CN108512029A - A kind of ultra wide band Random Laser scattering material, laser device and preparation and application based on amorphous bismuthates - Google Patents
A kind of ultra wide band Random Laser scattering material, laser device and preparation and application based on amorphous bismuthates Download PDFInfo
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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
- H01S3/30—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range using scattering effects, e.g. stimulated Brillouin or Raman effects
- H01S3/307—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range using scattering effects, e.g. stimulated Brillouin or Raman effects in a liquid
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Abstract
The present invention relates to a kind of ultra wide band Random Laser scattering material, laser device and preparation and application based on amorphous bismuthates, which includes the chemical composition of following molar percentage：Bi2O3：45 65%, B2O3：20 35%, Ga2O3：0 20%.In high temperature melting after required raw material is mixed, it anneals near glass transformation temperature after the repressed molding of high-temperature fusant, then bulk material ball is clayed into power, obtained dusty material is used to build the various constructions that can provide Random Laser Resonant feedback such as suspension, solid preform, substrate spin-coating film, by the type for changing gain media, with the laser deexcitation of different wave length, ultra wide band Random Laser is observed in the broad spectral range of 530 870nm.Production method of the present invention is simple, flexible form, can be used for optic communication, stored digital and energy conversion and other field well.
Description
Technical field
The present invention relates to laser device technical field more particularly to regulatable ultra wide band Random Laser scattering material, swash
Optical device and preparation and application.
Background technology
In recent years, the research of Random Laser becomes the heat subject of micro-nano laser field.Random Laser in mechanism of production and
There are many significant differences with conventional laser in the characteristics of luminescence, and Random Laser radiation, which is originated from, has photoactive unordered Jie
Matter provides bulk of optical feedback by the Multiple Scattering of radiant light in the medium, to obtain larger gain, is not necessarily to extra resonance chamber
Laser resonant can be realized.Random Laser has the characteristics that omnidirectional emission, and when viewing angle difference, line structure and transmitting
Intensity can also change, and the characteristics of luminescence is in time, space and spectrally random fluctuation.Compared with conventional laser, Random Laser
Remarkable advantage simple with preparation process, at low cost, and there is unique emission characteristics.
1966, former Soviet Union scientist Basov et al. [Prog.Quant.Electron.1970,1:107-185] it uses
The speculum that plane substitutes conventional laser resonant cavity is scattered, a kind of laser resonator that disresonance feedback is provided is constituted.
Nineteen sixty-eight, Letokhov [J.Exp.Theor.Phys.1968,26:835-840] for the first time in theoretical calculation random gain media
Light amplification behavior.Accidental laser has unique physical mechanism, has in the basic research of micro-nano photonic propulsion great
Research significance, and in integreted phontonics, nano photoelectronic devices, optical sensing, the generation of special wave band laser, laser anti-counterfeit, medicine
The numerous areas such as imaging have broad application prospects.
However, the efficient controllable Random Laser reported so far is mainly the scattering center (example by using crystalline state
Such as ZnO, ZrO2And TiO2) come what is realized, for example, 1994, Brown Univ USA Lawandy professors [Nature, 1994,
368:436-438] dye solution containing nano titania scattering particles is experimentally reported for the first time and can be realized is excited spoke
Penetrate amplification.1999, Northwestern Univ USA Hu Cao taught [Phys.Rev.Lett.1999,82:2278-2281] et al. pass through
Nano granular of zinc oxide realizes relevant Random Laser output.However, the scattering center of above-mentioned crystalline state is typically by chemistry way
Diameter obtains, and with preparing, complicated, of high cost, production benefit is low and is difficult to realize the significant drawback integrated on a large scale.
Chinese patent document CN105762634A disclose a kind of adjustable fexible film accidental laser of degree of polarization and its
Preparation method.Accidental laser is membrane structure, is made of polyvinyl alcohol, polyalcohol, dyestuff nematic droplets, polyalcohol
It is located at dyestuff nematic droplets in the film of polyvinyl alcohol composition.The present invention is based on the optics of nematic liquid crystal respectively to different
Property, under the conditions of laser pump (ing), by the polyvinyl alcohol film of mechanical stretching nematic droplets containing dyestuff, change nematic phase
Orientation of the liquid crystal molecule in polyvinyl alcohol film realizes the adjustable Random Laser outgoing of degree of polarization, and Random Laser polarization side
To being parallel to draw direction.
But this kind of accidental laser construction is only limitted to membrane structure, using liquid crystal material as scatterer, has of high cost, hardly possible
To realize the significant drawback of ultra wide band.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of ultra wide band Random Laser scattering material based on amorphous bismuthates
Material, laser device and preparation and application.
Technical scheme is as follows：
A kind of ultra wide band Random Laser scattering material, the scattering material include the chemical composition of following molar percentage：
Bi2O3：45-65%, B2O3：20-35%, Ga2O3：0-20%.
, according to the invention it is preferred to, which includes the chemical composition of following molar percentage：Bi2O3：50-
65%, B2O3：20-30%, Ga2O3：10-20%.
, according to the invention it is preferred to, which includes the chemical composition of following molar percentage：Bi2O3：65%,
B2O3：20%, Ga2O3：15%.
According to the present invention, the preparation method of the ultra wide band Random Laser scattering material, including steps are as follows：
By mole being uniformly mixed after weighing each component, melt, by melt compression moulding after annealing, then to being obtained
It obtains material and carries out ball milling, the powder after ball milling is scattering material.
, according to the invention it is preferred to, the average grain diameter of the powder after ball milling is 4~5 μm.
According to the preparation method of scattering material of the present invention, it is preferred that melting temperature is 1050-1100 DEG C；
Preferably, annealing temperature is 350-360 DEG C, annealing time 1-3h.Annealing carries out near glass transformation temperature.
According to the present invention, a kind of ultra wide band Random Laser device, including above-mentioned scattering material and gain media composition answer
Fit and carrier, the complex load in the carrier；Or the complex being made of above-mentioned scattering material and gain media
The form of flakiness is made as laser device.
Laser device according to the present invention, it is preferred that the gain media is laser dye, rare earth ion or/and half
Conductor quantum dot；
Preferably, the mass ratio of scattering material and gain media is 10000~5000：1.
Diversified forms, including suspended substance, solid preform, waveguide junction can be used in laser device according to the present invention, complex
Structure etc.；
Preferably, when complex is suspended substance, scattering material is dispersed in water, gain media is added and is uniformly dispersed i.e.
Obtain suspended substance；
When complex is solid preform, scattering material high pressure is suppressed into flakiness, gain media solution is uniformly coated
To sheet surface to get the complex of solid preform form；Gain media solution penetrates into the hole of solid preform；
When complex is waveguiding structure, dispersion is dispersed in water to obtain suspension, uniform suspension is coated
To carrier surface, then gain media solution is uniformly coated to surface and obtains film, the as complex of waveguiding structure form.
According to the present invention, diversified forms can be used in the carrier, it is preferred that transparent four cubitainer, glass plate can be used
Deng the transparent preferred cuvette of four cubitainers.When complex is suspended substance, suspended substance can be packed into transparent four cubitainer
In to get to laser device.When complex is solid preform or waveguiding structure, complex is directly as laser device.
According to the present invention, using above-mentioned scattering material (amorphous bismuthates material powder) as strong scattering center, by changing
The type adjustable gain curve of variable-gain medium, Random Laser is generated in 530-870nm wide wave-length coverages.
According to the present invention, the application of the above-mentioned ultra wide band Random Laser device based on amorphous bismuthates, as Random Laser
Device is in optic communication, stored digital and field of energy conversion application.
The present invention proposes a kind of amorphous state bismuthic acid salt material composition strong scattering center for utilizing and easily preparing high yield benefit, utilizes
Refractive index builds various geometry structures for the amorphous state bismuthic acid salt material of 2.378-2.118 in the spectral region of 400-1500nm
The Random Laser device made, the type by changing gain media adjust optical gain plot, in visible light to closely red
Effective laser resonant, pumping threshold are observed in outer wide spectral range.With previously reported based on crystalline state strong scattering center
Random Laser it is suitable.The result shows that amorphous state medium, which can be used as, facilitates interaction of laser with material, random Jie of structure amplification
Matter and the trusted platform for making high efficiency light emitting device.
The principle of the present invention：
The present invention substitutes the strong scattering center of traditional crystalline state with non-crystalline material, by multiple light scattering provide light feedback come
Emit coherent photons, to realize efficient Random Laser resonance, by adding different gain medias, in 530-
Laser is formed in the ultra wide band range of 870nm.
Each raw material role of the present invention：Bi2O3And B2O3For Network former, Ga2O3For Network modifier, B3+With
Ga3+All it is heavy metal ion, there is larger ionic polarizability, assigns the higher refractive index of glass.Laser dye, rare earth from
Son, semiconductor-quantum-point etc. are used as gain media, to observe Random Laser in 530-870nm wave-length coverages.
The beneficial effects of the invention are as follows：
The present invention selects amorphous bismuthic acid salt material to realize 530-870nm's using single dispersing element as scattering medium
Ultra wide band Random Laser；Production method is simple, flexible form, can make suspension, solid preform, waveguide type accidental laser
Part；It can be used for the fields such as optic communication, stored digital and energy conversion.
Description of the drawings
Fig. 1：The structural schematic diagram of the ultra wide band Random Laser device of embodiment 1.
Fig. 2：The sample that embodiment 1 obtains excites generated normalized emission spectra under different pump energies.
Fig. 3：The structural schematic diagram of the ultra wide band Random Laser device of embodiment 2.
Fig. 4：The sample that embodiment 2 obtains excites generated normalized emission spectra under different pump energies.
Fig. 5：The structural schematic diagram of the ultra wide band Random Laser device of embodiment 3.
Fig. 6：The sample that embodiment 3 obtains excites generated normalized emission spectra under different pump energies.
Specific implementation mode
The present invention will be further described with reference to the accompanying drawings and detailed description, but not limited to this.
Embodiment 1
The chemical composition of the amorphous state bismuthic acid salt material of the present embodiment is Bi2O3：65mol%；B2O3：20mol%；Ga2O3：
15mol%.The pure Bi of glass raw material Analysis about Selection2O3、B2O3、Ga2O3.By mole dispensing, after ground and mixed is uniform, it is placed in
In alumina crucible, melt at a certain temperature, it will be attached in glass transformation temperature after melt on stainless steel compression moulding
Nearly annealing 2h, then carries out ball milling, using the powder after ball milling as strong scatterer, powder is dispersed in water to be formed to bulk material
The suspension of 15mg/mL.1mL or more suspension is taken, Rhodamine 101-ethanol solution, the ultrasonic disperse 1 of 0.1mL 10mM is added
Minute, suspended substance is obtained, suspended substance is fitted into transparent cuvette and is swashed at random to get to the ultra wide band based on amorphous bismuthates
Optical device.Structural schematic diagram is as shown in Figure 1.
Use pulse laser (wavelength：532nm, pulsewidth：25ps, repetitive rate：1Hz) sample prepared by deexcitation, Ke Yiguan
Wide spontaneous amplification radiation is observed, with the increase of energy, laser spiking is present in 610nm.Swash under different pump energies
Normalized emission spectra is as shown in Figure 2 caused by hair.
Embodiment 2
The chemical composition of the amorphous state bismuthic acid salt material of the present embodiment is Bi2O3：65mol%；B2O3：20mol%；Ga2O3：
15mol%.The pure Bi of glass raw material Analysis about Selection2O3、B2O3、Ga2O3.By mole dispensing, after ground and mixed is uniform, it is placed in
In alumina crucible, melt at a certain temperature, by after glass melt on stainless steel compression moulding in Glass Transition temperature
Anneal 2h near degree, then carries out ball milling to bulk material, and using the powder after ball milling as strong scatterer, powder passes through tablet press machine
High pressure suppresses flakiness (pressure 10MPa).By the polyethylene alcohol-water solution of 10mL 0.12g/mL and 1mL 10mM rhodamines
6G- ethanol solutions mix.30 μ l mixed solutions are drawn with liquid-transfering gun to drop on thin slice, are allowed to penetrate into the gap of solid preform, are dried
Case dries half an hour to get to the ultra wide band Random Laser device based on amorphous bismuthates.Structural schematic diagram is as shown in Figure 3.
Use pulse laser (wavelength：480nm, pulsewidth：25ps, repetitive rate：1Hz) sample prepared by deexcitation, Ke Yiguan
Wide spontaneous amplification radiation is observed, with the increase of energy, laser spiking is present in 575nm.Swash under different pump energies
Normalized emission spectra is as shown in Figure 4 caused by hair.
Embodiment 3
The chemical composition of the amorphous state bismuthic acid salt material of the present embodiment is Bi2O3：65mol%；B2O3：20mol%；Ga2O3：
15mol%.The pure Bi of glass raw material Analysis about Selection2O3、B2O3、Ga2O3.After mixing, it is placed in alumina crucible,
It melts, will nearby anneal 2h in glass transformation temperature after glass melt on stainless steel compression moulding at a certain temperature,
Then ball milling is carried out to bulk material, using the powder after ball milling as strong scatterer.Powder is dispersed in water to form 15mg/mL's
Suspension takes 0.2mL spin coatings (spin speed on a glass substrate：6000rpm, spin-coating time：30s).By 1mL 0.3g/mL's
The ethanol solution of the rhodamine 800 of polyvinyl alcohol water solution and 0.25mL 10mM uniformly mixes, and takes 0.2mL uniformly to drop in above
On sample, spin coating obtains the polyvinyl alcohol film (spin speed containing rhodamine 800：6000rpm, spin-coating time：60s), dry
Half an hour is to get to the ultra wide band Random Laser device based on amorphous bismuthates.Structural schematic diagram is as shown in Figure 5.
Use pulse laser (wavelength：680nm, pulsewidth：25ps, repetitive rate：1Hz) sample prepared by deexcitation, Ke Yiguan
Wide spontaneous amplification radiation is observed, with the increase of energy, laser spiking is present in 710nm.Swash under different pump energies
Normalized emission spectra is as shown in Figure 6 caused by hair.
Comparative example 1
As described in Example 1, unlike：
The chemical composition of amorphous state bismuthic acid salt material is Bi2O3：40mol%；B2O3：40mol%；Ga2O3：20mol%.
Use pulse laser (wavelength：680nm, pulsewidth：25ps, repetitive rate：1Hz) sample prepared by deexcitation, due to oxygen
The reduction for changing bi content leads to the reduction of sample refractive index, and then scattering power reduces, and increases pumping threshold, reduces output effect
Rate.
Claims (10)
1. a kind of ultra wide band Random Laser scattering material, which is characterized in that the scattering material includes the change of following molar percentage
Learn composition：Bi2O3：45-65%, B2O3：20-35%, Ga2O3：0-20%.
2. ultra wide band Random Laser scattering material according to claim 1, which is characterized in that the scattering material includes as follows
The chemical composition of molar percentage：Bi2O3：50-65%, B2O3：20-30%, Ga2O3：10-20%.
3. ultra wide band Random Laser scattering material according to claim 1, which is characterized in that the scattering material includes as follows
The chemical composition of molar percentage：Bi2O3：65%, B2O3：20%, Ga2O3：15%.
4. the preparation method of any one of the claim 1-3 ultra wide band Random Laser scattering materials, including steps are as follows：
By mole being uniformly mixed after weighing each component, melt, by melt compression moulding after annealing, then to obtained material
Material carries out ball milling, and the powder after ball milling is scattering material.
5. the preparation method of ultra wide band Random Laser scattering material according to claim 4, which is characterized in that after ball milling
The average grain diameter of powder is 4~5 μm.
6. the preparation method of ultra wide band Random Laser scattering material according to claim 4, which is characterized in that melting temperature
It is 1050-1100 DEG C；
Preferably, annealing temperature is 350-360 DEG C, annealing time 1-3h.
7. a kind of ultra wide band Random Laser device, including claim 1-3 any one of them scattering material and gain media group
At complex and carrier, the complex load in the carrier；Or be made of above-mentioned scattering material and gain media
Complex makes the form of flakiness as laser device.
8. laser device according to claim 7, which is characterized in that the gain media be laser dye, rare earth from
Son or/and semiconductor-quantum-point；
Preferably, the mass ratio of scattering material and gain media is 10000~5000：1.
9. laser device according to claim 7, which is characterized in that the complex is using suspended substance, solid preform
Or waveguiding structure form；
When complex is suspended substance, scattering material is dispersed in water, gain media is added and is uniformly dispersed up to suspended substance；
When complex is solid preform, scattering material high pressure is suppressed into flakiness, gain media solution is uniformly coated to thin
Piece surface to get solid preform form complex；Gain media solution penetrates into the hole of solid preform；
When complex is waveguiding structure, dispersion is dispersed in water to obtain suspension, uniform suspension is coated to load
Body surface face, then gain media solution is uniformly coated to surface and obtains film, the as complex of waveguiding structure form.
10. the application of ultra wide band Random Laser device of the claim 1-3 any one of them based on amorphous bismuthates, as with
Machine laser device is in optic communication, stored digital and field of energy conversion application.
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Cited By (2)
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| CN115215544A (en) * | 2022-07-25 | 2022-10-21 | 昆明理工大学 | Semiconductor laser-induced color-changing lead-free glass and preparation method and application thereof |
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