CN103311784A - PDLC (polymer dispersed liquid crystal) optical fiber doped with dye and metal nanoparticles and optical fiber random laser - Google Patents
PDLC (polymer dispersed liquid crystal) optical fiber doped with dye and metal nanoparticles and optical fiber random laser Download PDFInfo
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- CN103311784A CN103311784A CN2013102389202A CN201310238920A CN103311784A CN 103311784 A CN103311784 A CN 103311784A CN 2013102389202 A CN2013102389202 A CN 2013102389202A CN 201310238920 A CN201310238920 A CN 201310238920A CN 103311784 A CN103311784 A CN 103311784A
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Abstract
The invention discloses a PDLC (polymer dispersed liquid crystal) optical fiber doped with dye and metal nanoparticles. The optical fiber comprises a hollow optical fiber body and a PDLC polymer solidified in the optical fiber body and doped with the dye and the metal nanoparticles, an indium tin oxide (ITO) conductive layer is axially coated on the outer surface of the optical fiber body, an ITO conductive layer identical with the inner diameter of the optical fiber body in width is formed on the outer layer of the hollow optical fiber body by a vacuum magnetron sputtering method, a homogeneous solution is prepared by PDLCs and an ethanol solution of the laser dye and the metal nanoparticles according to a certain mass ratio, is absorbed into the hollow optical fiber body through the capillary effect and fills up the inner diameter of the hollow optical fiber body through light solidifying to enable the refractive index of the polymer to be larger than that of the optical fiber, and positive and negative voltage is connected through the ITO conductive layer to form an electric field to change axial directions of liquid crystal molecules so as to control outputting of random lasers. The PDLC optical fiber doped with the dye and the metal nanoparticles can be applied to aspects of optical communication, sensing, biomedicine, tunable narrow-band coherent light sources and the like.
Description
Technical field
The present invention relates to laser technology field, relate in particular to regulatable PDLC optical fiber and the optical fiber accidental laser thereof of mixing dyestuff and metal nanoparticle.
Background technology
In recent years, Random Laser has become the popular research field of international laser educational circles.The unordered medium of Random Laser radiation source self-activation provides bulk of optical feedback by the repeatedly scattering of radiant light in medium, thereby obtains bigger gain, need not the extra resonance chamber.Random Laser has attracted increasing concern owing to unique physical mechanism with in the potential application of photoelectron and biomedical aspect.Many active and passive materials can be used to produce Random Laser, for example: ZnO powder, polymer, dye-doped liquid crystal, dye adulterated PDLC.Recent years, discover that the metal Nano structure body can greatly strengthen semiconductor quantum well, rare earth, the spontaneous radiation rate of dyestuff, this is because the mutual resonance between radiation center and the metal surface plasma influences.Utilize these characteristics, some researchers have reported that accidental laser is the noncoherent radiation that is produced by metal nanoparticle.They have observed the enhancing of narrowing of radiation spectrum and radiation intensity.This is the characteristic feature of incoherent accidental laser.
PDLC (PDLC) is with low molecular weight liquid crystal (liquidcrystal, be abbreviated as LC) mix mutually with prepolymer, under certain condition through polymerization reaction, forming micron order or nano level liquid crystal droplet is evenly dispersed in the macromolecule network, the material that the dielectric anisotropy acquisition of recycling liquid crystal molecule has the electro-optic response characteristic, it operates mainly between scattering states and the clear state and has certain gray scale.Polymer dispersed liquid crystal film is with liquid crystal and the polymer membrane material in conjunction with a kind of excellent combination property that obtains.Liquid crystal molecule has given polymer dispersed liquid crystal film significant electro-optical characteristic, makes it be subjected to paying close attention to widely, and wide application prospect is arranged.PDLC (PDLC) material is at adjustable window, and fields such as flat panel display and tunable Bragg grating are widely studied and use.The method of general formation PDLC structure is the homogeneous mixture that comprises reactive single aggressiveness and liquid crystal (LC) molecule with light initiation polymerization.These prepolymers generally are solvent-free, low viscosity.The size of LC drop depends on concentration and the curing radiation light intensity of LC.The refractive index n of common polymer
pBe modulated to the ordinary index of refraction n close to liquid crystal
0During no on-load voltage, liquid crystal molecule forms the drop of random distribution, namely forms refringence at liquid crystal molecule and polymer contact-making surface, and this causes the light scattering in PDLCs.In case add voltage, axially will the arranging along the direction of electric field of liquid crystal molecule, liquid crystal molecule and polymer since the scattering that refringence forms will disappear.
Yet metal nanoparticle is seldom paid close attention to as the scattering particles in dye-doped liquid crystal or PDLC accidental laser.It is that these materials can strengthen multiple scattering and the gain of light by the experiment of three kinds of different materials (PDLC, metallic and dyestuff) that few people do the gain random medium.And this gain media also is not applied in the hollow optic fibre.
Summary of the invention
In order to solve the problems of the technologies described above, the present invention proposes a kind of PDLC PDLC optical fiber of mixing dyestuff and metal nanoparticle, it comprises: hollow optic fibre, the PDLC polymer of mixing dyestuff and metal nanoparticle that solidifies in the hollow optic fibre, the hollow optic fibre outer surface is coated with tin indium oxide ITO conductive layer vertically, it is characterized in that:
The outer vacuum magnetic-control sputtering method that adopts of described hollow optic fibre forms the ITO conductive layer wide with the optical fiber internal diameter; PDLC PDLC is made homogeneous phase solution with the ethanolic solution of laser dye and metal nanoparticle with the certain mass ratio, suck described hollow optic fibre with the pore effect, fill full described hollow optic fibre internal diameter through illumination curing and make refractive index polymer greater than optical fibre refractivity; It is axial to connect generating positive and negative voltage formation electric field change liquid crystal molecule by the ITO conductive layer, the output of control Random Laser.
Wherein, described hollow optic fibre internal diameter is commercially available 8 μ m to 1000 μ m hollow optic fibres.
Wherein, ultrasonic or with concentrated acid corrosion fiber outer layer protection resin with acetone, optical fiber embedded adopt the vacuum magnetic-control sputtering method to form the ITO conductive layer in the high-accuracy glass template, conductive layer and optical fiber internal diameter are wide.
Wherein, be with the trimethylolpropane triacrylate monomer for the PDLC PDLC solution of mixing dyestuff and metallic that in hollow optic fibre, solidifies; The N-vinyl pyrrolidone; Rose-red; N-phenylglycine; Sad; Liquid crystal; Laser dye; The metal nanoparticle ethanolic solution stirred 2 hours than Hybrid Heating shading with the certain mass mark, make and mix, the homogeneous phase solution that forms, the shared mass fraction scope of each component is in the homogeneous phase solution: trimethylolpropane triacrylate 40.00wt% to 50.00wt%; N-vinyl pyrrolidone 5.00wt% to 10.00wt%; Rose-red 0.10wt% to 1.00wt%; N-phenylglycine 5.00wt% to 10.00wt%; Sad 5.00wt% to 10.00wt%; Liquid crystal 30.00wt% to 40.00wt%; Laser dye 1.00wt% to 2.00wt%; Metal nanoparticle ethanolic solution 1.00wt% to 3.00wt%.
Wherein, the metal nanoparticle of selecting for use can have surface plasmon resonance fluorescence to strengthen the laser dye of selecting for use.
Wherein, described polymer homogeneous phase solution sucks hollow optic fibre by capillary effect, carries out illumination curing by ultraviolet curing lamp or Nd:YAG laser afterwards.
Wherein, the interior cure polymer refractive index of described hollow optic fibre is greater than optical fibre refractivity.
The invention allows for a kind of optical fiber accidental laser, it comprises: PDLC PDLC optical fiber, AC power and the pump light source of mixing dyestuff and metal nanoparticle as mentioned above expand and converge light path, it is characterized in that: pump light converges light path formation bar shaped light beam through expanding, vertical irradiation along fiber axis to the ITO conductive layer area, form the Random Laser outgoing; Add alternating voltage by the ITO conductive layer and between the ITO conductive layer, form electric field to change liquid crystal molecule axial, the output of control Random Laser.
The PDLC optical fiber accidental laser that uses regulation and control of the present invention to mix dyestuff and metal nanoparticle can guarantee the directed output of Random Laser; No working fluid in the hollow optic fibre is cure polymer, does not have precipitation, Stability Analysis of Structures; The Random Laser threshold value will significantly reduce compared to other optical fiber accidental lasers, and outgoing intensity significantly strengthens; By electric field controls Random Laser outgoing intensity, break-make.
Description of drawings
Fig. 1 is the apparatus structure schematic diagram consistent with the embodiment of the invention;
Fig. 2 is the PDLC optical fiber structure schematic diagram of mixing dyestuff and metal nanoparticle consistent with the embodiment of the invention, wherein, 1 be the Nd:YAG laser, 2 for GRENLOND mirror group, 3 for collimation extender lens group, 4 is speculum, 5 for cylindrical lens, 6 for the PDLC heart optical fiber of mixing dyestuff and metal nanoparticle, 7 for AC power, 8 for Random Laser output, 9 for the ITO conductive layer, 10 for the PDLC polymer, 11 of mixing dyestuff and metal nanoparticle be hollow optic fibre.
Specific implementation method
The present invention will be further described below in conjunction with the drawings and specific embodiments.
Operation principle of the present invention is: mix the PDLC polymer of dyestuff and metal nanoparticle in hollow optic fibre internal diameter solidification process, the liquid crystal molecule of feasible micron or nano-scale, dye molecule, metal nanoparticle evenly are solidificated in the network structure of polymer formation, form rock-steady structure.With cylindrical lens pump light being pooled the bar shaped laser spot vertically shines on the optical fiber through the ITO film, when making alive not, random distribution is vowed in the sensing of liquid crystal, polymer and liquid crystal refraction index do not match, pump light is by the liquid crystal molecule scattering, multiple scattering takes place, form coherent feedback, working as surfaces of metal nanoparticles plasma resonance wavelength and exciting light simultaneously is complementary, metal nanoparticle local surface plasma resonance field will effectively strengthen near the radiation efficiency of the dye molecule of nano particle, when gaining greater than loss stimulated radiation take place and amplify.Mix the refractive index of PDLC polymer of dyestuff and metal nanoparticle greater than the refractive index of hollow optic fibre, form two-dimentional local, utilize total reflection to make outgoing Random Laser local in optical fiber, form directed output; When making alive, by the control voltage swing, overcome polymer network to the anchoring energy of liquid crystal molecule, make liquid crystal molecule point to and vow that unification is along direction of an electric field, the coupling that liquid crystal particle refractive index and refractive index polymer acquire a certain degree, scattering power changes, Random Laser outgoing intensity, and break-make changes thereupon.
Mix the PDLC optical fiber preparation of dyestuff and metal nanoparticle and handle, comprise following steps:
(1) selects the commercially available internal diameter size (8～1000um) of hollow optic fibre for use; hollow optic fibre is handled; ultrasonic 5 minute remove optical fiber surface protection coated with resins less than the hollow optic fibre of 100um with acetone for internal diameter, corrode clean drying up for the hollow optic fibre of internal diameter greater than 100um with strong acid.The optical fiber of handling is embedded prefabricated high-accuracy glass template, only expose the part of optical fiber upper surface and lower surface, utilize the vacuum magnetic control film coating sputtering technology to plate the ITO film wide with the hollow optic fibre internal diameter vertically in the optical fiber upper and lower surface.
(2) with monomer (trimethylolpropane triacrylate); Cross-linking monomer (N-vinyl pyrrolidone); Light trigger (rose-red); Coinitiator (N-phenylglycine); Surfactant (sad); Liquid crystal; Laser dye; The metal nanoparticle ethanolic solution stirred 2 hours than Hybrid Heating shading with the certain mass mark, made to mix the homogeneous phase solution of formation.The shared mass fraction scope of each component is in the solution: trimethylolpropane triacrylate 40.00wt% to 50.00wt%; N-vinyl pyrrolidone 5.00wt% to 10.00wt%; Rose-red mass fraction 0.10wt% to 1.00wt%; N-phenylglycine matter 5.00wt% to 10.00wt%; Sad 5.00wt% to 10.00wt%; Liquid crystal 30.00wt% to 40.00wt%; Laser dye 1.00wt% to 2.00wt%; Metal nanoparticle ethanolic solution 1.00wt% to 3.00wt%.Utilize capillary effect that the polymer homogeneous phase solution is sucked hollow optic fibre, cause phase separation method with polymerization afterwards and make polymer cure, be specially and use the Nd:YAG laser with the 532nm wavelength,
Light intensity uniform irradiation optical fiber 5min～1min is cured or is cured with ultraviolet curing lamp, changes intensity of illumination and light application time control liquid crystal molecule size, and the polymer threshold voltage.Simultaneously, select for use metal nanoparticle can have surface plasmon resonance fluorescence to strengthen the laser dye of selecting for use.After the polymer cure, the cure polymer refractive index is greater than optical fibre refractivity.
As shown in Figure 1, the regulatable PDLC optical fiber accidental laser of mixing dyestuff and metal nanoparticle comprises following steps:
(1) Nd:YAG shoot laser 1 sees through ITO conductive layer 9 through the bar shaped pump light vertical irradiation that GRENLOND mirror group 2, collimator and extender set of lenses 3, speculum 4, cylindrical lens 5 focus on.
(2) the bar shaped pump light shines the PDLC polymer 10 of mixing dyestuff and metal nanoparticle in the hollow optic fibre 11, forms Random Laser outgoing 8.
(3) AC power 7 connects ITO conductive layer 9, and the AC power electrode is the arc-shaped electrode that closes with optical fiber ITO laminating, and it is axial to form the electric field controls liquid crystal molecule between the ITO layer, regulation and control Random Laser outgoing 8.
The present invention realizes mixing the Random Laser outgoing of the PDLC optical fiber accidental laser of dyestuff and metal nanoparticle, and to the electric light regulation and control output of Random Laser.
The invention has the advantages that the PDLC polymer that will mix dyestuff and metal nanoparticle first combines with hollow optic fibre; Compare with the liquid crystal cell Random Laser, optical fiber structure forms two-dimentional local to emergent light, the directed output of Random Laser; Compare with general hollow optic fibre Random Laser, no working fluid in the hollow optic fibre is cure polymer, does not have precipitation, Stability Analysis of Structures, and the local surface resonance of metal nanoparticle helps to reduce the Random Laser threshold value, strengthens outgoing intensity; Can carry out regulation and control to the outgoing Random Laser by voltage.Can be in optical communication, sensing, biomedicine, aspects such as tunable narrow-band coherent source obtain to use.
The above only is preferred implementation of the present invention; be noted that for those skilled in the art; under the prerequisite that does not break away from the principle of the invention, can also make the some improvements and modifications that can expect, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (8)
1. PDLC PDLC optical fiber of mixing dyestuff and metal nanoparticle, it comprises: hollow optic fibre, the PDLC polymer of mixing dyestuff and metal nanoparticle that solidifies in the hollow optic fibre, the hollow optic fibre outer surface is coated with tin indium oxide ITO conductive layer vertically, it is characterized in that:
The outer vacuum magnetic-control sputtering method that adopts of described hollow optic fibre forms the ITO conductive layer wide with the optical fiber internal diameter; PDLC PDLC is made homogeneous phase solution with the ethanolic solution of laser dye and metal nanoparticle with the certain mass ratio, suck described hollow optic fibre with the pore effect, fill full described hollow optic fibre internal diameter through illumination curing and make refractive index polymer greater than optical fibre refractivity; It is axial to connect generating positive and negative voltage formation electric field change liquid crystal molecule by the ITO conductive layer, the output of control Random Laser.
2. the PDLC PDLC optical fiber of mixing dyestuff and metallic as claimed in claim 1 is characterized in that, described hollow optic fibre internal diameter is commercially available 8 μ m to 1000 μ m hollow optic fibres.
3. the PDLC PDLC optical fiber of mixing dyestuff and metallic as claimed in claim 1 or 2; it is characterized in that; ultrasonic or with concentrated acid corrosion fiber outer layer protection resin with acetone; optical fiber is embedded employing vacuum magnetic-control sputtering method formation ITO conductive layer in the high-accuracy glass template, and conductive layer and optical fiber internal diameter are wide.
4. the PDLC PDLC optical fiber of mixing dyestuff and metallic as claimed in claim 1, it is characterized in that the PDLC PDLC solution of mixing dyestuff and metallic that is used for solidifying is with the trimethylolpropane triacrylate monomer in hollow optic fibre; The N-vinyl pyrrolidone; Rose-red; N-phenylglycine; Sad; Liquid crystal; Laser dye; The metal nanoparticle ethanolic solution stirred 2 hours than Hybrid Heating shading with the certain mass mark, make and mix, the homogeneous phase solution that forms, the shared mass fraction scope of each component is in the homogeneous phase solution: trimethylolpropane triacrylate 40.00wt% to 50.00wt%; N-vinyl pyrrolidone 5.00wt% to 10.00wt%; Rose-red 0.10wt% to 1.00wt%; N-phenylglycine 5.00wt% to 10.00wt%; Sad 5.00wt% to 10.00wt%; Liquid crystal 30.00wt% to 40.00wt%; Laser dye 1.00wt% to 2.00wt%; Metal nanoparticle ethanolic solution 1.00wt% to 3.00wt%.
5. as claim 1 or the 4 described PDLC PDLC optical fiber of mixing dyestuff and metal nanoparticle, it is characterized in that the metal nanoparticle of selecting for use can have surface plasmon resonance fluorescence to strengthen the laser dye of selecting for use.
6. as claim 1 or the 4 described PDLC PDLC optical fiber of mixing dyestuff and metallic, it is characterized in that, described polymer homogeneous phase solution sucks hollow optic fibre by capillary effect, carries out illumination curing by ultraviolet curing lamp or Nd:YAG laser afterwards.
7. as claim 1 or the 6 described PDLC PDLC optical fiber of mixing dyestuff and metallic, it is characterized in that the cure polymer refractive index is greater than optical fibre refractivity in the described hollow optic fibre.
8. optical fiber accidental laser, it comprises: expand as PDLC PDLC optical fiber, AC power and the pump light source of mixing dyestuff and metal nanoparticle as described in claims 1 and converge light path, it is characterized in that: pump light converges light path formation bar shaped light beam through expanding, vertical irradiation along fiber axis to tin indium oxide ITO conductive layer area, form the Random Laser outgoing; Add alternating voltage by the ITO conductive layer and between the ITO conductive layer, form electric field to change liquid crystal molecule axial, the output of control Random Laser.
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| CN103944057A (en) * | 2014-04-18 | 2014-07-23 | 南开大学 | Dye laser based on novel SMOF |
| CN104218445A (en) * | 2014-08-21 | 2014-12-17 | 杭州电子科技大学 | Method for manufacturing nanometer laser device arrays |
| CN104242047A (en) * | 2014-08-21 | 2014-12-24 | 杭州电子科技大学 | Method for implementing dynamic nano laser array |
| CN104953449A (en) * | 2015-04-16 | 2015-09-30 | 合肥工业大学 | Polymer optical-fiber random laser based on metal nanoparticle scattering |
| CN105006729A (en) * | 2015-08-20 | 2015-10-28 | 电子科技大学 | Random laser, random resonant cavity manufacture method and small particle concentration detection method |
| CN105826805A (en) * | 2016-05-24 | 2016-08-03 | 中国计量大学 | Random fiber laser capable of realizing magnetic regulation |
| CN106785867A (en) * | 2016-12-27 | 2017-05-31 | 东南大学 | A kind of PDLC accidental laser and preparation method thereof and control method |
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| CN113328325B (en) * | 2021-04-22 | 2023-10-31 | 江苏度微光学科技有限公司 | Flexible polymer random laser and preparation method thereof |
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