Laser plasma plume kinetic spectroscopy of the nitrogen and carbon species

The formation and decay of carbon and nitrogen atoms, CN radicals and C₂ molecules were monitored using spatial‐ and time‐resolved emission spectroscopy in a plasma plume formed during laser ablation of a graphite target in nitrogen atmosphere. A simple exponential model was used to explain the effect of the individual chemical reactions and plasma dynamics on the measured kinetic characteristics. The succession of emissions C → N → CN was observed in the time‐resolved spectra, supporting the suggestion that the CN radical is formed mainly by the direct reaction C + N → CN or C₂ + N₂ → 2CN. The formation of CN radical was enhanced by the additional generation of atomic nitrogen through the RF discharge. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Study of the plume generated by Nd:YAG laser ablation of a hydroxyapatite target

The plume generated by Nd:YAG laser ablation of a hydroxyapatite target has been investigated in vacuum and at 0.1 and 0.2 mbar of water vapor. The investigation has been carried out by means of fast intensified CCD imaging with the aid of bandpass interferential filters that allow the following single species to be isolated: neutral calcium, calcium oxide radicals and neutral oxygen. Results obtained in vacuum reveal that expansion takes place at a constant velocity of about 2᎒⁴ m/s for the atomic species and about 3᎒³ m/s for the molecular ones and that emission is completely dominated by emissive neutral calcium. When ablation is carried out in a water atmosphere, the background gas confines the species in the leading edge of the plume, which results in the formation of a planar shock wave at 0.1 mbar and a spherical shock wave at 0.2 mbar. Comparison of the images with those obtained at 0.1 mbar of Ne has revealed the existence of chemical reactions between the plume and the water atmosphere, leading to the formation of calcium oxide radicals. In that case, plume emission is dominated by these molecular species.     

Spectroscopic measurements of excited particles in a N2 gas RF plasma-assisted carbon laser ablation

In this work, we investigated a carbon plasma plume produced by laser ablation of a graphite target in a nitrogen gas environment. The spatial distributions of C and N atoms were measured by time-resolved absorption spectroscopy. The spatial distributions of the relative densities of CN radicals, C₂, and C₃ molecules were measured using time-resolved emission spectroscopy. We determined that nitrogen gas produced an increase in carbon atom and molecule densities in the ablation plume. It was observed that the addition of RF plasma to the plume increased the CN radicals and C atom densities, and decreased the C₂ and C₃ molecule densities. The RF plasma changed the evolution of various fractional species of C, N, CN, C₂, and C₃ in the ablation plume. The chemical reactions with and without RF plasma were explained using the evolution and density of the fractional species of C, N, CN, C₂, and C₃in the plume. PACS 52.38.Mf; 42.62.Fi; 33.20.-t; 81.05.Uw     

Double-pulse laser ablation applied to reactive PLD method for synthesis of carbon nitride film: A second laser shot delay

Carbon nitride films were deposited using ablation of graphite target by second harmonic radiation of Nd:YAG laser in nitrogen atmosphere. To produce high hardness films, the deposited particles should have sufficient kinetic energy to provide their efficient diffusion on a substrate surface for formation of crystal structure. However, a shock wave is arisen in ambient gas as a consequence of laser plasma explosive formation. This shock wave reflected from the substrate interacts with plume particles produced by the first laser pulse and decreases their kinetic energy. This results in decrease of film crystallinity. To improve film quality, two successive laser pulses was proposed to be used. At adjusting time delay, the particles induced by the second pulse wilt serve as a piston, which will push forward both stopped particles ablated by the first pulse and arisen from chemical reactions in ambient gas. An X-ray photoelectron spectroscopy (XPS) analysis of deposited films has shown an increase of content of sp ³ carbon atoms corresponding to crystalline phase, if double-pulse configuration is employed. The luminescence of excited C₂ and CN molecules in laser plume at different distances from the target was studied to optimize the delay between laser pulses.     

Radiation Characteristics of Air in the Ultraviolet and Vacuum Ultraviolet Regions of the Spectrum behind the Front of Strong Shock Waves

Experiments on the measurement of air emission intensity behind the front of incident shock wave were carried out in a shock tube at an initial pressure of 0.25 Torr and shock wave velocities of 6.3–8.4 km/s. The emission intensity was measured in absolute units both in the form of an integral spectral distribution in a wavelength range of 120?400 nm (panoramic spectra) and as the time evolution of emission at the individual atomic lines of nitrogen and oxygen atoms. The results of the measurements demonstrated that the emission in air behind a shock wave in the vacuum ultraviolet region of 120–200 nm had a much higher radiation flux level than the emission in a range of 200–900 nm.     

Carbon nitride films by RF plasma assisted PLD: Spectroscopic and electronic analysis

Carbon nitride (CNx) thin films have been grown on Si 〈1 0 0〉 by 193 nm ArF ns pulsed laser ablation of a pure graphite target in a low pressure atmosphere of a RF generated N₂ plasma and compared with samples grown by PLD in pure nitrogen atmosphere. Composition, structure and bonding of the deposited materials have been evaluated by X-ray photoelectron spectroscopy (XPS), and Raman scattering. Significant chemical and micro-structural changes have been registered, associated to different nitrogen incorporation in the two types of films analyzed. The intensity of the reactive activated species is, indeed, increased by the presence of the bias confined RF plasma, as compared to the bare nitrogen atmosphere, thus resulting in a different nitrogen uptake in the growing films. The process has been also investigated by some preliminary optical emission studies of the carbon plume expanding in the nitrogen atmosphere. Optical emission spectroscopy reveals the presence of many excited species like C⁺ ions, C atoms, C₂, N₂; and CN radicals, and N₂⁺ molecular ions, whose relative intensity appears to be increased in the presence of the RF plasma. The films were also characterised for electrical properties by the “four-probe-test method” determining sheet resistivity and correlating surface conductivity with chemical composition.     

Characterization of ablation plumes and carbon nitride films produced by reactive pulsed laser deposition in the presence of a magnetic field

x ) films in a nitrogen atmosphere within the range 5×10^-4–4×10^-1 Torr. In the presence of a magnetic field, the emission intensities of N₂ (second positive system) and CN species in the graphite ablation plumes were altered significantly, depending on the pressure of the N₂ environment. Corresponding to an intense CN emission, a magnetic field-induced enhancement of N incorporation – for example, up to 37% at an N₂ pressure of 300 mTorr – and the formation of sp³ tetrahedral CN bonding were both observed in the films. This suggests that the arrival of CN species at the substrate surface with kinetic energies is important for film deposition. Received: 27 August 1997/Accepted: 8 September 1997     

Shadowgraphic and emission imaging spectroscopic studies of the laser ablation of graphite in an Ar gas atmosphere

Laser ablation of graphite in an Ar atmosphere at 560 Torr was done using a nanosecond-pulse Nd:YAG laser (1064 nm) at a fluence of 12 J/cm². Dynamics in the ejection of carbon species and in their confinement near the graphite surface (<1 mm) due to their numerous collisions with Ar atoms were investigated by shadowgraphy, emission imaging, and emission spectroscopy at delay times of 0.01-100 7s following the laser irradiation. A shock wave was generated, and temporally and spatially dependent emissions from Ar⁺ and Ar were observed in addition to those from carbon species (C, C⁺, and C₂) and the Bremsstrahlung radiation from a hot plasma. We suggest that the dissipation of the kinetic and thermal energies of the carbon species, their backward motion, and their collisions with each other lead to the formation of clusters and particles through the interaction with Ar atoms.     

Emission properties of laser ablation of SnO2: Sb transparent conducting film and KTiOPO4 crystal

Optical emission spectra of Nd:YAG laser ablation of KTiOPO₄ (KTP) crystal and SnO₂:Sb transparent conducting thin film were recorded and analyzed in vacuum and in air. The integral intensities of spectral lines from laser-ablated KTP crystal were obtained as functions of distance from the target surface and laser power density in vacuum and in air. The ambient gas effects on pulsed laser ablation of target were discussed. We also performed laser ablation of SnO₂:Sb transparent conducting thin film in air and the electron temperature and full-width at half-maximum (FWHM) of atomic and ionic spectral lines in the plasma were quantified using Boltzmann plot method and Lorentzian fit, respectively. Integral intensities of atomic and ionic Sn spectral lines were also obtained as functions of distance from the target surface and laser irradiance. The intensity ratio of ionic and atomic Sn spectral lines as a function of laser power density was got which gives some information about the variation of ionization ratio with laser irradiance in the plasma produced by high-power laser.     

Plasma characterization and room temperature growth of carbon nanotubes and nano-onions by excimer laser ablation

The deposition of carbon nanotubes and carbon nano-onions at room temperature using excimer laser radiation to ablate mixed graphite-metal targets is described. Our deposition conditions are in contrast to other investigations on the pulsed laser deposition of carbon nanotubes that have employed high temperatures and high pressures. We find that the formation of these carbon nanostructures is dependent on the ambient gas employed during ablation. In the presence of O₂ gas, carbon nanotubes and nano-onions are produced, while inert atmospheres such as Ar yield amorphous carbon. High-resolution, in situ, time-resolved emission spectroscopy has been used to track the evolution of species (C₂, C₃, Ni/Co) in the ablation plume. Spectral fits on low and high-resolution spectra reveal that the vibrational-rotational temperatures for C₂ produced in O₂ remain at ∼5000 K for nearly 20 μs but drop rapidly in Ar. Details of the formation of carbon nanotubes and nano-onions, and in situ time-resolved optical emission spectroscopy are described.     

Effect of ambient nitrogen pressure on the formation and spatio-temporal behaviour of C<Subscript>2</Subscript> and CN

We report the effect of ambient gas on the formation as well as propagation behaviour of ablated species C₂ and CN within the carbon plasma created by focussing a high-power Nd:YAG (λ = 1064 nm) laser onto the rotating graphite target in the nitrogen ambient. The formation of C₂ takes place earlier as well as nearer the target compared to that of CN which forms later and far from the target, in 1.2 mbar pressure of N₂ gas. Peak arrival time vs. nitrogen gas pressure plot shows a shock wave-like dependence t ∝ p ⁿ in the pressure range 1.2–120 mbar (collisional regime) which indicates plume confinement with increases in ambient pressure. At higher pressure, thermalization takes place.     

Gas pressure effects on the structure of CNx thin films deposited by laser ablation

Carbon nitride thin films with different nitrogen concentration have been deposited at different N₂ and N₂/Ar mixed partial pressures. Time-integrated optical emission spectroscopy measurements have been performed to gather information on the nature of the chemical species present in the plasma. Both the CN and C₂ molecular species have been observed. Fast photography imaging of the expanding plume revealed the change of the dynamics from a free expansion at low pressure to a shock wave formation followed then by the plume stopping upon increasing the gas pressure values. Raman and XPS spectroscopy measurements performed on the deposited thin films revealed that the films, structure strongly depends on the dynamics of the expansion plasma regime rather than on the partial pressure at which the deposition takes place.     

Spatial and temporal study of shock waves generated by laser ablation for Ti target

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Growth mechanisms for single-wall carbon nanotubes in a laser-ablation process

Mechanisms proposed in the literature are compared with a current scenario for the formation of single-wall carbon nanotubes in the laser-ablation process that is based on our spectral emission and laser-induced fluorescence measurements. It is suggested that the carbon which serves as feedstock for nanotube formation not only comes from the direct ablation of the target, but also from carbon particles suspended in the reaction zone. Fullerenes formed in the reaction zone may be photo-dissociated into C₂ and other low molecular weight species, and also may serve as feedstock for nanotube growth. Confinement of the nanotubes in the reaction zone within the laser beam allows the nanotubes to be ‘purified’ and annealed during the formation process by laser heating. Received: 2 November 2000 / Accepted: 3 November 2000 / Published online: 23 March 2001     

Low temperature plasma assisted atomic layer deposition in nitrogen carrier gas studied by optical emission spectroscopy

A low temperature plasma assisted atomic layer deposition process from tetrakis (dimethylamino)-titanium (TDMAT) and oxygen plasma was investigated using optical emission spectroscopy in a commercial TFS-500 atomic layer deposition reactor in industrial-like conditions with different plasma powers to optimize the plasma-assisted deposition process and to develop a tool for process control. The major emitting species recognized were the nitrogen first followed by the second positive system, carbon monoxide, nitrogen monoxide (γ)-system, atomic carbon and atomic nitrogen. The process measurements were compared to background measurements to see the process induced differences. CH _x appearance in the plasma lowered the intensities of CO, NO and N₂ 1st⁺ system peaks. Also, the nitrogen atom content varied in the process measurements. By monitoring the affected species and vibrational temperature, the effect of TDMAT oxidation on the surface could be seen through the resulting changes in the plasma emission.     

紫外激光烧蚀Cu产生等离子体辐射特性

通过时间分辨的光谱测量技术,测定了308 nm XeCl紫外激光烧蚀金属Cu在氮气环境中诱导产生等离子体的发射光谱及其强度随时间分布,实验结果表明等离子体辐射光谱线主要由原子光谱线、一价离子光谱线及连续辐射背景光组成,各种光谱线的数目、辐射强度、持续时间不同。结合实验结果对等离子辐射机理进行了探讨,认为电子通过逆韧致辐射获得较高的能量,连续辐射主要来自高能电子的韧致辐射,原子和一价离子的激发主要是通过电子与原子、离子的碰撞传能以及电子与离子的复合产生,并用其定性地解释了所观察的实验现象。     

脉冲激光制备类金刚石薄膜及原位激光等离子体发射光谱

用ＹＡＧ脉冲激光轰击真空室内的石墨靶,可以形成包含碳素的激光等离子体,并在硅或石英衬氏上淀积形成某种类型的碳膜。用光学多道分析仪原位测量了激光等离子体的发射光谱,给出反应空间可能存在的反应基团有碳原子、碳离子、碳分子等,用拉曼光谱研究了薄膜的结构,证明所形成的薄膜为类金刚石膜,并得出碳原子和碳离子与薄膜的类金刚石结构有关。制备过程中,氢的参与有利于薄膜中金刚石成分的形成。空间分辨的原位激光等离子体发射光谱表明,在反应空间存在薄膜形成的最佳位置。     

Early stage of the material removal during ArF laser ablation of graphite

Material removal during ArF excimer laser ablation of graphite at atmospheric pressure was investigated by two independent methods; 1) by observation of the propagating properties of the shock wave generated by the carbonaceous ejecta and 2) by in situ measurement of the size distribution of carbon nanoparticles condensing in the ablation plume. This latter was carried out by a scanning mobility particle sizer system based on a differential mobility analyser. The performed measurements indicate that the material removal during ArF laser ablation consists of two steps at fluences above the threshold fluence. First, a thin layer of carbon (of the order of 1 nm) is removed by a quick desorption process, leading to shockwave formation. This process takes place in a ns time scale, and desorption rate estimations reveal that this can not be explained by thermal surface evaporation. Since to our knowledge there is no thermal process that could account for the estimated desorption rate, it is argued that this is a fast photochemical (i.e. non-thermal) process. The size distribution of the condensed nanoparticles related to this step shows a rising edge at diameters below 10 nm. At fluences above the ablation threshold, the majority of the material is ejected in the second phase, resulting in condensation of carbon nanoparticles, peaking at 50 nm diameters in the size spectrum. Both shockwave formation and material removal are also detected well below the ablation threshold fluence, which is attributed to the photochemical process. PACS 61.46.+w; 81.16.Mk     

Application of time-resolved digital holographic microscopy in studies of early femtosecond laser ablation

We studied evolution of femtosecond laser ablation by employing novel method of time-resolved off-axis digital holographic microscopy. Phase and amplitude profiles of early shock front and ablation plume dynamics of irradiated tempered steel were reconstructed from the digital holograms. In order to gain additional information, digital holographic microscopy was combined with plasma emission imaging. By using both techniques simultaneously we studied material response to multi-pulse irradiation, shock wave propagation, ablation plume formation and plasma emission. The significant changes in ablation performance were observed when using multi-pulse irradiation if compared to widely investigated single-shot regime.     

Hardnes and resistivity of amorphous carbon thin films deposited by laser ablation

Amorphous carbon thin films were deposited by laser ablation of a graphite target, using the fundamental line of a 5 ns Nd:YAG laser. Deposition was carried out as a function of the plasma parameters (mean kinetic ion energy and plasma density), determined by means of a planar probe. In the selected working regimes the optical emission from the plasma is mainly due to atomic species, namely C⁺ (426.5 nm); however, there is also emission from other atomic species and molecular carbon. The hardness and resistivity could be varied in the range between 10 and 25 GPa, and 10⁸ and 10¹¹ Ω cm, respectively. The maximum values were obtained at a 200 eV ion energy and 6×10¹³ cm⁻³ plasma density, where the maximum quantity of C–C sp³ bonds was formed, as confirmed by Raman spectroscopy.