Color center formation in soda lime glass and NaCl single crystals with femtosecond laser pulses

The high instantaneous powers associated with femtosecond lasers can color many nominally transparent materials. Although the excitations responsible for this defect formation occur on subpicosecond time scales, subsequent interactions between the resulting electronic and lattice defects complicate the evolution of color center formation and decay. These interactions must be understood in order to account for the long term behavior of coloration. In this work, we probe the evolution of color centers produced by femtosecond laser radiation in soda lime glass and single crystal sodium chloride on different time scales, from microseconds to hundreds of seconds. By using an appropriately chosen probe laser focused through the femtosecond laser spot, we can follow the changes in coloration due to individual or multiple femtosecond pulses, and follow the evolution of that coloration for a long time after femtosecond laser radiation is terminated. For the soda lime glass, the decay of color centers is well described in terms of bimolecular annihilation reactions between electron and hole centers. Similar processes appear to operate in single crystal sodium chloride. PACS 82.50.Pt; 78.55.Qr; 78.55.Fv; 78.47.+p     

Infrared femtosecond laser pulse induced permanent reduction of Eu3+ to Eu2+ in a fluorozirconate glass

We report what is believed to be the first observation of permanent photoreduction of Eu(3+) to Eu(2+) in transparent and colorless Eu(3+) -doped fluorozirconate glass at room temperature, using an infrared femtosecond laser. Difference absorption and electron-spin-resonance spectra of the glass before and after laser irradiation showed that a portion of the Eu(3+) ions in the focused part of the laser inside the glass were reduced to Eu(2+) ions after laser irradiation. It is suggested that Eu(3+) ions act as electron-trapping centers, whereas active sites in the glass matrix act as hole-trapping centers, leading to the formation of Eu(2+) ions. The observed phenomenon is inferred to be useful in the fabrication of optical memory devices with high storage density and waveguide-type micro-optical devices.     

Fabrication of an integrated Raman sensor by selective surface metallization using a femtosecond laser oscillator

We demonstrate that a Raman sensor integrated with a micro-heater, a microfluidic chamber, and a surface-enhanced Raman scattering (SERS) substrate can be fabricated in a glass chip by femtosecond laser micromachining. The micro-heater and the SERS substrate are fabricated by selective metallization on the glass surface using a femtosecond laser oscillator, whereas the microfluidic chamber embedded in the glass sample is fabricated by femtosecond laser ablation using a femtosecond laser amplifier. We believed that this new strategy for fabricating multifunctional integrated microchips has great potential application for lab-on-a-chips.     

Optical properties of structurally modified glasses doped with gold ions

We report on the optical properties of a structurally modified silicate glass doped with Au ions. The area in the vicinity of the focal point of an 800-nm femtosecond laser in a glass sample became gray as a result of the formation of color centers after laser irradiation and turned red because of precipitation of Au nanoparticles after further annealing at 550 degrees C for 30 min. When the glass was excited by UV light at 365 nm, yellowish-white and orange-yellow emissions were observed in the laser-irradiated and the Au-nanoparticle-precipitated area, respectively. An optical Kerr shutter experiment showed that the Au nanoparticle-precipitated glass had an ultrafast nonlinear optical response, and the third-order nonlinear susceptibility was estimated to be approximately 10(-11) esu.     

Threshold effect in femtosecond laser induced nanograting formation in glass: influence of the pulse duration

Recently, femtosecond laser direct writing in porous glass is emerging as a powerful technique for building arbitrary 3D hollow micro/nanostructures in bulk glass materials. In this study, we investigate the pulse duration dependence of laser intensity window for inducing a single nanocrack inside porous glass by femtosecond laser direct writing. We find that the window for a single nanocrack increases with the pulse duration, while the roughness of side walls in the nanocracks becomes higher for pulses longer than ~300 fs. When the femtosecond laser pulses of an optimized duration of ~200 fs are chosen, a sufficiently broad range of laser intensity (~44 % of the structuring threshold) for creating a single nanocrack can be obtained, while smooth sidewalls required by nanofluidic applications can still be maintained. The reported results will be beneficial not only for the development of the 3D femtosecond laser micro/nanostructuring techniques, but also for gaining a deeper understanding of the physical mechanism behind the nanograting formation induced by femtosecond laser irradiation in glass and other transparent materials.     

Micromachining soda-lime glass by femtosecond laser pulses

The physical process of forming a modified region in soda-lime glass was investigated using 1 kHz intense femtosecond laser pulses from a Ti: sapphire laser at 775 nm. Through the modifications induced by the femtosecond laser radiation using selective chemical etching techniques, we fabricated reproducible and defined microstructures and further studied their morphologies and etching properties. Moreover, a possible physical mechanism for the femtosecond laser modification in soda-lime glass was proposed.     

Fabrication of 3D microfluidic structures inside glass by femtosecond laser micromachining

Femtosecond lasers have opened up new avenues in materials processing due to their unique characteristics of ultrashort pulse widths and extremely high peak intensities. One of the most important features of femtosecond laser processing is that a femtosecond laser beam can induce strong absorption in even transparent materials due to nonlinear multiphoton absorption. This makes it possible to directly create three-dimensional (3D) microfluidic structures in glass that are of great use for fabrication of biochips. For fabrication of the 3D microfluidic structures, two technical approaches are being attempted. One of them employs femtosecond laser-induced internal modification of glass followed by wet chemical etching using an acid solution (Femtosecond laser-assisted wet chemical etching), while the other one performs femtosecond laser 3D ablation of the glass in distilled water (liquid-assisted femtosecond laser drilling). This paper provides a review on these two techniques for fabrication of 3D micro and nanofluidic structures in glass based on our development and experimental results.     

Formation mechanism of element distribution in glass under femtosecond laser irradiation

We report on the formation mechanism of element distribution in glass under high-repetition-rate femtosecond laser irradiation. We simultaneously focused two beams of femtosecond laser pulses inside a glass and confirmed the formation of characteristically shaped element distributions. The results of the numerical simulation in which we considered concentration- and temperature-gradient-driven diffusions were in excellent qualitative agreement with the experimental results, indicating that the main driving force is the sharp temperature gradient. Since the composition of a glass affects its refractive index, absorption, and luminescence property, the results in this study provide a framework to fabricate a functional optical device such as optical circuits with a high-repetition-rate femtosecond laser.     

Femtosecond laser-induced long-lasting phosphorescence in Pr^3＋-doped ZnO-B2O3-SiO2 glass

This paper studies the phenomenon of long-lasting phosphorescence induced by a femtosecond laser in Pr3 -doped ZnO-B2O3-SiO2 glass. With the glass irradiated by a focused femtosecond laser for a short time, the emission of strong reddish long-lasting phosphorescence from the irradiated part of the glass can be observed. The emission peaks are located at 495 and 603 nm in wavelength, showing that the long-lasting phosphorescence originates from the emission of Pr^3 . The intensity of the phosphorescence decreases in inverse proportion to time after the removal of the laser. By analysing the absorption and electron spin resonance spectra of the glass, we find that colour-centres are induced in the glass matrix after the irradiation of the femtosecond laser. A possible mechanism has been provided to account for the generation of long-lasting phosphorescence.     

A novel femtosecond-laser formation of CdS nanocrystallites in zirconia matrices

A novel method for direct laser writing of two-dimensional cadmium sulfide (CdS) semiconductor nanoparticle microstructures is reported. A two photon or a higher-order multiphoton absorption process, originating from femtosecond laser pulses, was used to decompose CdS precursors dispersed in a zirconia thin film previously dip-coated on a glass substrate. The kinetics of nanoparticle formation as a function of laser power were monitored in situ by photoluminescence spectroscopy. Raman spectroscopy was also performed to characterize the structural changes of the zirconia matrix under irradiation and to verify the formation of CdS nanoparticles. Results show that CdS nanoparticles were formed by two-photon absorption (TPA) with or without the help of an additional carbazole photoinitiator.     

Mode improvement of a femtosecond laser beam by the spatially self-focusing effect in solid material

The self-focusing effect of femtosecond pulses in a thin piece of BK7 glass is researched through experiment and calculation. The spatial-mode improvement of the femtosecond laser beam is observed. Against the incident pulse with spatial wings, a Gauss-like spatial mode is obtained due to the spatially self-focusing effect in a solid material. The femtosecond pulse propagation in the thin glass plate is analyzed by the amended propagation equation, and the theoretical result shows a qualitative agreement with the experimental result. According to the analysis, the mode improvement of the femtosecond laser beam is resulted from the combination with the self-focusing and dispersion effects in the solid material.     

Self-assembled volume vortex grating induced by femtosecond laser pulses in glass

We presented a microfabrication process for optical volume vortex grating inside glass by femtosecond laser pulses. The self-trapped filament of femtosecond laser pulses can induce hundreds μm-long region refractive-index changes in glass. We realized the restructured optical vortex beams using a collimated He–Ne laser beam. The maximum first-order diffraction efficiency was about 19.6%. The volume vortex grating structure fabricated in glass is polarization dependent.     

单次飞秒激光脉冲在玻璃内部产生多次微爆的研究

在入射能量不同的情况下，用近红外飞秒激光脉冲在重钡火石玻璃（ZBaF15）内部产生了色心和微爆，在熔融石英的内部产生了多次微爆现象.实验表明：入射能量较高时，色心的中间会产生微爆；在松聚焦条件下，一个飞秒激光脉冲在透明介质内会激发多次微爆.基于飞秒激光脉冲在透明介质内的自聚焦效应和自由电子等离子体的自散焦效应，理论分析了多次微爆产生的原因；也讨论了飞秒激光脉冲诱导玻璃折射率改变的机理.     

Water-assisted femtosecond laser ablation for fabricating three-dimensional microfluidic chips

When the femtosecond laser focused in the water, the breakdown will be induced. The generated high-speed jet and shock wave can be used to etch silica glass for fabricating three-dimensional (3D) microfluidic chips. We present a simple and practical method to produce 3D multilayer microfluidic chips in silica glass. This method offers high design flexibility and fabricating feasibility. We also introduce a convenient cleaning method for diluting and ejecting the ablated debris from microchannel. Therefore, the femtosecond laser induced high-speed jet and shock wave can be used to fabricate complex microfluidic chips in silica glass. Experimental results show that the diameter of microchannel is uniform and the complexity of the microfluidic chip is under control. As a proof of principle, we demonstrate the feasibility of the fabricating process by using the water-assisted femtosecond laser ablation.     

Generating optical vortex with computer-generated hologram fabricated inside glass by femtosecond laser pulses

We introduce a novel method to generate the optical vortex with computer-generated hologram (CGH) fabricated inside glass by femtosecond laser pulses. The CGH was directly written inside glass by femtosecond laser pulses induced microexplosion without any pre- or post-treatment of the material. We also realized the restructured optical vortex beams of both the transmission and reflection pattern with high fidelity using a collimated He-Ne laser beam. The total diffractive efficiency of both the transmission and reflection pattern is about 4.79%.     

Formation of defects in lithium fluoride ceramics upon irradiation with femtosecond laser pulses

The interaction between femtosecond laser radiation in the filamentation mode and lithium fluoride optical ceramics is investigated experimentally. It is shown that irradiating optical ceramics based on lithium fluoride with femtosecond laser pulses in the near infrared spectral region effectively produces luminescence centers characteristic of radiation-colored single crystals.     

Study of the microstructural transformations of borate glass and barium metaborate crystals induced by femtosecond laser

This paper describes the microstructural transformations of borate glass and barium metaborate crystals induced by femtosecond laser. Such structural transformations were verified by Raman spectroscopy. The borate glass is transformed into low temperature (LT) phase of barium metaborate (BaB_2O_4) crystals after being irradiated for 10 min by a femtosecond laser. In addition, after 20 min of irradiation, high temperature (HT) phase of BaB_2O_4 crystals is also produced. Further studies demonstrate that LT phase BaB_2O_4 crystals are formed in the HT phase BaB_2O_4 crystals after femtosecond laser irradiation for 10 s.     

Sm3+ photoreduction in BaCl2 nanophases precipitated fluoroaluminate glasses under femtosecond laser irradiation

Photoreduction of samarium-doped BaCl(2)-modified aluminofluoride glass by femtosecond laser irradiation and x-ray irradiation were investigated. Photoluminescence of samarium ions indicated that photoreduction of Sm(3+)→Sm(2+) efficiently occurred in glass samples containing more than 5 mol.% BaCl(2) after femtosecond laser irradiation, while dramatic change was not observed by x-ray irradiation. Transmission electron microscope results revealed that BaCl(2) nanophases only precipitated from glass matrix with a high BaCl(2) content by focusing femtosecond laser irradiation. Samarium ions were selectively incorporated into the precipitated nanophases, resulting in the enhancement of Sm(3+) photoreduction under lower laser power.     

Mechanism study of femtosecond laser induced selective metallization (FLISM) on glass surfaces

We investigate the mechanism of selective metallization on glass surfaces with the assistance of femtosecond laser irradiation followed by electroless plating. Irradiation of femtosecond laser makes it possible to selectively deposit copper microstructures in the irradiated area on glass surfaces coated with silver nitrate films. The energy-dispersive X-ray (EDX) analyses reveal that silver atoms are produced on the surface of grooves formed by laser ablation, which serve as catalysis seeds for subsequent electroless copper plating.     

飞秒激光诱导Li2O-Nb2O5-SiO2玻璃析晶拉曼谱研究

通过使用波长 800nm、重复频率 250kHz的飞秒激光脉冲聚焦进Li2O-Nb2O5-SiO2组分的玻璃内部,空间选择性诱导出铌酸锂微晶.为了进一步地研究辐照区域晶体的生长机制,使用显微拉曼光谱仪分析了玻璃样品辐照区域不同位置的结构变化.研究表明,在飞秒激光辐照一段时间后的聚焦区域,由于非线性效应和热累积效应形成了一个高温辐射梯度场,在激光辐照中心区域超过玻璃的析晶温度而促使玻璃熔融析晶.