Picosecond nonlinear optical response of Ba0.5Sr0.5TiO3 thin films fabricated by pulsed laser deposition

Well-crystallized Ba_0.5Sr_0.5TiO₃ thin films with good surface morphology were prepared on MgO(1 0 0) substrates by pulsed laser deposition technique at a deposition temperature of 800 °C under the oxygen pressure of 2 × 10⁻³ Pa. X-ray diffraction and atomic force microscopy were used to characterize the films. The full width at half maximum of the (0 0 2) Ba_0.5Sr_0.5TiO₃ rocking curve and the root-mean-square surface roughness within the 5 μm × 5 μm area were 0.542° and 0.555 nm, respectively. The nonlinear optical properties of the films were determined by a single beam Z-scan method at a wavelength of 532 nm with laser duration of 55 ps. The results show that Ba_0.5Sr_0.5TiO₃ thin films exhibit a fast third-order nonlinear optical response with the nonlinear refractive index and nonlinear absorption coefficient being n₂ = 5.04 × 10⁻⁶ cm²/kW and β = 3.59 × 10⁻⁶ (m/W), respectively.     

Structural and electrical characterisation of La0.5Ca0.5MnO3 thin films grown by pulsed laser deposition

Thin films of perovskite manganite, with nominal composition La_0.5Ca_0.5MnO₃, have been prepared by pulsed laser deposition on (1 0 0) SrTiO₃, (1 0 0) LaAlO₃, (1 0 0) Si and YSZ/CeO₂-buffered (1 0 0) Si substrates. Structural and electrical characterisation was performed on the films. The magneto-transport properties of all the thin films depart from the bulk behaviour. The LCMO film grown on buffered Si shows an insulator–metallic transition around 130–150 K while the one deposited directly on Si displayed a similar behaviour under a melting field of 1 T. However, that transition is absent in the films grown on LAO and STO. We suggest that appropriate stress values induced by the substrate favour the formation of metallic percolative paths.     

Picosecond and femtosecond pulsed laser ablation and deposition of quasicrystals

A Nd:glass laser with pulse duration of 250 fs and 1.3 ps has been used to evaporate a Al₆₅Cu₂₃Fe₁₂ quasicrystalline target. The gaseous phase obtained from the ablation process has been characterised by several techniques such as emission spectroscopy, quadrupole mass spectrometry and ICCD imaging, used to study the plume composition, energy and morphology. The results show that the ablation processes in the short-pulse regimes are very different to the nanosecond one. In particular the plume angular distribution shows a characteristic high cosine exponent and the composition is completely stoichiometric and independent from the laser fluence. Furthermore the mass spectra indicate the presence of clusters, both neutral and ionised and the emission from the target suggest a rapid thermalisation leading to the melting of the surface. To clarify the ablation process some films have been deposited, on oriented silicon, at different experimental conditions and analysed by scanning electron microscopy, atomic force microscopy, energy dispersive X-ray analysis and X-ray diffraction. The analyses show the presence of nanostructured films retaining the target stoichiometry but consisting of different crystalline and non crystalline phases. In particular the nanostructure supports the hypothesis of the melting of the target during the ablation and a mechanism of material ejection is proposed for both picosecond and femtosecond regimes.     

K负载Ce0.5Mn0.5O2催化剂对柴油机碳烟氧化性能的影响

采用柠檬酸络合法制备了不同KNO3负载量的xK-Ce_0.5Mn_0.5O₂系列催化剂,采用热重分析仪对其催化碳烟颗粒(PM)的活性进行评价,并用Coats-Redfern法进行氧化动力学分析,同时采用XRD,H2-TPR,Raman,XPS等技术对催化剂样品内部结构进行探究。结果表明:KNO₃负载使得少部分钾离子进入晶格内部,导致铈锰固溶体产生更多晶格缺陷,提高了催化剂中活性氧的含量。其余的KNO3则与Mn物种发生反应产生了具有更高催化活性的钾锰矿,改变了碳烟与催化剂的接触状态,提升了催化剂的活性。催化剂活性与KNO₃的负载量也有一定关系,当x=0.2时,催化剂的活性达到最佳,碳烟氧化所需要的活化能最低。     

Nanosecond pulsed laser ablation of silicon in liquids

Laser fluence and laser shot number are important parameters for pulse laser based micromachining of silicon in liquids. This paper presents laser-induced ablation of silicon in liquids of the dimethyl sulfoxide (DMSO) and the water at different applied laser fluence levels and laser shot numbers. The experimental results are conducted using 15 ns pulsed laser irradiation at 532 nm. The silicon surface morphology of the irradiated spots has an appearance as one can see in porous formation. The surface morphology exhibits a large number of cavities which indicates as bubble nucleation sites. The observed surface morphology shows that the explosive melt expulsion could be a dominant process for the laser ablation of silicon in liquids using nanosecond pulsed laser irradiation at 532 nm. Silicon surface’s ablated diameter growth was measured at different applied laser fluences and shot numbers in both liquid interfaces. A theoretical analysis suggested investigating silicon surface etching in liquid by intense multiple nanosecond laser pulses. It has been assumed that the nanosecond pulsed laser-induced silicon surface modification is due to the process of explosive melt expulsion under the action of the confined plasma-induced pressure or shock wave trapped between the silicon target and the overlying liquid. This analysis allows us to determine the effective lateral interaction zone of ablated solid target related to nanosecond pulsed laser illumination. The theoretical analysis is found in excellent agreement with the experimental measurements of silicon ablated diameter growth in the DMSO and the water interfaces. Multiple-shot laser ablation threshold of silicon is determined. Pulsed energy accumulation model is used to obtain the single-shot ablation threshold of silicon. The smaller ablation threshold value is found in the DMSO, and the incubation effect is also found to be absent.     

Ca0.5Sr0.5TiO3弹性和热学性质的第一性原理研究

利用能量最小原理, 确定了Ca_0.5Sr_0.5TiO₃晶体中4c位置的Ca/Sr原子对称分布, 建立了Ca_0.5Sr_0.5TiO₃稳定的晶体结构, 在此基础上利用基于密度泛函理论第一性原理的平面波超软赝势方法, 采用局域密度近似和广义梯度近似函数, 计算了Ca_0.5Sr_0.5TiO₃的晶格参数、弹性常数、体弹模量、剪切模量、杨氏模量、泊松比, 并基于Christoffel方程的本征值研究了平面声波的特征, 基于Cahill和Cahill-Pohl模型研究了最小热导率的特征. 计算结果表明: Ca_0.5Sr_0.5TiO₃晶格参数和实验值很接近, 体弹模量大于剪切模量, [100], [010], [001]晶向的杨氏模量、泊松比、普适弹性常数(A^U)以及杨氏模量三维图均显示了弹性各向异性; 平面声波在(010), (001)平面呈现各向异性, 在(100)平面呈现各向同性, 平面声波大小与平均横波和平均纵波的数值很接近. Cahill模型最小热导率在各平面呈现各向同性, Cahill-Pohl模型最小热导率在高温时趋于恒定. 准谐德拜模型下Ca_0.5Sr_0.5TiO₃ 晶体的摩尔热容和热膨胀系数与CaTiO₃晶体的接近, 并且高温下具有稳定的热膨胀性能. 计算所得禁带宽度为2.19 eV, 导带底主要是Ti-3d与O-2p态电子贡献; 由电荷布居和电荷密度图理论证实Ca_0.5Sr_0.5TiO₃具有稳定的Ti-O八面体结构.     

散射光信号与石墨-二氧化硅激光辐照烧蚀阈值的关系

石墨-二氧化硅作为无机添加材料,广泛应用于各类航空航天器烧蚀涂层领域,其在高温下具有较高的反应吸热焓,在高能激光烧蚀领域具有良好的应用前景。目前,关于石墨-二氧化硅的高能激光烧蚀研究较少,尤其在高能激光烧蚀中的反应时间和烧蚀阈值难以确定。针对此问题,利用近红外探测器对激光辐照样品表面的散射光进行实时探测,并对其散射光曲线进行微分拟合处理。基于此散射光信号,结合样品烧蚀后的形态结构分析,研究了石墨-二氧化硅在不同激光功率密度下的反应时间阈值。研究结果表明:在激光输出功率密度为500 W/cm~2持续辐照10 s时,散射光拟合曲线持续升高无突变,表明未发生明显的烧蚀;当激光功率密度升高至1 000~1 500 W/cm~2时,散射光微分拟合曲线出现明显转折点,对应的反应时间阈值分别为1.5 s和0.8 s。     

单相Na0.5Bi0.5Ti1-xMnxO3陶瓷中的多铁性

溶胶凝胶法制备了Na0.5Bi0.5Ti1-xMnxO3(x=0,0.02,0.04)陶瓷样品,X射线衍射(XRD)分析表明陶瓷样品均形成了单一的钙钛矿(ABO3)型结构且没有杂质相的形成.随着Mn含量的增加,XRD峰向高角度方向移动,表明Mn离子进入Na0.5Bi0.5TiO3晶格.掺杂样品均表现出室温铁磁性和铁电性.磁测量表明样品中存在复杂的磁相互作用,包括铁磁,反铁磁和顺磁相互作用.以上结果表明,通过Mn的掺杂可以使铁电材料Na0.5Bi0.5TiO3转变为多铁材料.     

Femtosecond laser ablation of DAST

High rate femtosecond (fs) laser ablation of the organic salt 4-N,N-dimethylamino-4-N-methyl-stilbazolium tosylate (DAST), an organic crystal with very high optical nonlinearities has been demonstrated. The threshold fluence and the ideal fluence range for damage free ablation for the wavelengths 550, 600, and 775 nm have been determined and the quality of the produced grooves has been investigated. The threshold fluences are in the order of 10–70 mJ/cm² and the ideal fluence range for damage free ablation is ranging from 30 to 300 mJ/cm², depending on the wavelength. The optimal focussing for ablation has been investigated and first results towards the structuring of a ridge waveguide are presented. We conclude that this method is most promising for waveguide patterning of DAST surfaces for integrated optics applications.     

Morphology of ablation craters generated by fs laser pulses in LiNbO3

The surface morphology of the ablation craters generated in LiNbO₃ by 130 fs laser pulses at 800 nm has been investigated by AFM/SNOM microscopy. The single pulse fluence corresponding to the ablation threshold has been estimated to be ≈1.8 J/cm².A complex structure including random cone-shaped protrusions is observed inside the ablated crater. The scale of the protrusion spacing is in the submicron range and the heights are typically of a few tens of nanometers. At and outside the crater rim a novel quasi-periodic wave-like topography pattern is observed in both types of microscopy techniques. The average wavelength, that is slightly dependent on pulse fluence, is (500-800 nm) comparable to the light wavelength. This novel topography feature keeps a close similarity with a Fresnel diffraction pattern by an absorbing circular obstacle or impact wave pattern produced by a combination of heat and shock wave (resemble that of impact crater). It is proposed that the obstacle is associated to the strongly nonlinear multiphoton absorption at the peak of the pulse profile. The energy deposited by nonlinear absorption of such profile causes ablation of both the crater and the rippled structure.     

一维纳米材料SmPO4·0.5H2O的制备及光学性质

以氧化钐和H₃PO₄为原材料,在无模板剂的情况下,用水热法通过调控pH、时间和温度制备了SmPO₄·0.5H₂O一维纳米材料,并提出其可能形成机理。用X射线粉末衍射（XRD）、透射电镜（TEM,HRTEM和SAED）、红外光谱（IR）和能谱（EDS）对产物的物相结构、微观形貌和组成进行了表征。用紫外-可见吸收光谱研究了产物的光学性质。研究结果表明,实验所制备的产物全部是六方晶系结构,形貌都为一维纳米线。反应体系的pH值、温度和时间的改变对纳米线的长径比有影响,但对其相结构基本都没有影响。分析得到最佳水热制备条件为pH=5、温度和时间分别为130℃和8 h,产物的结晶性、分散性和均匀性都达到最好。光学性质研究表明,该类产物在300~350 nm的紫外区域有吸收宽峰,是属于基质O^2-→P⁵⁺、Sm³⁺的电荷迁移。在350~450 nm处的可见光区域内也有一组吸收峰,是属于Sm³⁺的4f内层电子间的f-f跃迁吸收。依据该类吸收峰,得到禁带宽度在4.67~5.50 eV之间。pH值和温度对产物光学性能均有影响。     

XPS investigation on Upilex-S polyimide ablated by pulse TEA CO2 laser

Laser ablation of Upilex-S polyimide films 80 μm thick was performed in air using a pulse TEA CO₂ laser with wavelength 9.3 μm. A halo surrounding the hole was observed, which is covered with sub-micro particles. Pieces of ablation products protrude from the ablated surface, leading to considerable roughness of the ablated area. Chemical and structural changes of Upilex-S polyimide film surface irradiated by the pulse TEA CO₂ laser in air were analyzed by X-ray photoelectron spectroscopy (XPS). Relative C content in the ablated area was found to be higher, whilst both O and N contents were lower than in the untreated area. This means that TEA CO₂ laser ablation released both the O and N atoms. Also, the peak areas corresponding with carbonyl group (C=O) in the imide system were reduced much more and a new component at 287.0 eV assigned to the amide structure (N---C=O) was detected after laser ablation. These suggest that the pyrolysis of the Upilex-S polyimide was the decomposition of the imide ring between the nitrogen/aromatic carbon atom and carbonyl carbon atom. In addition, another new component arising from >C=O groups was also detected for higher fluence (7.83 J/cm²), and its peak areas is very small. This result indicates that the slight oxidation may take place with higher fluence during laser ablation in air. Based on above-mentioned experimental results, a possible thermally-induced decomposition path of Upilex-S polyimide ablated by TEA CO₂ laser is presented.     

飞秒激光对高反膜的破坏及其超快动力学过程

研究了800nm飞秒激光照射下45°高反膜ZrO2-Si O2的破坏及其超快动力学过程。利用原子力显微镜和扫描电镜观察了材料的烧蚀形貌,测量了破坏阈值与脉冲宽度、烧蚀深度与脉冲能量的依赖关系。随着脉冲宽度从50fs增加到900fs,其烧蚀阈值从0.35J/cm2增加到1.78J/cm2。烧蚀深度与激光能流密度近似成对数关系。当激光强度略高于烧蚀阈值时,材料很快被烧蚀到几百纳米,烧蚀深度表现出明显的层状特性。同时,利用建立的抽运探针实验系统,测量了高强度抽运脉冲作用下材料对探针光的反射率随延迟时间的变化,揭示了薄膜烧蚀的超快动力学过程。实验结果表明高反膜表层的材料对烧蚀特性有重要影响。     

Non-resonant microwave absorption and critical current density in YBa2Cu3Ox films prepared by laser ablation

High-quality YBa₂Cu₃O_x superconducting thin films have been prepared on (100)MgO substrates by the laser ablation technique, and characterized by non-resonant microwave absorption (NRMA) with a field modulation, magnetization and four-probe measurements. The pinning properties derived from the NRMA spectra for various YBa₂Cu₃O_x films are correlated with the critical current densities T_c. A relatively high-J_c film prepared from YBa₂Cu₃O_x composition target using a Nd:YAG laser shows a derivative spectrum and a large hysteresis in the NRMA spectra. The highest-J_c film prepared from an YBa₂Cu₄O_x composition (YBa₂Cu₃O_x+CuO) target using an ArF excimer laser does not show a derivative NRMA spectrum, suggesting a strong pinning property.     

Ultraviolet and visible Raman spectroscopy characterization of diamond–like carbon film growth by pulsed laser deposition

Laser-induced removal of flash from heat sinks in integrated circuit (IC) packages has been studied. It is found that flash can be effectively removed from heat sinks in plastic IC packages by laser deflashing. An optical microscope, an α-step surface profiler and X-ray photoelectron spectroscopy are used to analyze the deflashing efficiency. Laser deflashing of IC packages is based on laser ablation of flash materials. With an increase of laser fluence, the ablation rate increases. The laser fluence is selected between the ablation threshold of flash materials and that of heat-sink materials. An acoustic wave is generated by laser ablation of flash materials. Acoustic wave detection is used to monitor the surface cleanness during laser deflashing and to determine the ablation threshold of flash materials. Received: 18 April 2001 / Accepted: 14 September 2001 / Published online: 17 October 2001     

Fabrication of high-aspect-ratio microstructures using excimer laser

An excimer laser micromachining system is developed to study the ablation of high-aspect-ratio microstructures. The study examines the ablation efficiency, specifically, the impact of changing major laser operating parameters on the resulting microstructural shapes and morphology. The study focuses on glass, although results on silicon and aluminum are also included for comparison. In ablating grooved structures, the ablation depth has been observed to be linearly proportional to the operating parameters, such as the pulse number and fluence. The results specifically indicate that ablation at low fluence and high repetition rates tends to form a V-shaped cross-section or profile, while a U-shaped profile can be obtained at high fluence and low repetition rate. The ablation rate or ablated volume has then been quantified based on the ablation depth measured and the ablated profile observed. The threshold fluence has also been obtained by extrapolating experimental data of ablation rate. The extrapolation accuracy has been established by the good agreement between the extrapolated value and the one predicted by Beer's law. Moreover, a one-dimensional analytical solution has been adopted to predict the ablated volume so as to compare with the experimental data. The reasonable agreement between the two indicates that a simple analytical solution can be used for guiding or controlling further laser operations in ablating glass structures. Finally, the experimental results have shown that increasing the repetition rate favors the morphology of ablated surfaces, though the effect of repetition rate on ablation depth is insignificant.     

Transverse laser induced thermoelectric voltage effect in tilted La0.5Sr0.5CoO3 thin films

The transverse laser induced thermoelectric voltage effect has been investigated in tilted La_0.5Sr_0.5CoO₃ thin films grown on vicinal cut LaAlO₃ (1 0 0) substrates when films are irradiated by pulse laser at room temperature. The detected voltage signals are demonstrated to originate from the transverse Seebeck effect as the linear dependence of voltage on tilted angle in the range of small tilted angle. The Seebeck coefficient anisotropy ΔS of 0.03 μV/K at room temperature is calculated and its distorted cubic structure is thought to be responsible for this. Films grown on a series of substrates with different tilted angles show the optimum angle of 19.8° for the maximum voltage. Film thickness dependence of voltage has also been studied.     

Identification of non-thermal and thermal processes in femtosecond laser-ablated aluminum

Non-thermal and thermal processes due to femtosecond laser ablation of aluminum (Al) at low, moderate, and high-fluence regimes are identified by Atomic Force Microscope (AFM) surface topography investigations. For this purpose, surface modifications of Al by employing 25 fs Ti: sapphire laser pulses at the central wavelength of 800 nm have been performed to explore different nano- and microscale features such as hillocks, bumps, pores, and craters. The mechanism for the formation of these diverse kinds of structures is discussed in the scenario of three ablation regimes. Ultrafast electronic and non-thermal processes are dominant in the lower fluence regime, whereas slow thermal processes are dominant at the higher fluence regime. Therefore, by starting from the ablation threshold three different fluence regimes have been chosen: a lower fluence regime (0.06–0.5 J cm^?2 single-shot irradiation under ultrahigh vacuum condition and 0.25–2.5 J cm^?2 single-shot irradiation in ambient condition), a moderate-fluence regime (0.25–1.5 J cm^?2 multiple-shot irradiation), and a high-fluence regime 2.5–3.5 J cm^?2 multiple-shot irradiation. For the lower fluence (gentle ablation) regime, around the ablation threshold, the unique appearance of individual, localized Nano hillocks typically a few nanometers in height and less than 100 nm in diameter are identified. These Nano hillock-like features can be regarded as a nonthermal, electronically induced phase transition process due to localized energy deposition as a result of Coulomb explosion or field ion emission by surface optical rectification. At a moderate-fluence regime, slightly higher than ablation threshold multiple-pulse irradiation produces bump-formation and is attributed to ultrafast melting (plasma formation). The high-fluence regime results in greater rates of material removal with highly disturbed and chaotic surface of Al with an appearance of larger protrusions at laser fluence well above the ablation threshold. These nonsymmetrical shapes due to inhomogeneous nucleation, cluster formation, and resolidification of a metallic surface after melting are attributable to slow thermal processes (ps time scale).     

Effect of spot size on cone formation in a XeCl laser ablation of polyethersulfone films

Radiation from the UV excimer lasers, with the fluence above the ablation threshold, can etch the polymer surfaces by photoablation. In some cases different microstructures may appear on the surface during the laser ablation. In this paper the effect of the laser spot size on the cone formation on polyethersulfone films has been investigated. The experiments have been performed with a XeCl laser at the wavelength of 308 nm and at the fluences of 70 and 100 mJ/cm² at air. For the investigation of the effect of the laser spot size on cone formation, the samples were irradiated at two different laser spot sizes of w₁ and w₂ = 0.1 w₁. The morphology of the processed surface was studied by scanning electron microscopy (SEM). It has shown that the shape, size and density of cones change with the change of the laser spot size. Also, the number of pulses and the pulse repetition rate which are needed for threshold of cone formation are affected by the laser beam spot size on the surface.     

Crystallization of amorphous Ge2Sb2Te5 films induced by a single femtosecond laser pulse

Crystallization is achieved in amorphous Ge₂Sb₂Te₅ films upon irradiation with a single femtosecond laser pulse. Transmission electron microscopy images evidence the morphology of the crystallized spot which depends on the fluence of the femtosecond laser pulse. Fine crystalline grains are induced at low fluence, and the coarse crystalline grains are obtained at high fluence. At the damage fluence, ablation of the films occurs.