阅读说明：本技术 自组装聚集激光器及其制备方法 (Self assembly aggregation laser device and preparation method thereof ) 是由 杨中民 刘旺旺 虞华康 胡蓉蓉 臧启光 唐本忠 于 2019-08-09 设计创作，主要内容包括：本发明公开了一种自组装聚集激光器的制备方法及自组装聚集激光器。该自组装聚集激光器的制备方法包括如下步骤：(1)将增益材料与聚合物溶于良性溶剂,形成均一相的前驱体溶液；(2)将前驱体溶液加入到含有表面活性剂的非良性溶剂中,聚合物自组装形成尺寸可控的聚合物微球,增益材料进入聚合物微球中使得增益材料呈聚集状态；(3)在脉冲光激发下,聚合物微球为增益材料提供高效光反馈,实现回音壁模式的自组装聚集激光出射。该自组装聚集激光器的增益材料在聚集前不发光、聚集后发光高效,可有效避免传统有机激光严重的浓度猝灭效应,为提升激光材料的光学增益提供新的途径。(The invention discloses a kind of preparation method of self assembly aggregation laser device and self assembly aggregation laser devices.The preparation method of the self assembly aggregation laser device includes the following steps: that gain material and polymer are dissolved in good solvent by (1), forms the precursor solution of homogeneous phase；(2) precursor solution is added in the non-benign solvent containing surfactant, polymer self assembles form the controllable polymer microballoon of size, and gain material, which enters in polymer microballoon, makes gain material in coherent condition；(3) under pulsed light excitation, polymer microballoon provides efficiency light feedback for gain material, realizes the self assembly aggregation laser outgoing of Whispering-gallery-mode.The gain material of the self assembly aggregation laser device is luminous efficient after not shining, assembling before aggregation, can effectively avoid the serious concentration quenching effect of traditional organic laser, provides new approach for the optical gain of improving laser material.)

1. a kind of preparation method of self assembly aggregation laser device, which comprises the steps of:

(1) gain material and polymer are dissolved in good solvent, form precursor solution；

(2) precursor solution is added in the non-benign solvent containing surfactant, the polymer self assembles shape At polymer microballoon, the gain material enters in the polymer microballoon, so that the gain material is formed in coherent condition State of aggregation gain material；

(3) under pulsed light excitation, the polymer microballoon provides efficiency light feedback for gain material, realizes Whispering-gallery-mode The outgoing of self assembly aggregation laser.

2. the preparation method of self assembly aggregation laser device according to claim 1, which is characterized in that the gain material packet It includes with one of organic laser material, aggregation-induced emission molecule and hydridization perovskite to-receptor structure or more Kind.

3. the preparation method of self assembly aggregation laser device according to claim 2, which is characterized in that it is described have to-by The organic laser material of body structure includes phenylenevinylene's derivative, azepine anthracene derivant, benzene thiophene derivative, two acyls One of imine derivative is a variety of；

The aggregation-induced emission molecule includes tetraphenyl ethylene and its derivative, tetraphenyl ethylene-triphenylamine derivative, 9,10- bis- Phenyl vinyl anthracene and its derivative, triphenylamine, boron system aggregation-induced emission molecule and its derivative, silicon systems aggregation-induced emission Molecule and its derivative it is one or more；

The hydridization perovskite includes chain alkyl metal perovskite, organic metal perovskite, one in full-inorganic metal perovskite Kind is a variety of.

4. the preparation method of self assembly aggregation laser device according to claim 1 to 3, which is characterized in that described The concentration range of gain material in precursor solution is 0.5mg/mL-50mg/mL, and the polymer in the precursor solution is dense Degree range is 1mg/mL-100mg/mL.

5. the preparation method of self assembly aggregation laser device according to claim 1 to 3, which is characterized in that described Polymer includes epoxy resin, polymethyl methacrylate, polystyrene, polypropylene, polyacrylamide, polyamide, poly- carbonic acid One of ester, polyethylene are a variety of.

6. the preparation method of self assembly aggregation laser device according to claim 1 to 3, which is characterized in that described Surfactant is distearoylphosphatidylethanolamine-polyethylene glycol, cetyl trimethylammonium bromide, detergent alkylate sulphur One of sour sodium, lecithin, alkyl glucoside are a variety of.

7. the preparation method of self assembly aggregation laser device according to claim 1 to 3, which is characterized in that described Surfactant concentration ranges in non-benign solvent are 0.1mg/mL-10mg/mL.

8. the preparation method of self assembly aggregation laser device according to claim 1 to 3, which is characterized in that described The diameter of polymer microballoon is 1 μm -200 μm.

9. the preparation method of self assembly aggregation laser device according to claim 1 to 3, which is characterized in that described Good solvent be tetrahydrofuran, hexane, hexamethylene, methylene chloride, chloroform, n,N-Dimethylformamide, dimethyl sulfoxide, One of alcohols, ethers are a variety of；The non-benign solvent is water, methane, hexane, hexamethylene, methylene chloride, three chloromethanes One of alkane, alcohols, ethers are a variety of.

10. the preparation method of self assembly aggregation laser device according to claim 1 to 3, which is characterized in that institute The volume ratio for stating good solvent and the non-benign solvent is 1:1.5-99.

11. the preparation method of self assembly aggregation laser device described in a kind of claim 1-10 any one be prepared from group Fill aggregation laser device.

Technical field

The present invention relates to laser technology fields, more particularly to a kind of self assembly aggregation laser device and preparation method thereof.

Background technique

The dye molecule (such as rhodamine) that traditional organic laser uses shines well under weak solution state, but with poly- Collection degree increase leads to luminescence queenching, seriously limits its development, this is also limitation organic laser gain material light amplification ability Principal element.In addition, traditional organic laser needs complicated technology of preparing to construct resonant cavity (such as Fabry Perot chamber, light Sub- crystal microcavity, distributed Feedback chamber etc.), there is preparation complexity, preparation cost is high, the low disadvantage of quality factor.Aggregation laser A kind of type of laser in contrast, its main feature is that gain material (weak solution state) before aggregation do not shine or shine it is weak, As aggregation extent (concentrated solution or solid-state) increases, luminous efficiency is sharply promoted, and is cooperateed in accumulation process and generated high-quality The optical resonator of the factor forms laser emitting under pump light excitation.

Summary of the invention

Based on this, it is necessary to provide a kind of simple micro-cavity structure preparation, low cost, high optical gain, high-quality-factor Self assembly aggregation laser device and preparation method thereof.

A kind of preparation method of self assembly aggregation laser device, includes the following steps:

(1) gain material and polymer are dissolved in good solvent, form the precursor solution of homogeneous phase；

(2) precursor solution is added in the non-benign solvent containing surfactant, the polymer is from group Dress forms polymer microballoon, and the gain material enters in the polymer microballoon, so that the gain material is in coherent condition Form state of aggregation gain material；

(3) under pulsed light excitation, the polymer microballoon provides efficiency light feedback for gain material, realizes echo wall die The self assembly aggregation laser of formula is emitted.

In one of the embodiments, the gain material include organic laser material with typical to-receptor structure, Aggregation-induced emission molecule and the hydridization perovskite one or more of new by aggreation induction synthesis.

It is described in one of the embodiments, that have the organic laser material to-receptor structure include that phenylenevinylene spreads out One of biology, azepine anthracene derivant, benzene thiophene derivative, diimide derivative are a variety of；

The aggregation-induced emission molecule includes tetraphenyl ethylene and its derivative, tetraphenyl ethylene-triphenylamine derivative, 9, 10- diphenylacetylene anthracene and its derivative, triphenylamine, boron system aggregation-induced emission molecule and its derivative, silicon systems aggregation lure Lead the one or more of light emitting molecule and its derivative；

The hydridization perovskite includes chain alkyl metal perovskite, organic metal perovskite, full-inorganic metal perovskite In it is one or more.

The aggregation laser launch wavelength range is 400nm-900nm in one of the embodiments,.

The concentration range of the gain material in the precursor solution is 0.5mg/mL- in one of the embodiments, 50mg/mL, the polymer concentration range in the precursor solution are 1mg/mL-100mg/mL.

In one of the embodiments, the polymer include epoxy resin, polymethyl methacrylate, polystyrene, One of polypropylene, polyacrylamide, polyamide, polycarbonate, polyethylene are a variety of.

The surfactant is distearoylphosphatidylethanolamine-polyethylene glycol, ten in one of the embodiments, One of six alkyl trimethyl ammonium bromides, neopelex, lecithin, alkyl glucoside are a variety of.

The surfactant concentration ranges in the non-benign solvent are 0.1mg/mL- in one of the embodiments, 10mg/mL。

The diameter of the polymer microballoon is 1 μm -200 μm in one of the embodiments,.

The good solvent is tetrahydrofuran, hexane, hexamethylene, methylene chloride, three chloromethanes in one of the embodiments, One of alkane, n,N-Dimethylformamide, dimethyl sulfoxide, alcohols, ethers are a variety of；The non-benign solvent is water, first One of alkane, hexane, hexamethylene, methylene chloride, chloroform, alcohols, ethers are a variety of.

The volume ratio 1:1.5-99 of the good solvent and the non-benign solvent in one of the embodiments,.

A kind of self assembly aggregation laser device that the preparation method of the self assembly aggregation laser device is prepared.

Self assembly aggregation laser device of the invention has the beneficial effect that: aggregation laser shines in coherent condition and significantly mentions It rising, is conducive to further increase optical gain, self assembly aggregation laser device of the invention does not need additionally to construct optical resonator, Resonant cavity is formed by polymer self assembles in the solution, has the characteristics that low preparation cost, Gao Guangxue quality factor, it should be from group Filling aggregation laser device is one useful supplement of existing laser type, and will be in necks such as tunable laser, biochemistry sensings Domain has potential application.

In the preparation method of self assembly aggregation laser device of the invention, gain material and polymer are dissolved in good solvent, It is non-benign it is solvent-induced under, gain material from solution be precipitated enter polymer in become coherent condition, the gain of coherent condition The luminous functional group of material and interpolymer interaction, so that final gain material luminescent properties are sharply promoted, polymer exists Since surface tension effects are self-assembled into the controllable polymer microballoon of size in accumulation process, high optics quality factor can be used as Whispering-gallery-mode (WGM) microcavity realizes WGM Mode for Laser under pump light excitation.Gain material of the invention and tradition are organic Laser dye is far from each other, and gain material of the invention is luminous efficient after not shining, assembling before aggregation, and optical gain is with poly- Collection degree increases and increases, it is possible to prevente effectively from the serious concentration quenching effect of traditional organic laser, is further improving laser The optical gain of material provides new approach, has benefited from the high stability and dynamic optical gain characteristic of gain material, so that aggregation Laser is in high-performance, tunable laser, and biochemistry sensing, there is important potential application in the fields such as light-matter interaction.

Detailed description of the invention

Fig. 1 is the luminescent spectrum for the state of aggregation gain material that the non-benign solvent that water content is 0% and 90% participates in preparation；

Fig. 2 is the fluorescence photo for the state of aggregation gain material that the non-benign solvent that water content is 0% and 90% participates in preparation；

Fig. 3 is the schematic illustration that self assembly described in an embodiment prepares aggregation laser device；

Fig. 4 is the optical photograph for the polymer microballoon that self assembly described in an embodiment prepares aggregation laser device；

Fig. 5 is Laser emission spectrum of the polymer microsphere sample shown in Fig. 4 under pulsed light pumping；

It is the relational graph that changes with pump power of laser peak integrated intensity of polymer microsphere sample that Fig. 6, which is shown in Fig. 4,.

Description of symbols

1: gain material；2: polymer；3: good solvent；4: Whispering-gallery-mode feeds back schematic diagram；5: non-benign solvent；6: Polymer microballoon.

Specific embodiment

To facilitate the understanding of the present invention, a more comprehensive description of the invention is given in the following sections with reference to the relevant attached drawings.In attached drawing Give presently preferred embodiments of the present invention.But the invention can be realized in many different forms, however it is not limited to this paper institute The embodiment of description.On the contrary, purpose of providing these embodiments is keeps the understanding to the disclosure more thorough Comprehensively.

Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more phases Any and all combinations of the listed item of pass.

One embodiment of the invention provides a kind of preparation method of self assembly aggregation laser device, includes the following steps:

(1) gain material and polymer are dissolved in good solvent, form the precursor solution of homogeneous phase, gain material and poly- Close the quality such as 1:100-50:100 of object.The concentration range of gain material in the precursor solution is 0.5mg/mL- 50mg/mL, the polymer concentration range in the precursor solution are 1mg/mL-100mg/mL.

(2) precursor solution is added in the non-benign solvent containing surfactant, the non-benign solvent In surfactant concentration ranges be 0.1mg/mL-10mg/mL, the mixture of the good solvent and the non-benign solvent Product is than being 1:1.5-1:99.The polymer self assembles form the controllable polymer microballoon of size, the polymer microballoon it is straight Diameter is 1 μm -200 μm, and polymer microballoon can be used as the Echo Wall microcavity of high optics quality factor, forms Whispering-gallery-mode and swashs Light.Gain material enters in polymer microballoon, so that gain material forms state of aggregation gain material in coherent condition；State of aggregation increases The luminous functional group of beneficial material and interpolymer interaction, cause to shine quickly enhancing.

(3) under pulsed light excitation, polymer microballoon provides efficiency light feedback for gain material, realizes Whispering-gallery-mode The outgoing of self assembly aggregation laser, aggregation laser launch wavelength range are 400nm-900nm.

Further, gain material includes having typical case to-the organic laser material of receptor (D-A) structure, aggregation inducing Shine (AIE) molecule and the hydridization perovskite one or more of new by aggreation induction synthesis；

Further, having the typical organic laser material to-receptor (D-A) structure includes phenylenevinylene's derivative (such as CNDPASDB, Chinese Isosorbide-5-Nitrae-bis- (cyano -4- diphenylaminostyrene base) -2,5- diphenyl benzene), naphthazine One of derivative (such as CNDPA), benzene thiophene derivative, imidodicarbonic diamide (PDI) derivative are a variety of, wherein right For example trans- 1,4- diphenylethyllene benzene (DSB) of phenylene ethylene derivative, cyano replace phenylenevinylene's derivative (CNDSB), 1, Bis- (cyano -4- diphenylaminostyrene the base) -2,5- diphenyl benzenes (CNDPASDB) of 4-, cyano replace diphenyl -1 2,5-, 4- diphenylethyllene benzene) bis- [1- cyano -2- (4- diphenyl amino) phenyl) vinyl] benzene of (CNDPDSB), 1,4- (TPCNDSB) etc.；Aggregation-induced emission molecule (AIE) includes tetraphenyl ethylene (TPE), tetraphenyl ethylene derivative, tetraphenyl ethylene-three Anil (TPE-TPA-DCM), 9,10- diphenylacetylene anthracene (DSA), 9,10- diphenylacetylene anthracene derivant, three Aniline, boron system aggregation-induced emission molecule, boron system aggregation-induced emission molecule derivant, silicon systems aggregation-induced emission molecule, silicon It is the one or more of aggregation-induced emission molecule derivant.Synthesizing new hydridization perovskite by aggreation induction includes length It is alkyl group metal perovskite, organic metal perovskite, one or more in full-inorganic metal perovskite.Wherein chain alkyl metal Perovskite, such as molecular formula are C_nH_2n+1NH₃)₂PbX₄Compound, n >=8, wherein X=Cl, Br, I, such as (C₁₆H₃₃NH₃)₂PbI₄Deng.Organic metal perovskite, such as molecular formula are CH₃NH₃PbX₃Compound, X=Cl, Br, I.Full-inorganic calcium metal titanium Mine, such as molecular formula are such as CsPbX₃Compound, X=Cl, Br, I.

Further, polymer includes epoxy resin, polymethyl methacrylate (PMMA), polystyrene (PS), poly- third One of alkene, polyacrylamide (PAM), polyamide (PA), polycarbonate (PC), polyethylene (PE) are a variety of.

Further, surfactant is distearoylphosphatidylethanolamine-polyethylene glycol (DSPE-PEG), hexadecane One of base trimethylammonium bromide (CTAB), neopelex, lecithin, alkyl glucoside (APG) are a variety of.

Preferably, good solvent is the organic solvent for having high-dissolvability to polymer and dyestuff；For example, good solvent can be with It is sub- for tetrahydrofuran (THF), hexane, hexamethylene, methylene chloride, chloroform, n,N-Dimethylformamide (DMF), dimethyl One of sulfone (DMSO), alcohols, ethers are a variety of.

Non-benign solvent is generally the solvent for having low solubility to polymer and dyestuff；For example, non-benign solvent can be with For one of water, methane, hexane, hexamethylene, methylene chloride, chloroform, alcohols, ethers or a variety of.