polymer microcavity, and an output port. In this embodiment, the pump laser is an optical parametric oscillation laser, the pulse width is less than 7 ns, the working wavelength is 520 nm, and the output power is tunable. And focusing a laser light source to one point on the equator of the polymer micro-cavity laser, and outputting the laser output by the polymer micro-cavity laser through an output port of the optical wavelength division multiplexer.
The laser spectrum of the bottle-shaped polymer PMMA microcavity laser based on the gain of the aggregation-induced emission dye TCzP-BDTO obtained in this example is shown in FIG. 3. As can be seen from fig. 3, the center wavelength of the output laser light of the polymer microcavity laser in this embodiment is near 610nm, and when the pump power is increased, the output intensity of the microcavity laser is also increased.
Example 3
(1) The raw materials required for preparing the precursor material of the bottle-shaped epoxy resin micro-cavity laser based on the gain of the aggregation-induced emission dye comprise: epoxy resin A glue, epoxy resin B glue, aggregation-induced emission dye TPA-BDTO and tetrahydrofuran solvent.
(2) According to the epoxy resin curing condition, the mass ratio of the epoxy resin A glue to the epoxy resin B glue is 3:1, and 0.3g of the A glue and 0.1g of the B glue are weighed and used as polymer fluid for standby.
(3) Weighing 2mg of dye TPA-BDTO according to the mass percentage of the solute to the solvent of 0.2 percent, placing the dye TPA-BDTO in a 1.5 ml serum bottle, injecting 1g of tetrahydrofuran solvent, covering the bottle cap, and carrying out ultrasonic oscillation until the dye is completely dissolved to obtain the dye solution.
(4) Taking 0.1g of the epoxy resin B glue obtained in the step (2) according to the volume ratio of the dye solution to the polymer fluid of 1:5, placing the epoxy resin B glue into a 1.5 ml serum bottle, dropwise adding 0.1ml of the dye solution obtained in the step (2), covering the bottle, uniformly stirring, and evaporating to remove the redundant tetrahydrofuran solvent;
(5) and (3) adding 0.3g of the epoxy resin A glue obtained in the step (2) into the mixed solution obtained in the step (4), and stirring by magnetic force until the epoxy resin A glue is completely and uniformly mixed to obtain a precursor solution for preparing the polymer microcavity.
(6) Cutting a section of commercial optical fiber with the length of 5cm, clamping two ends of the commercial optical fiber by using a clamp, heating and melting the middle part by using a carbon dioxide laser, and uniformly stretching the two ends by using a stepping motor to obtain a bidirectional tapered fiber with the diameter of 1-50 mu m; and taking one of the two-way tapered fibers, and cutting the two-way tapered fiber from the finest part by using a tungsten steel knife to obtain the single tapered fiber.
(7) And (3) selecting a single-cone fiber with the diameter of the narrowest part of the fiber about 20 mu m, dipping one drop of the precursor solution obtained in the step (5), transferring the drop to the middle part of a bidirectional cone fiber with the diameter of the narrowest part of the fiber about 10 mu m, and forming a bottle-shaped microcavity under the action of surface tension. The diameter of the bottle-shaped micro-cavity is 10-200 μm.
(8) And selecting a bottle-shaped microcavity with the diameter of 60 mu m as a polymer microcavity laser, coupling another bidirectional tapered optical fiber with an equatorial plane at the position with the largest diameter, and packaging to obtain the bottle-shaped polymer microcavity laser based on the gain of the aggregation-induced emission dye.
The schematic structural diagram of the working device of the polymer microcavity laser obtained in this embodiment is shown in fig. 1, and includes five parts, namely a pump laser, a Wavelength Division Multiplexer (WDM), a holder, a polymer microcavity, and an output port. In this embodiment, the pump laser is an optical parametric oscillation laser, the pulse width is less than 7 ns, the working wavelength is 520 nm, and the output power is tunable. And focusing a laser light source to one point on the equator of the polymer micro-cavity laser, and outputting the laser output by the polymer micro-cavity laser through an output port of the optical wavelength division multiplexer.
The laser spectra of the bottle-shaped polymer epoxy microcavity laser based on the gain of the aggregation-induced emission dye TPA-BDTO obtained in this example, which are output under different power pumping, are shown in fig. 4. As can be seen from fig. 4, in this embodiment, the center wavelength of the output laser light of the polymer micro-cavity laser is around 658 nm, and when the pump power is increased, the output intensity of the micro-cavity laser is also increased.
Example 4
(1) The raw materials required for preparing the precursor material of the bottle-shaped polymethyl methacrylate (PMMA) microcavity laser based on the gain of the aggregation-induced emission dye comprise: solid particles of PMMA polymer, an aggregation-induced emission dye TPA-BDTO and a tetrahydrofuran solvent.
(2) Weighing 0.35 g of PMMA solid particles according to the mass percentage of the solute to the solvent being 35%, placing the PMMA solid particles into a 2ml serum bottle, injecting 1g of tetrahydrofuran solvent, covering the bottle cap, and heating in a water bath until the PMMA solid particles are completely dissolved to obtain the polymer fluid.
(3) Weighing 2mg of dye TPA-BDTO according to the mass percentage of the solute to the solvent of 0.2 percent, placing the dye TPA-BDTO in a 1.5 ml serum bottle, injecting 1g of tetrahydrofuran solvent, covering the bottle cap, and carrying out ultrasonic oscillation until the dye is completely dissolved to obtain the dye solution.
(4) According to the volume ratio of the dye solution to the polymer fluid of 1:5, 0.2 ml of the completely dissolved dye solution is dropwise added into a serum bottle filled with 1ml of the polymer fluid, and the mixture is magnetically stirred until the mixture is completely and uniformly mixed, so that the precursor solution for preparing the polymer microcavity is obtained.
(5) Cutting a section of commercial optical fiber with the length of 5cm, clamping two ends of the commercial optical fiber by using a clamp, heating and melting the middle part by using a carbon dioxide laser, and uniformly stretching the two ends by using a stepping motor to obtain a bidirectional tapered fiber with the diameter of 1-50 mu m; and taking one of the two-way tapered fibers, and cutting the two-way tapered fiber from the finest part by using a tungsten steel knife to obtain the single tapered fiber.
(6) And (3) selecting a single-cone fiber with the diameter of 20 microns at the narrowest part, dipping one drop of the precursor solution obtained in the step (4), transferring the drop to the middle part of a bidirectional cone fiber with the diameter of 10 microns at the narrowest part, and forming a bottle-shaped microcavity under the action of surface tension. The diameter of the bottle-shaped micro-cavity is 10-200 μm.
(7) And selecting a bottle-shaped microcavity with the diameter of 60 mu m as a polymer microcavity laser, coupling another bidirectional tapered optical fiber with an equatorial plane at the position with the largest diameter, and packaging to obtain the bottle-shaped polymer microcavity laser based on the gain of the aggregation-induced emission dye.
The schematic structural diagram of the working device of the polymer microcavity laser obtained in this embodiment is shown in fig. 1, and includes five parts, namely a pump laser, a Wavelength Division Multiplexer (WDM), a holder, a polymer microcavity, and an output port. In this embodiment, the pump laser is an optical parametric oscillation laser, the pulse width is less than 7 ns, the working wavelength is 520 nm, and the output power is tunable. And focusing a laser light source to one point on the equator of the polymer micro-cavity laser, and outputting the laser output by the polymer micro-cavity laser through an output port of the optical wavelength division multiplexer.
The laser spectra of the bottle-shaped polymer PMMA microcavity laser based on the gain of the aggregation-induced emission dye TPA-BDTO and output by different power pumps are shown in FIG. 5. As can be seen from FIG. 5, in this embodiment, a single-mode laser output can be obtained when the pumping power reaches 91 μ W or more, and the central wavelength of the output laser is around 651 nm. When the pumping power is increased, the output intensity of the microcavity laser is also increased. FIG. 6 is a schematic diagram of the linewidth of the output laser of a bottle-shaped polymer PMMA microcavity laser for further analyzing the gain of the aggregation-induced emission dye TPA-BDTO, wherein the corresponding laser half-peak width is 0.34nm, and the corresponding quality factor is as high as 2 × 103. The threshold condition of laser output in this embodiment is much lower than that of other types of lasers, and it is also proved that the method for preparing the microcavity laser provided by the invention has simple process and can obtain the polymer microcavity laser with high quality factor.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.

Claims (10)

1. A preparation method of a bottle-shaped polymer micro-cavity laser based on aggregation-induced emission dye gain is characterized by comprising the following steps:
(1) dissolving raw materials for preparing the polymer microcavity in a solvent, and uniformly dissolving to obtain a polymer fluid;
(2) dissolving a solid dye with aggregation-induced emission properties in a tetrahydrofuran solvent, and uniformly mixing to obtain a dye solution; dripping the dye solution into the polymer fluid obtained in the step (1), and uniformly mixing to obtain a precursor solution;
(3) heating and softening the middle part of the quartz fiber by a melt drawing method, and drawing to obtain a bidirectional tapered optical fiber;
(4) adding the precursor solution in the step (2) into the thinnest part of the bidirectional tapered optical fiber in the step (3), self-assembling a polymer microcavity to obtain a bottle-shaped microcavity, and curing;
(5) and (4) numbering another bidirectional tapered optical fiber B, coupling the bidirectional tapered optical fiber B with the equatorial plane at the position with the largest diameter of the bottle-shaped microcavity obtained in the step (4), and packaging to obtain the bottle-shaped polymer microcavity laser based on the gain of the aggregation-induced emission dye.
2. The method for preparing a bottle-shaped polymer microcavity laser based on aggregation-induced emission dye gain according to claim 1, wherein the raw material for preparing the polymer microcavity in step (1) is one or more of polymethyl methacrylate, epoxy resin and polystyrene; the solvent is more than one of acetone, toluene, ethyl acetate, tetrahydrofuran and N, N-dimethylformamide.
3. The method for preparing a bottle-shaped polymer microcavity laser based on aggregation-induced emission dye gain according to claim 1, wherein the mass of the raw material for preparing the polymer microcavity in step (1) is 30% -40% of the mass of the solvent.
4. The method for preparing a bottle-shaped polymer microcavity laser based on the gain of aggregation-induced emission dye as claimed in claim 1, wherein the solid dye with aggregation-induced emission property in the step (2) is 2, 6-bis (4- (3, 6-di-tert-butyl-9H-aminooxazol-9-yl) phenyl) -4, 8-bis ((2-ethylhexyl) oxy) benzo [1,2-b:4,5-b']Dithiophene 1,1,5,5-tetraoxide and triphenylamine-benzo [1,2-b:4,5-b']-one or more of dithiophene 1,1,5, 5-tetraoxide.
5. The method for preparing a bottle-shaped polymer microcavity laser based on aggregation-induced emission dye gain according to claim 1, wherein the mass of the solid dye with aggregation-induced emission property in the step (2) is 0.1% -1.0% of the mass of the solvent.
6. The method for preparing a bottle-shaped polymer microcavity laser based on aggregation-induced emission dye gain according to claim 1, wherein the volume ratio of the dye solution to the polymer fluid in the step (2) is 1:10 to 1: 1.
7. The method for preparing a bottle-shaped polymer microcavity laser based on aggregation-induced emission dye gain according to claim 1, wherein in the step (3), the fusion-drawing method is to melt the middle part of the optical fiber by a heating source and uniformly draw the two ends of the optical fiber along the axial direction, so as to obtain the bidirectional tapered fiber with the diameter of the narrowest part of 1 μm to 50 μm.
8. The method for preparing a bottle-shaped polymer microcavity laser based on aggregation-induced emission dye gain according to claim 1, wherein the step (4) of preparing the polymer microcavity comprises: dipping the precursor solution in the step (2), transferring the precursor solution to the thinnest part of the bidirectional tapered optical fiber in the step (3), and automatically forming a bottle-shaped microcavity by precursor liquid drops under the action of surface tension; the size of the cavity of the bottle-shaped micro-cavity is 10-200 μm.
9. The method for preparing a bottle-shaped polymer microcavity laser based on aggregation-induced emission dye gain according to claim 1, wherein the packaging in step (5) comprises: connecting a pump light source with one end of the coupled bidirectional tapered optical fiber B, and connecting a light wavelength division multiplexer with the other end of the coupled bidirectional tapered optical fiber B; when the packaged laser works, the pump light source excites one point on the equator of the polymer microcavity laser through the coupled bidirectional tapered optical fiber B, and laser output by the polymer microcavity laser is output through the output port of the optical wavelength division multiplexer.
10. A bottle-shaped polymer microcavity laser based on the gain of aggregation-induced emission dye prepared by the preparation method as claimed in any one of claims 1 to 9.
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