飞秒激光诱导TiO2金红石相变的激光显微拉曼光谱研究

利用激光显微拉曼光谱仪研究了近红外飞秒激光脉冲诱导TiO2金红石晶体所引起的相变.实验发现当激光的脉冲功率为1.0μJ/脉冲时,随着飞秒激光辐照脉冲数的增加,金红石相的Eg模式强度增强,而A1g模式强度减弱,飞秒激光的非线性效应在晶体内部诱导产生了色心;当激光辐照脉冲数为2.5×106时,锐钛矿石相出现;随着激光辐照脉冲数的增加,锐钛矿相的拉曼振动模式强度增强,金红石相的拉曼振动模式强度减弱.     

飞秒强激光对二氧化钛金红石晶体相变的影响

该文章报道了利用显微激光拉曼光谱仪研究近红外飞秒强激光脉冲诱导二氧化钛金红石单晶所引起的相变.实验辐照时间为60s,当激光辐照平均功率增加时,锐钛矿相的拉曼振动模式强度增强,金红石相的拉曼振动模式强度减弱.通过金红石相和锐钛矿相粉体等拉曼光谱的实验,肯定了随着辐照激光功率的增大,.可以通过拉曼光谱中锐钛矿A1g B1g(515 cm-1)振动模式标志峰和金红石相Eg(445 cm-1)振动标志峰分别对应面积的比判断其相变量.     

采用拉曼光谱技术研究纳米锐钛矿到金红石的相转变

采用化学沉淀法制备出40nm的锐钛矿，并用拉曼光谱对纳米和块体锐钛矿到金红石的相转变过程进行了研究。实验结果表明：对于块体锐钛矿，在950℃保温1h，金红石的特征峰446cm^-1开始出现，随着温度的升高，金红石的特征峰446，610和231cm^-1继续增强，锐钛矿的特征峰639，515和397cm^-1逐渐减弱。在1100℃保温1h，锐钛矿转变为金红石；对于纳米锐钛矿，在900℃保温1h后几乎全部转变为金红石，比块体（微米级）锐钛矿到金红石的相转变温度降低了200℃。     

工业纯钛微弧氧化膜的结构及拉曼光谱分析

采用微弧氧化技术,用处理电压为300,350,400,450,500 V在工业纯钛表面制备了5块氧化膜试样,利用扫描电镜和拉曼光谱研究了处理电压对氧化膜结构的影响.结果表明:氧化膜表面布满了微孔,其尺寸随处理电压的升高而增加,而微孔密度则旱相反的变化趋势.氧化膜主要由锐钛矿和金红石相组成,其相含量与处理电压的大小密切相关.当处理电压较低时,氧化膜主要由锐钛矿相组成;随着处理电压的升高,氧化膜中金红石相的相对含量增加;当处理电压在400～450 V时,金红石相含量增加迅速,并成为主晶相.     

激光辐照对氧化锌光谱学性能的影响

本文以拉曼光谱,PL光谱等表征手段研究准分子激光辐照氧化锌晶格微结构及其光谱性能的影响。当能量密度超过一定阈值时,会造成晶格畸变,诱导产生附加的拉曼振动模式:布里渊区A点的TA模,位于70cm-1左右以及500～600cm-1之间的LO模。准分子激光辐照与未辐照区之间存在晶格畸变逐渐减弱的过渡区。采用共聚焦的方法,Z-向逐点扫描,可以估算一定激光能量密度下,辐照对氧化锌材料的影响区深度。     

纳米二氧化钛的红外辐照相变

以四氯化钛为原料 ,采用溶胶凝胶法技术合成路线 ,可以获得平均粒径在 30到 4 0纳米的二氧化钛粉末。在X—射线衍射 (XRD)和拉曼散射 (Raman)测试技术下 ,分析得到红外干燥方式下可使锐钛矿向金红石相转化 ,同时由于TiO2 纳米晶粒的尺寸效应以及弱的结晶性和局部格点不完善 ,使得Raman光谱特征峰向低波数移动。此外 ,随着反应温度的提高 ,逐步有金红石相产生 ,而 4 48cm- 1Eg 活性模对温度的依赖性体现了反斯托克斯现象。     

球磨处理的TiO2光谱特征及其光催化性能研究

为改变TiO₂的颗粒尺寸和提高其光催化性能,采用高能球磨法处理TiO₂粉末,研究球磨时间对样品微观形貌、晶体结构、拉曼光谱、荧光光谱和光催化性能的影响;分析荧光光谱和光催化性能之间的关系,确定光催化机理为快速判断其光催化性能提供依据。结果表明：随着球磨时间的增加样品颗粒由规则形状变成无规则形状且表面变得粗糙。所有样品均主要为锐钛矿结构,有少量的金红石结构,随着球磨时间的增加金红石结构的（110）衍射峰逐渐增强说明在球磨过程中少量的TiO₂发生了相转变,晶粒尺寸先减小后增加。所有样品均出现锐钛矿型TiO₂拉曼散射峰,而未发现金红石晶型的拉曼散射峰。各个拉曼峰的半高宽随着球磨时间的增加都有所增加,这表明样品的表面质量下降,表面缺陷和氧空位逐渐增加导致。所有样品在470 nm附近均出现荧光峰,且球磨后的样品该荧光峰得到增强,经过球磨后的TiO₂样品在397,452,483,500和536 nm等处出现荧光峰,且球磨4 h后的TiO₂荧光峰强度最强,表明其表面缺陷和氧空位含量最多,与拉曼光谱分析结果是一致的。随着辐照时间的增加到100 min所有样品的降解率均有所提升且100 min后所有样品对甲基橙的降解率超过60%。经过球磨后的TiO₂样品的降解率都比未球磨的样品高,且球磨4 h的样品的降解率最高,表明其光催化性能最好。在光催化反应过程中,氧空位和缺陷成为俘获光生电子的中心,以致于光生电子与空穴的复合被有效地禁止。氧空位促使样品对氧气的吸收,氧气与氧空位俘获的光生电子发生相互作用而形成氧自由基,对有机物的氧化起到关键作用,因此表面缺陷和氧空位越多,即激子光致发光峰越强,其光催化性能越好。采用球磨法可提高TiO₂粉末的光催化性能,并通过激子光致发光峰的强弱可快速定性地判断光催化性能的表现。     

热处理对爆轰合成的纳米TiO_2混晶的结构相变的影响

采用爆轰法制备了纳米TiO2混晶体,初步研究了不同煅烧温度(600℃和720℃)和不同煅烧时间(1 h,2 h,3.5 h和5 h)对其微结构和结构相变行为的影响,并应用热动力学理论讨论了从锐钛矿相到金红石相的结构相变过程和相变机理.研究表明:随着煅烧温度的升高和煅烧时间的增加,纳米TiO2的粒径逐渐增大,混晶中金红石相的含量逐渐提高.与常规方法制备的纳米TiO2不同的是,在相同煅烧温度和煅烧时间下金红石相的平均生长速率明显低于锐钛矿相.锐钛矿相完全相变为金红石的温度也明显低于常规方法报道的相变温度.该研究会对控制纳米TiO2晶体尺寸和批量合成提供一定的理论和实验指导.     

激光诱导水体中DOM的荧光猝灭特性分析

以355 nm激光为激发光源,在实验室中用激光诱导荧光(LIF)方法以不同浓度的腐殖酸为测量样品研究了水体中溶解有机物(DOM)的荧光猝灭特性.研究表明,随着腐殖酸浓度的增加,水拉曼散射强度逐渐减弱,当浓度为40 mg·L-1时,水拉曼散射信号几乎完全被DOM的荧光基态分子所吸收,而DOM的荧光强度随着浓度的增加,先是线性增加,当浓度为16 mg·L-1时,荧光强度达到最大,再继续增加腐殖酸浓度,荧光强度则缓慢降低.因此,通过对不同浓度下腐殖酸荧光猝灭特性的分析,可以更加有效的实现水体中DOM浓度的探测.     

高重复频率激光在非掺杂氧化铋玻璃中诱导TiO2晶体析出

使用聚焦后的800nm,150 fs,250 kHz的高重复频率飞秒脉冲激光研究它在非掺杂氧化铋玻璃内部三维选择性的诱导析晶.通过拉曼光谱测定发现析出的晶体是TiO2且为金红石相.研究表明,经过250 kHz的飞秒激光辐照一段时间后,玻璃内部由于脉冲能量的连续累积会使得激光辐照区域出现热累积效应,达到玻璃的析晶温度后诱导晶体析出.通过连续移动激光束,可以实现连续刻写TiO2晶线,通过EDX测试显示聚焦区域出现了由于热累积效应而形成热驱动使得离子发生迁徙.实验结果表明这种方法适用于在透明介质材料中三维选择性刻写晶体以制备集成光学器件.     

Phase transformation at the surface of TiO<Subscript>2</Subscript> single crystal irradiated by femtosecond laser pulse

Phase transformation of a titanium oxide crystal irradiated by a femtosecond laser from rutile to anatase was studied by Raman spectroscopy. In the case of the high temperature phase of TiO₂ single crystal rutile, irradiated by the 120 fs, 800 nm, 250 kHz femtosecond laser with an average power of 300 mW for a short time, the intensity of Raman active mode E_g (446 cm^-1) of TiO₂ would decrease, while that of A_1g (611 cm^-1) increased, which indicated the color-center-defect-cluster was formed. After the longer irradiation time (less than 600 s), four new Raman active modes would occur, so a part of rutile in the irradiated region was transformed into anatase phase. As the irradiation time increased, the component of anatase increased to a constant, while that of rutile decreased. By this means, we can selectively induce anatase on the rutile surface through controlling the femtosecond laser exposure region. We suggest that this technique can be applied to fabricate micro patterns of anatase. PACS 52.38.Dx; 36.20.Ng; 36.40.Ei; 42.62.-b; 42.65.Dr     

Raman study of phase transformation of TiO2 rutile single crystal irradiated by infrared femtosecond laser

Titanium dioxide (TiO₂) rutile single crystal was irradiated by infrared femtosecond (fs) laser pulses with repetition rate of 250 kHz and phase transformation of rutile TiO₂ was observed. Micro-Raman spectra show that the intensity of E_g Raman vibrating mode of rutile phase increases and that of A_1g Raman vibrating mode decreases apparently within the ablation crater after fs laser irradiation. With increasing of irradiation time, the Raman vibrating modes of anatase phase emerged. Rutile phase of TiO₂ single crystal is partly transformed into anatase phase. The anatase phase content transformed from rutile phase increased to a constant with increasing of fs pulse laser irradiation time. The study indicates the more stable rutile phase is transformed into anatase phase by the high pressure produced by fs pulse laser irradiation.     

The application of Raman and anti-stokes Raman spectroscopy for in situ monitoring of structural changes in laser irradiated titanium dioxide materials

The use of Raman and anti-stokes Raman spectroscopy to investigate the effect of exposure to high power laser radiation on the crystalline phases of TiO₂ has been investigated. Measurement of the changes, over several time integrals, in the Raman and anti-stokes Raman of TiO₂ spectra with exposure to laser radiation is reported. Raman and anti-stokes Raman provide detail on both the structure and the kinetic process of changes in crystalline phases in the titania material. The effect of laser exposure resulted in the generation of increasing amounts of the rutile crystalline phase from the anatase crystalline phase during exposure. The Raman spectra displayed bands at 144 cm⁻¹ (A1g), 197 cm⁻¹ (Eg), 398 cm⁻¹ (B1g), 515 cm⁻¹ (A1g), and 640 cm⁻¹ (Eg) assigned to anatase which were replaced by bands at 143 cm⁻¹ (B1g), 235 cm⁻¹ (2 phonon process), 448 cm⁻¹ (Eg) and 612 cm⁻¹ (A1g) which were assigned to rutile. This indicated that laser irradiation of TiO₂ changes the crystalline phase from anatase to rutile. Raman and anti-stokes Raman are highly sensitive to the crystalline forms of TiO₂ and allow characterisation of the effect of laser irradiation upon TiO₂. This technique would also be applicable as an in situ method for monitoring changes during the laser irradiation process.     

Silver-Doping Induced Lattice Distortion in TiO2 Nanoparticles

The Ag-doping effects on Ti02 nanoparticles are investigated by means of x-ray diffraction （XRD） and Raman scattering spectroscopy. XRD and Raman results indicate that Ag-doping stabilizes the rutile phase in TiO2. We find an Ag-doping induced lattice expansion in both anatase and rutile phases. The Ag-doping has different influences on the lattice distortion for anatase and rutile phases, that is, the e/a-value for the anatase phase decreases with 0.5% Ag-doping and then increases with 1~ Ag-doping while that for the rutile phase shows a gradual increase with increasing Ag-doping. We have ascribed the different variations of lattice distortion due to Ag-doping to the change of interracial interaction between the anatase and rutile phases induced by different Ag concentrations.     

Laser-induced crystalline phase transition from rutile to anatase of niobium doped TiO2

The investigation of the laser-induced crystalline phase transition of niobium doped TiO₂ single crystal is discussed in this paper. The TiO₂ single crystal was studied by using Raman spectroscopy and electron backscatter diffraction before and after irradiation by 266?nm?ns laser at the threshold intensity of 56?MW/cm². Experimental results show an evidence of anatase phase formation from rutile single crystal. Moreover, the analysis of the experimentally obtained and calculated crystallographic texture indicates that the converted TiO₂ layer has a polycrystalline structure with the preferred orientations. According to the Raman spectroscopy the amount of anatase phase increases with the number of laser pulses indicating the dose-dependent conversion process.     

纳米二氧化钛材料的相变和声子限制效应(英文)

拉曼光谱用于研究二氧化钛材料的相变和声子限制效应。化学溶液方法制备了TiO2纳米晶材料。其平均粒度为 6 8- 2 7 9nm。最低频率 1 5 2cm- 1 Eg 模随粒度减小出现蓝移和加宽。在声子限制模型下 ,理论上对不同粒度的TiO2 纳米晶 (6 8,1 0 3和 2 7 9nm)的频移和线宽进行计算 ,结果与实验吻合得很好。研究了TiO2 纳米晶锐钛矿 -金红石相变 ,其相变温度为 6 5 0 - 6 90℃ ,比体块TiO2 的相变温度 1 0 0 0℃低 ,表明了相变的尺寸效应     

Femtosecond laser-induced stimulation of a single neuron in a neuronal network

We demonstrated the stimulation of neurons at a single-cell level in cultured neuronal network by a focused femtosecond laser. When the femtosecond laser was focused on a neuron loaded with a fluorescent calcium indicator, the fluorescence intensity immediately increased at the laser spot, suggesting that intracellular Ca²⁺ increases in the neuronal cell due to the femtosecond laser irradiation. The probability of Ca²⁺ elevation at the laser spot depended on the average laser power, irradiation time, and position of the focal point along the optical axis, indicating that the femtosecond laser activates neurons because of multiphoton absorption. Moreover, after laser irradiation of a single neuron cultured on multielectrode arrays, the evoked electrical activity of the neurons was demonstrated by electrophysiological systems, which concluded that the focused femtosecond laser could achieve stimulating a single neuron in a neuronal network with high spatial and temporal resolution.