Detection of neutral products formed during excimer laser ablation of polyimide by UV and VUV laser photoionization/mass spectrometry

Some of the neutral species which are produced in the laser ablation of polyimide have been characterized using multiphoton ionization/time of flight mass spectrometry. Three different wavelengths (193 nm, 157 nm, and 118 nm) have been used in an attempt to effect soft ionization of the products formed during or after the initial laser ablation of the polymer. Neutral photo-ablation products detected using this scheme range from atomic to high molecular weight species which, depending on the probe wavelength, include pure carbon clusters as well as a broad distribution of heteroatom containing clusters. However, there is virtually no overlap in the mass spectra recorded at each probe wavelength. When probing with 193 nm, marked changes are observed in the mass spectra as a function of the probe flux used. At moderate fluxes, pure carbon clusters (fullerenes) are observed. The identification of a large distribution of species other than pure carbon clusters is in dramatic contrast to the recent observation [W.R. Creasy, J.T. Brenna: Chem. Phys. 126, 453 (1988)] of the positively charged ionic species produced, which are solely carbon clusters. These results suggest that the neutral and ionic products observed after ablation of the polymer are due to both condensation of the atomic and molecular fragments which form during the ablation laser pulse and nascent polymer fragments. Various implications of this result for the unambiguous determination of the true ablation product distribution are discussed.     

High Power Continuous-Wave and Acousto-Optic Q-Switched Nd：GdVO4 Laser Operated at 912 nm

We present a high power and efficient operation of the ^4F3/2 → ^4I9/2 transition in Nd：GdVO4 at 912nm. In the cw mode, the maximum output power of 8.6 W is achieved when the incident pump power is 40.3 W, leading to a slope efficiency of 33.3% and an optical-optical efficiency of 21.3%. To the best of our knowledge, this is the highest cw laser power at 912nm obtained with the conventional Nd：GdVO4 crystal. Pulsed operation of 912nm laser has also been realized by inserting a small aeousto-optie （A-O） Q-Switch inside the resonator. As a result, the minimal pulse width of 20ns and the average laser power 1.43 W at the repetition rate of lOkHz are obtained, corresponding to 7.1 kW peak power. We believe that this is the highest laser peak power at 912nm. Furthermore, duration of 65ns has also been acquired when the repetition rate is 100 kHz.     

Diagnostics of laser-ablated carbon plumes by photoionization using a tunable laser

Tunable laser pulses at wavelengths from 250 to 880 nm were fired at plumes produced by laser ablation of a carbon target in He atmosphere. We observed an electrical current due to photoionization, which roughly reflected the behavior of carbon clusters in the plume. The photoionization current had dynamic temporal variations, comprising a rapid increase at the beginning (T_D<0.2 ms, where T_D is the time after a YAG laser pulse for laser ablation irradiates the target), a gradual increase for 0.2D<3 ms, and a slow decrease for T_D>7 ms. The increasing phase of the photoionization current was synchronized with the decreasing phase of C₂ radical density. For He gas pressures lower than 0.8 Torr no photoionization current was detected. The growth rate of the photoionization current was higher for a higher He gas pressure.     

Diamond-like-carbon films produced by magnetically guided pulsed laser deposition

We have compared the quality of carbon films deposited with magnetically guided pulsed laser deposition (MGPLD) and conventional pulsed laser deposition (PLD). In MGPLD, a curved magnetic field is used to guide the plasma but not the neutral species to the substrate to deposit the films while, in conventional PLD, the film is deposited with a mixture of ions, neutral species and clusters. A KrF laser pulse (248 nm) was focused to intensities of 10 GW/cm² on a carbon source target and a magnetic field strength of 0.3 T was used to steer the plasma around a curved arc to the deposition substrate. Electron energy loss spectroscopy was used in order to measure the fraction of sp³ bonding in the films produced. It is shown that the sp³ fraction, and hence the diamond-like character of the films, increased when deposited only with the pure ion component by MGPLD compared with films produced by the conventional PLD technique. The dependence of film quality on the laser intensity is also discussed. Received: 7 December 2000 / Accepted: 20 August 2001 / Published online: 2 October 2001     

Working Pressure Dependence of Properties of Al2O3 Thin Films Prepared by Electron Beam Evaporation

The effects of working pressure on properties of Al2O3 thin films are investigated. Transmittance of the Al2O3 thin film is measured by a Lambda 900 spectrometer. Laser-induced damage threshold （LIDT） is measured by a Nd：YAG laser at 355 nm with a pulse width of 7ns. Microdefects were observed under a Nomarski microscope. The samples are characterized by optical properties and defect, as well as LIDT under the 355 nm Nd：YAG laser radiation. It is found that the working pressure has fundamental effect on the LIDT. It is the absorption rather than the microdefect that plays an important role on the LIDT of Al2O3 thin film.     

A novel route to aligned nanotubes and nanofibres using laser-patterned catalytic substrates

We describe the generation of aligned carbon nanotube bundles and films by pyrolysis of solid organic precursors (for example 2-amino-4,6-dichloro-s-triazine, s-triaminotriazine) at 950-1050 °C over laser-patterned thin metal (Fe, Co, Ni) films, deposited on silica substrates. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) studies reveal that surface roughness of the laser-etched catalytic substrates plays a key role in achieving control of nanotube growth. We believe that, during the etching process, the energised (ablated) metal clusters condense and recrystallise evenly, possibly as the metal oxide, within the edges or surface of the eroded regions. During pyrolysis these catalytic particles, embedded in the silica substrates, are responsible for carbon agglomeration and subsequent tube axial growth, suggesting that nanotube alignment strongly depends upon the etching conditions (for example laser power, pulse duration, and focal distance). The pyrolysed products (usually nanotubes or nanofibres) were characterised by SEM, high-resolution transmission electron microscopy (HRTEM), electron energy loss spectroscopy (EELS) and energy dispersive X-ray spectroscopy (EDX). Samples containing only small amounts of amorphous carbon and other carbonaceous particles are notably absent. We observe that the degree of graphitisation is dependent upon the catalyst and the organic precursor. Interestingly, a nitrogen content З% was detected within the nanofibres, which exhibit corrugated graphite-like morphologies. This pyrolytic method may be used to advantage in generating aligned heteroatomic nanostructures such as B_xC_yN_z systems.     

Growth dynamics of carbon-metal particles and nanotubes synthesized by CO2 laser vaporization

To study the growth of carbon-Co/Ni particles and single-wall carbon nanotubes (SWNTs) by 20 ms CO₂ laser-pulse irradiation of a graphite-Co/Ni (1.2 at. %) target in an Ar gas atmosphere (600 Torr), we used emission imaging spectroscopy and shadowgraphy with a temporal resolution of 1.67 ms. Wavelength-selected emission images showed that C₂ emission was strong in the region close to the target (within 2 cm), while for the same region the blackbody radiation from the large clusters or particles increased with increasing distance from the target. Shadowgraph images showed that the viscous flow of carbon and metal species formed a mushroom or a turbulent cloud spreading slowly into the Ar atmosphere, indicating that particles and SWNTs continued to grow as the ejected material cooled. In addition, emission imaging spectroscopy at 1200 °C showed that C₂ and hot clusters and particles with higher emission intensities were distributed over much wider areas. We discuss the growth dynamics of the particles and SWNTs through the interaction of the ambient Ar with the carbon and metal species released from the target by the laser pulse.     

Laser Induced Damage Threshold at 355 and 1064nm of Ta2O5 Films of Different Phases

Ta2O5 films axe deposited on fused silica substrates by conventional electron beam evaporation method. By annealing at different temperatures, Ta2 O5 films of amorphous, hexagonal and orthorhombic phases are obtained and confirmed by x-ray diffractometer （XRD） results. X-ray photoelectron spectroscopy （XPS） analysis shows that chemical composition of all the films is stoichiometry. It is found that the amorphous Ta2 O5 film achieves the highest laser induced damage threshold （LIDT） either at 355 or 1064nm, followed by hexagonal phase and finally orthorhombic phase. The damage morphologies at 355 and 1064nm are different as the former shows a uniform fused area while the latter is centred on one or more defect points, which is induced by different damage mechanisms. The decrease of the LIDT at 1064nm is attributed to the increasing structural defect, while at 355nm is due to the combination effect of the increasing structural defect and decreasing band gap energy.     

Ultra-Fast Decay Process of Electrons in LiNbO3 Crystal Induced by Femtosecond Pulse

Temporal evolution of absorption induced by single femtosecond pulse （13Ors, 800nm） with high intensity in LiNbO3 is obtained using the probe shadow imaging technique in order to investigate light-induced electron relaxation processes. By saturating the polaron density with a high intensity laser pulse, ultra-fast decay process on picosecond time scale is observed. The decay time constant is about 141 ps and it is attributed to the direct interband electron-hole recombination process.     

Laser-Duration Dependence of Emission Properties of High-Order Harmonic Generation

Quantitative investigations are made for the laser-duration dependence of the emission properties of high-order harmonic generation （HHG）. HHG emission properties produced by few-cycle lasers show some useful characteristics. The cutoff energy is less than that by laser for infinite duration. The single energy distribution pulse decreases much faster than its duration as the laser duration grows. A two-cycle laser with carrier-envelope phase of 0° can produce a single distribution pulse peaked at the laser carrier phase 1.22 rad and spanned 1.18 rad with the cutoff energy 2.9Up ＋ Ip and a bandwidth 0.63Up, where Up is the ponderomotive potential of the laser field and Ip is the atomic ionization potential.     

Emission of neutral molecules during UV laser ablation of a photolabile triazeno polymer

The neutral products of irradiating a photolabile triazeno-polymer with a pulsed laser at 248 nm (KrF excimer) were studied with time-of-flight (TOF) mass spectrometry. At fluences below 1.3 J/cm², N₂ is by far the most intense neutral product. Phenyl radical (mass 76) production was also observed. The leading edge of the N₂ TOF signal shows a shoulder corresponding to kinetic energies of about 1.1 eV, followed by a long tail that lasts hundreds of microseconds. The tail is attributed to delayed emission of reaction products from the polymer. The kinetic energy of the fast peak is attributed to direct ejection of products from surface sites undergoing exothermic decomposition. The fluence dependence of the N₂ signal is highly nonlinear and is shown to fit an Arrhenius equation.     

Femtosecond laser-induced fragmentation and cluster formation studies of solid phase trinitrotoluene using time-of-flight mass spectrometry

We use surface-femtosecond laser mass spectrometry to study the fragments/products formed when trinitrotoluene (TNT) is subjected to femtosecond laser pulse irradiation and to study the conditions under which TNT is removed from a solid surface. In surface-femtosecond laser mass spectrometry a compound is deposited on a solid substrate and is desorbed into vacuum by femtosecond irradiation forming a plume of ionized and neutral species. The positive or negative ions are then accelerated by an electric potential and allowed to drift in the field-free region of a time-of-flight mass spectrometer. The mass-to-charge ratio of each ion is obtained using the value of the accelerating field and the ion flight time. In this paper we report femtosecond laser mass spectra for the positive ions formed by desorbing TNT with 130 fs pulses centered at 800 nm for fluences ranging from 7 to 1.4 × 10⁵ J/m². The conditions under which TNT removal and ionization occur are also discussed.     

Dynamics of single-wall carbon nanotube synthesis by laser vaporization

The key spatial and temporal scales for single-wall carbon nanotube (SWNT) synthesis by laser vaporization at high temperatures are investigated with laser-induced luminescence imaging and spectroscopy. Graphite/(Ni, Co) targets are ablated under typical synthesis conditions with a Nd:YAG laser at 1000 °C in a 2-in. quartz tube reactor in flowing 500-Torr Ar. The plume of ejected material is followed for several seconds after ablation using combined imaging and spectroscopy of Co atoms, C₂ and C₃ molecules, and clusters. The ablation plume expands in stages during the first 200 7s after ablation and displays a self-focusing behavior. Interaction of the plume with the background gas forms a vortex ring which segregates and confines the vaporized material within a ~1-cm³ volume for several seconds. Using time-resolved spectroscopy and spectroscopic imaging, the time for conversion of atomic and molecular species to clusters was measured for both carbon (200 7s) and cobalt (2 ms) at 1000 °C. This rapid conversion of carbon to nanoparticles, combined with transmission electron microscopy analysis of the collected deposits, indicate that nanotube growth occurs over several seconds in a plume of mixed nanoparticles. By adjusting the time spent by the plume within the high-temperature zone using these in situ diagnostics, single-walled nanotubes of controlled (~100 nm) length were grown and the first estimate of a growth rate on single laser shots (0.2 7m/s) was obtained.     

超短脉冲激光烧蚀石墨产生的喷射物的时间分辨发射光谱研究

本文使用不同激光能流(18 J/cm²–115 J/cm²)和脉冲宽度(50 fs–4 ps)的超短脉冲激光在真空中(4×10^-4 Pa)烧蚀高定向热解石墨. 通过测量烧蚀喷射物的时间分辨发射光谱研究喷射物的超快时间演化. 在喷射物发射光谱中, 观察到了C₂基团的天鹅带光谱系统, 416 nm附近C₁₅基团的由电子能级¹Σ_u⁺ 和¹Σ_g⁺之间的振动跃迁产生的光谱峰以及连续谱. 50 fs, 115 J/cm²的脉冲激光烧蚀产生的喷射物的连续谱的强度衰减分为快速下降和慢速下降两个阶段(以20 ns时间延迟为分界). 这表明连续谱是由两种不同的组分贡献的. 快速下降阶段, 连续谱主要由碳等离子体通过韧致辐射产生; 慢速下降阶段, 连续谱主要由烧蚀后期产生的大颗粒碳簇的热辐射贡献. 实验结果还揭示了激光能流的提高, 会明显增加喷射物中碳等离子体和激发态C₂的含量, 但对质量稍大的C₁₅的影响较小; 此外, 50 fs脉冲激光烧蚀产生的连续谱的存在时间会随着激光能流的减小而增大, 这说明低能流更有利于在烧蚀后期产生碳簇. 脉宽主要影响喷射物连续谱的时间演化. 4 ps脉冲激光烧蚀产生的连续谱的整个时间演化过程明显慢于50 fs脉冲产生的连续谱.     

Carrier-Envelope-Phase Dependence of Emission Properties of High-Order Harmonic Generation

The carrler-envelope-phase （CEP） dependence of the emission properties of high-order harmonic generation （HHG） are quantitatively investigated. Calculation shows that a two-cycle laser with CEP of 15° can produce a single energy distribution pulse peaked at 0.94 radian （tad） and spanned 1.29 tad with the cutoff energy 2.9Up ＋ Ip and a bandwidth 0.86Up （where Up is the ponderomotive potential of the laser field and Ip is the atomic ionization potential）. The CEP dependence of the energy and temporal localizations of the single distribution pulse show interesting 180° periodic structures. These characteristics may be useful in optimizing attosecond x-ray sources and measurements.     

Optical Limiting Properties of Two Soluble Polymer/Multi-Walled Carbon Nanotube Composites

Two soluble polymer grafted multi-walled carbon nanotubes （MWNTs）, including poly（N-vinylcarbazole）-MWNTs and poly（methyl methacrylate）-MWNTs, are synthesized. Their nonlinear optical properties and opticaJ limiting （OL） performances are investigated by z-scan method with 527nm nanosecond laser pulses. These grafted MWNTs dissolved in chloroform show much better optical limiting performance than those of MWNTs and C60 in toluene solution. Nonlinear absorption and nonlinear scattering mechanism are taken into consideration for explaining the observed results. The comparison of the experimental results shows that nonlinear absorption is the dominant mechanism for OL performance of these new samples.     

Configurations, Electronic Structure and Magnetic Ordering of Small Manganese Clusters

We investigate the configurations, electronic structures, and magnetic ordering of MnN （N = 2-13） clusters based on all-electron density functional theory. The Jahn-Teller effect plays an important role in determining the ground state of certain geometries. The magnetic ordering of the MnN dusters transits from ferromagnetic ordering for the smallest （ N = 2, 3） dusters to a near degeneracy state including ferromagnetic and ferrimagnetic ordering in the vicinity of N = 4-6 and to a clear ferrimagnetic ordering at N = 7 or beyond. N = 6 and 10 are the magic numbers for neutrai MnN （N = 2-13） dusters.     

Sixth Harmonic of A Nd：YVO4 Laser Generation In KBBF for ARPES

We report that a deep ultraviolet （DUV） laser from the sixth harmonic of a 1064nm laser has been firstly used as light source in an ultrahigh energy-resolution angle-resolved photoemission spectroscopy （ARPES）. The wavelength is 177.3nm obtained by using the second harmonic KBe2BO3F2 crystal with a frequency tripled 1064nm Nd：YVO4 laser. The large flux （10^14 - 10^15 photons/s） and narrow line width （0.26 meV） are suitable for the ultrahigh-energy resolution ARPES. The laser-ARPES can be a powerful tool to study the electronic structure at and near the Fermi level of the superconductor and correlated materials. The laser-ARPES has worked more than 500 h already.     

氨/乙醇混合团簇多光子电离质谱

用多光子电离技术结合飞行时间质谱仪对氨与乙醇混合团簇进行了研究。在脉冲激光波长分别为266,355nm和532nm条件下,仅在355nm作用下观测到团簇离子。主要的电离产物为质子化的（C2H5OH）n（NH3）mH＋（n=0—3,m=0—4）混合团簇离子,且各个序列的离子强度随m的增大而减小。经分析,氨与乙醇混合团簇电离后团簇离子发生内部质子化转移反应是形成质子化团簇离子的主要原因。不同尺寸团簇离子信号强度随电离激光光强变化的光强指数曲线显示,团簇均发生四光子电离过程。通过理论计算得到其中性和离子团簇的稳定结构,解离能,解离通道。并证实团簇发生电离解离时发生了团簇内质子转移反应。