晶体压致非晶化的拉曼散射研究

本文主要介绍压致非晶化研究的进展，其中包括我们对β—ＢａＢ＿２Ｏ＿４，ＬｉＢ＿３Ｏ＿５，Ｐｂ＿５Ｇｅ＿３Ｏ＿１１和Ｌｉ＿２Ｇｅ＿７Ｏ＿（１５）的拉曼散射研究结果。综述了压致非晶的结构特征，压致非晶转变机制和重新晶化过程。     

Three-dimensional photoprecipitation of oriented LiNbO3-like crystals in silica-based glass with femtosecond laser irradiation

We demonstrate crystals (LiNbO(3)-like) that were space-selectively nucleated and grown in the bulk of silica-based glass by femtosecond laser irradiation at a high repetition rate (typ. 300 kHz). Oriented crystals with their polar axis mostly aligned with or perpendicular to the laser scanning direction have been fabricated by manipulation of the temperature gradient in adjusting the laser parameters. The mechanism for the orientation of femtosecond laser-induced crystallization is briefly discussed.     

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.     

Thermochromism and Magnetic Phase Transition in an Organic Radical 1,3,5-Trithia-2,4,6-Triazapentalenyl

Thermochromic and magnetic properties of an organic radical, 1,3,5-trithia-2,4,6-triazapentalenyl (TTTA) crystal were investigated through polarized reflection and EPR measurements. TTTA shows a first-order magnetic phase transition with a wide thermal hysteresis loop near room temperature. The high temperature (HT) phase is paramagnetic due to a uniform one-dimensional stacking of the radical molecules, while the low temperature (LT) phase is diamagnetic due to strong dimerization along the stacking direction. The colors of the HT and LT phases are purple and green, respectively, and both phases show a strong dichroism. We also found that part of the LT phase changes to the HT phase by laser light irradiation. The experimental results suggest the possibility of optical control of magnetic bistabitity in TTTA crystal.     

Direct measurement of wave-front distortion induced during second-harmonic generation: application to breakup-integral compensation

The wave-front distortion of femtosecond laser pulses recorded with a Shack-Hartmann analyzer makes it possible to retrieve the nonlinear index of refraction of different glasses and the nonlinear phase shift induced during second-harmonic generation in beta-barium borate (BBO) crystal versus the phase mismatch. It is shown that the nonlinear phase shift induced in a 2-mm-thick BBO crystal allows compensation for up to a 2pi breakup-integral induced in a 4-cm fused-silica glass. The stability of the compensation is reported to be from 10 to 100 GW cm(-2).     

Structural and crystallization behavior of (Ba,Sr)TiO3 borosilicate glasses

Various glass samples were prepared by melt quench technique in the glass system [(Ba_{1? x} Sr _x ) TiO₃]–[2SiO₂–B₂O₃]–[K₂O] doped with 1?mole% of La₂O₃. Infrared spectra show the number of absorption peaks with different spliting in the wave number range from 450 to 4000?cm^?1. Absorption peaks occurs due to asymetric vibrational streching of borate by relaxation of the bond B–O of trigonal BO₃. Raman spectra show the Raman bands due to ring-type metaborate anions, symmetric breathing vibrations BO₃ triangles replaced by BO₄ tetrahedra, and symmetric breathing vibrations of six-member rings. The differential thermal analysis of a glass sample corresponding to composition x?=?0.0 shows crystallization temperature at 847°C and glass transition temperature at 688°C. X-ray diffraction (XRD) pattern of glass ceramic samples shows the major crystalline phase of BaTiO₃ whereas pyrochlore phases of barium titanium silicate. Scanning electron micrographs confirm the results of XRD as barium titanate is major crystalline phase along with pyrochlore phase of barium titanium silicate.     

高重复频率飞秒脉冲激光诱导钼酸镝玻璃表面析出β′-Dy2（MoO4）3和α-MoO3晶体

高重复频率飞秒脉冲激光辐照钼酸镝玻璃表面后,通过显微拉曼测试,发现在辐照区域内形成了含有MoO4四面体结构的β′-Dy2(MoO4)3晶体和含有MoO6八面体结构的α-MoO3晶体。通过电子能谱(EDS)测量辐照前后样品中钼(Mo)元素的含量,发现在辐照中心位置形成α-MoO3晶体相的区域内出现了明显的Mo元素缺失现象,表明了在高温场作用下,微爆现象引起了材料中心密度的降低。此外,随着辐照时间的增加辐照中心位置还出现了由Dy2(MoO4)3相向MoO3晶体α相的相变。这说明随着激光作用程度的加剧,中心区域Mo元素浓度降低,使得钼氧结构由MoO4四面体向MoO6八面体转变,导致在Mo元素浓度较低的区域更容易形成八面体结构的α-MoO3。     

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.     

Space-selective growth of frequency-conversion crystals in glasses with ultrashort infrared laser pulses

We report on space-selective growth of a second-harmonic-generation beta-BaB(2)O(4) (BBO) crystal inside a BaO-Al(2)O(3)-B(2)O(3) glass sample at the focal point of an 800-nm femtosecond laser beam. A spherical heated region was formed during the focused laser irradiation through observation with an optical microscope. We moved the heated region by changing the position of the focal point of the laser beam relative to the glass sample. We grew BBO crystal continuously in the glass sample by adjusting the moving speed of the heated zone. Our results demonstrate that functional crystals can be formed three dimensionally in glasses by use of a nonresonant ultrashort pulsed laser.     

Local phase-structure modification inside of lithium silicate glass by combined double-wavelength laser action

The process of local structure modification inside of lithium silicate glass under the combined laser action of two different wavelengths is considered. The first step is laser irradiation of ultrashort laser pulses with 532 nm wavelength, which is used to create of nucleation centers inside of the optically transparent glass. The crystallization of the structural modification areas was carried out by a photothermal action of CO₂ laser radiation with a 10.6 μm wavelength. The range of crystallization temperatures was defined and the kinetics of the phase transformations of the modified regions inside of the glass were studied. Duration of crystallization was about 10 min with a slow heating and 25 s at the fast heating to crystallization temperature.     

Effect of Ultrashort Pulsed Laser and X-Ray Irradiation on Au+ -Doped Glass

Au nanoparticles were precipitated inside Au+-doped glass samples after irradiation by femtosecond laser or x-ray. Femtosecond laser and X-ray irradiation result in decreasing of anneal temperature and critical size for the precipitation of Au nanoparticles.     

飞秒脉冲激光对YAG晶体的辐照作用的研究

采用波长为800nm，脉冲宽度为120fs的飞秒激光对提拉法和温梯法生长的YAG晶体进行辐照。并对辐照后的样品进行吸收光谱及电子顺磁共振谱(EPR)的检测。结果表明，提拉法的晶体在经过辐照后，255nm吸收峰减弱，同时在370nm处产生新的宽峰吸收，其产生原因是由于样品内部分Fe^3 转化成Fe^2 ，并有少量F^ 心生成。对比两种不同方法生长的晶体，温梯法生长的YAG晶体的抗激光辐照能力略优于提拉法生长的晶体。     

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.     

Three-dimension direct writing TiO<Subscript>2</Subscript> crystalline patterns in Bi-free glass using femtosecond laser

Crystalline TiO₂ was induced three dimensionally inside Bi-free glass sample by an 800 nm, 250-kHz femtosecond laser irradiation. Micro-Raman spectra analysis indicated that the laser-induced crystals in the focal point of the laser beam were monophase TiO₂ rutile. Continuous crystalline lines were written through moving the focal point of the laser beam inside the glass. The results demonstrate that this technique is a convenient method to engrave three-dimensional patterns of crystals for fabricating integrated optical devices in transparent materials.     

Optimal spectral phase control of femtosecond laser-induced up-conversion luminescence in Sm3+:NaYF4 glass

The spectral phase of the femtosecond laser field is an important parameter that affects the up-conversion(UC)luminescence efficiency of dopant lanthanide ions.In this work,we report an experi-mental study on controlling the UC lmiiinescence efficiency in Sm^3+:NaYF4 glass by 800-nm femtosec-ond laser pulse shaping using spectral phase modulation.The optimal phase control strategy efficiently enhances or suppresses the UC luminescence intensity.Based on the laser-power dependence of the UC luminescence intensity and its comparison with the luminescence spectrum under direct 266-nm fem-tosecond lciser irradiation,we propose herein an excitation model combining non-resonant two-photon absorption with resonance-media ted three-photon absorption to explain the experimental observations.     

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.     

Multilayer optical memory using femtosecond-laser induced fluorescence in rare-earth ion doped glass

We report three-dimensional fluorescent memory by recording optical bits with irradiation of femtosecond laser pulses at 800 nm and by reading photoluminescence change in Eu³⁺ doped glass. We produced multi-layered micro-bit patterns and read the blue emission from the 405 and 325 nm excitations due to permanent reduction of Eu³⁺ to Eu²⁺ in sodium borate glass by scanning the irradiated region in multilayers.     

Generation of femtosecond laser pulses at 396 nm in K_3B_6O_(10)Cl crystal

K_3B_6O_(10)Cl(KBOC), a new nonlinear optical crystal, shows potential advantages for the generation of deep ultraviolet(UV) light compared with other borate crystals. In this paper we study for the first time the second harmonic generation(SHG) of a femtosecond Ti:sapphire amplifier with this crystal. Laser power is obtained to be as high as 220 m W at the central wavelength of 396 nm with a 1-mm-long crystal, and the maximum SHG conversion efficiency reaches 39.3%. The typical pulse duration is 83 fs. The results show that second harmonic(SH) conversion efficiency has the room to be further improved and that the new nonlinear crystal is very suited to generate the high efficiency deep ultraviolet laser radiation below 266 nm.     

Femtosecond laser direct writing of TiO2 crystalline patterns in glass

Crystalline TiO₂ was induced three dimensionally inside a glass sample by 800-nm, 250-kHz femtosecond laser irradiation. Micro-Raman spectra and X-ray diffraction analysis indicated that the laser-induced crystals were monophase TiO₂ rutile. A periodic structure consisting of TiO₂ rutile crystalline lines was inscribed in the glass sample by continuously moving the focal point of the laser beam. This technique may be useful for fabricating integrated optical devices in glasses.     

Crystallization of 21.25Gd2O3-63.75MoO3-15B2O3 glass induced by femtosecond laser at the repetition rate of 250 kHz

We report the formation of β′-Gd₂(MoO₄)₃ (GMO) crystal on the surface of the 21.25Gd₂O₃-63.75MoO₃-15B₂O₃ glass, induced by 250 kHz, 800 nm femtosecond laser irradiation. The morphology of the modified region in the glass was clearly examined by scanning electron microscopy (SEM). By micro-Raman spectra, the laser-induced crystals were confirmed to be GMO phases and it is found that these crystals have a strong dependence on the number and power of the femtosecond laser pulses. When the irradiation laser power was 900 mW, not only the Raman peaks of GMO crystals but also some new peaks at 214 cm⁻¹, 240 cm⁻¹, 466 cm⁻¹, 664 cm⁻¹ and 994 cm⁻¹which belong to the MoO₃ crystals were observed. The possible mechanisms are proposed to explain these phenomena.