Pulsed laser deposition of metals in various inert gas atmospheres

The changes in the properties of laser deposited metal thin films were investigated in different inert gas atmospheres (He, Ne, Ar and Xe). With increasing inert gas pressure, the reduction of particle energy is accompanied by a strong increase of the deposition rate (especially in He atmosphere), a transition from compressive to tensile stress, and changes in structure and texture. This is explained by a reduction of surface mobility of the deposited particles, a decrease of implantation, resputtering and shot-peening effects. At high gas pressures, deposition conditions similar to sputtering or even thermal deposition are obtained. PACS 68.55.-a; 81.15.Fg     

Inhomogeneity of calcium phosphate coatings deposited by laser ablation at high deposition rate

Calcium phosphate coatings were deposited with a KrF excimer laser onto titanium alloy to study their homogeneity. Deposition was performed at a high deposition rate under a water vapour atmosphere of 45 Pa and at a substrate temperature of 575 °C. Samples were also submitted to annealing under the same conditions of deposition for different times just after deposition. The effects of the annealing were also investigated. The morphology of the coatings was studied by scanning electron microscopy. Their structure and phase distribution was analysed by X-ray diffractometry and infrared and micro-Raman spectroscopies. Besides the non-uniform thickness, the results reveal an inhomogeneity in the spatial distribution of calcium phosphate phases in the coatings. The phase distribution can be almost completely correlated with the deposition rate. High deposition rates (0.5 nm/pulse) occurring in the centre of deposition results in the formation of amorphous calcium phosphate, while lower deposition rates favour the presence of hydroxyapatite and alpha tricalcium phosphate. At intermediate deposition rates, beta tricalcium phosphate is found, probably because the superimposed effect of energetic particles bombardment. The annealing process promotes the crystallisation of the amorphous material. The importance of the deposition rate in the phases obtained is stated after comparing these results with a previous work where homogeneous hydroxyapatite coatings were obtained under the same conditions of laser fluence, temperature and pressure, but at lower deposition rates. Received: 22 November 2001 / Accepted: 12 March 2002 / Published online: 5 July 2002 RID="*" ID="*"Corresponding author. Fax: +34-93/402-1138, E-mail: jmfernandez@fao.ub.es     

Femtosecond pulsed-laser deposition of BaTiO<Subscript>3</Subscript>

The elemental composition and the surface morphology of thin films grown by laser ablation of barium titanate with femtosecond pulses at 620 nm laser wavelength have been systematically studied according to the experimental pulsed-laser deposition parameters : laser energy density, oxygen pressure, substrate temperature, target–substrate distance and substrate position (in- and off-axis geometry). Firstly, even at high temperature (700 °C), the deposits consist of coalesced particles up to 1-μm in size, mixed in a poorly crystallised tetragonal BaTiO₃ thin film. The particles formed in femtosecond pulsed-laser deposition induce a high surface roughness, which is observed whatever the experimental growth conditions and does not correspond to the droplets often observed during laser ablation in the nanosecond regime. As shown by plasma expansion dynamics, these particles propagate toward the substrate in the plasma plume with a low velocity, and are assumed to be produced by gas-phase reactions. Moreover, the cationic concentration evaluated through the Ba/Ti ratio strongly depends on the oxygen pressure in the ablation chamber and the angular position of the substrate along the normal to the target at laser impact. Indeed, the films appear to be enriched in the heavy element (Ba) when the substrate is located at high angular deviation. This fact is correlated to an increase in the lighter species (i.e. Ti) in the central part of the plasma plume. Received: 30 April 2002 / Accepted: 26 August 2002 / Published online: 8 January 2003 RID="*" ID="*"Corresponding author. Fax: +33-1/4354-2878, E-mail: millon@gps.jussieu.fr RID="**" ID="**"Also at: LSMCL, Université de Metz, 57078 Metz Cedex 3, France     

Effect of temperature on growth and structure of carbon nanotubes by chemical vapor deposition

The effect of temperature on growth and structure of carbon nanotubes (NTs) using chemical vapor deposition (CVD) has been investigated. Iron embedded silica was used to grow NTs in large quantity at various temperatures from 600 to 1050 °C with gas pressure fixed at 0.6 and 760 Torr, respectively. The growth and structure of the NTs are strongly affected by the temperature. At low gas pressure, the NTs are completely hollow at low temperature and bamboo-like structure at high temperature. While at high gas pressure, all the NTs are bamboo-like structure regardless of temperature. The diameter of NTs increases significantly with temperature. At low gas pressure the diameter gets bigger by mainly increasing the number of graphene layers of the wall of NTs, whereas at high gas pressure the diameter gets bigger by increasing both the number of graphene layers of the wall and the inner diameter of the NTs. This result indicates that the growth temperature is crucial in synthesizing NTs with different structures. The findings here are important for realizing controlled growth of NTs for their applications in different fields. Received: 20 November 2001 / Accepted: 21 November 2001 / Published online: 4 March 2002     

Studies of the collision frequency of ideal gas particles with the surfaces of the objects created using the ballistic deposition technique

This paper is a continuation of our studies of the collision frequency of ideal gas particles with the rough/fractal surfaces. Here, we applied a more realistic surface growth model, i.e. ballistic deposition for creation of fractal objects. We found that the collision frequency with irregular surfaces is the linear function of pressure and this frequency per unit pressure is quite a complicated function of the surface fractal dimension as well as the diameter of colliding particle. The collision frequency with rough surfaces cannot be exactly described by the analytical formula called the Langmuir-Hertz equation. However, we have stated that the deviations of the true collision frequency from the Langmuir-Hertz prediction are not huge and in typical catalytic studies the error introduced by replacing the true frequency by the Langmuir-Hertz prediction can be safely neglected. We have also studied the probability of finding on the surface an atom which has been hit a certain number of times by a gas particle. This probability reveals an interesting behaviour for small gas particles, i.e. it perfectly correlates with the number of directions from which the surface atom is accessible from the gas phase. We have also estimated the evolution of the adsorption energy distribution with the increasing fractal dimension of the surface in the ballistic deposition.     

The high deposition of microcrystalline silicon thin film by very high frequency plasma enhanced chemical vapour deposition and the fabrication of solar cells

This paper reports that the intrinsic microcrystalline silicon ($\mu $c-Si:H) films are prepared with plasma enhanced chemical vapour deposition from silane/hydrogen mixtures at 200\du\ with the aim to increase the deposition rate. An increase of the deposition rate to 0.88\,nm/s is obtained by using a plasma excitation frequency of 75\,MHz. This increase is obtained by the combination of a higher deposition pressure, an increased silane concentration, and higher discharge powers. In addition, the transient behaviour, which can decrease the film crystallinity, could be prevented by filling the background gas with Hchemical vapour deposition, plasma deposition, solar cells, crystallinityProgram supported by the State Key Development Program for Basic Research of China (Grant No 2006CB202601), and Basic Research Project of Henan Province in China (Grant No 072300410140).7280N, 7830G, 8115HThis paper reports that the intrinsic microcrystalline silicon ($\mu $c-Si:H) films are prepared with plasma enhanced chemical vapour deposition from silane/hydrogen mixtures at 200\du\ with the aim to increase the deposition rate. An increase of the deposition rate to 0.88\,nm/s is obtained by using a plasma excitation frequency of 75\,MHz. This increase is obtained by the combination of a higher deposition pressure, an increased silane concentration, and higher discharge powers. In addition, the transient behaviour, which can decrease the film crystallinity, could be prevented by filling the background gas with Hchemical vapour deposition, plasma deposition, solar cells, crystallinityProgram supported by the State Key Development Program for Basic Research of China (Grant No 2006CB202601), and Basic Research Project of Henan Province in China (Grant No 072300410140).7280N, 7830G, 8115HThis paper reports that the intrinsic microcrystalline silicon ($\mu $c-Si:H) films are prepared with plasma enhanced chemical vapour deposition from silane/hydrogen mixtures at 200\du\ with the aim to increase the deposition rate. An increase of the deposition rate to 0.88\,nm/s is obtained by using a plasma excitation frequency of 75\,MHz. This increase is obtained by the combination of a higher deposition pressure, an increased silane concentration, and higher discharge powers. In addition, the transient behaviour, which can decrease the film crystallinity, could be prevented by filling the background gas with Hchemical vapour deposition, plasma deposition, solar cells, crystallinityProgram supported by the State Key Development Program for Basic Research of China (Grant No 2006CB202601), and Basic Research Project of Henan Province in China (Grant No 072300410140).7280N, 7830G, 8115HThis paper reports that the intrinsic microcrystalline silicon ($\mu $c-Si:H) films are prepared with plasma enhanced chemical vapour deposition from silane/hydrogen mixtures at 200\du\ with the aim to increase the deposition rate. An increase of the deposition rate to 0.88\,nm/s is obtained by using a plasma excitation frequency of 75\,MHz. This increase is obtained by the combination of a higher deposition pressure, an increased silane concentration, and higher discharge powers. In addition, the transient behaviour, which can decrease the film crystallinity, could be prevented by filling the background gas with Hchemical vapour deposition, plasma deposition, solar cells, crystallinityProgram supported by the State Key Development Program for Basic Research of China (Grant No 2006CB202601), and Basic Research Project of Henan Province in China (Grant No 072300410140).7280N, 7830G, 8115HThis paper reports that the intrinsic microcrystalline silicon ($\mu $c-Si:H) films are prepared with plasma enhanced chemical vapour deposition from silane/hydrogen mixtures at 200\du\ with the aim to increase the deposition rate. An increase of the deposition rate to 0.88\,nm/s is obtained by using a plasma excitation frequency of 75\,MHz. This increase is obtained by the combination of a higher deposition pressure, an increased silane concentration, and higher discharge powers. In addition, the transient behaviour, which can decrease the film crystallinity, could be prevented by filling the background gas with H$_{2}$ prior to plasma ignition, and selecting proper discharging time after silane flow injection. Material prepared under these conditions at a deposition rate of 0.78\,nm/s maintains higher crystallinity and fine electronic properties. By H-plasma treatment before i-layer deposition, single junction $\mu $c-Si:H solar cells with 5.5{\%} efficiency are fabricated.     

Pressure limits for the vacuum arc deposition technique

Observations of the cathodic copper plasma expansion at low pressures of He, Ar, and SF₆ showed that, for background gas mass densities of ρ_g=1 to 4×10^-4 kg/m ³ and higher, the plasma and gas are separated into two volumes. A shock wave acts as a boundary between the two volumes. The boundary attains a stationary position once its expansion velocity decreases to the velocity of sound in the background gas. This position corresponds to a distance R_c to the cathode that agrees with a snowplow expansion model, giving R_c ^βf=E_r, where f is a function of the arc current and background gas characteristics, E _r is the erosion rate of the cathode, and β varies between 2.1 and 2.5. The interaction model is based on kinetic energy exchanges between two gas-like volumes without other energy losses. A maximum pressure limit for vacuum arc deposition is set for ρ_g /I=2 to 9×10^-6 kg/m³ A     

Influence of deposition parameters on hard Cr-Al-N coatings deposited by multi-arc ion plating

The Cr-Al-N coatings were synthesized at various substrate bias voltages and nitrogen partial pressures by multi-arc ion plating (M-AIP). The relationships between deposition parameters and coating properties were investigated. Morphologies, phase structures, hardness and adhesion strength of the coatings were analyzed by SEM, XRD, XPS, nano-indenter and scratch tester. The results indicated that with the increase of substrate bias voltages, the surface macroparticles and deposition rate reduced mainly for the resputtering phenomenon. The (Cr, Al)N solid-solution phase kept unchanged, but the Cr₂N and AlN phases disappeared gradually. Due to the change of phase structures and residual compressive stress, the hardness values decreased and the adhesion strength decreased initially and then increased. Similarly, with the increase of nitrogen partial pressures, the phase structures of CrAlN coatings varied from Cr + Cr₂N + (Cr,Al)N to Cr₂N + (Cr,Al)N. The surface macroparticles increased due to the decreasing resputtering efficiency, and the deposition rate increased initially and then decreased due to the resputtering phenomenon. With increasing nitrogen partial pressures, adhesion strength decreased initially and then increased. The microhardness increased mainly due to the increase of Cr₂N contents and decrease of metal macroparticles.     

Oriented growth of CoPt nanoparticles by pulsed laser deposition

The magnetic nanoparticles of Fe/FeCo/FePt, in the past, in a PLD system were grown by us using argon ambient gas pressure of about 0.1–75.0 mbar, as the ambient gas pressure can be used to tune the energy of the incident plasma plume species, the expansion volume, the growth duration, etc. which can control the particle size. In present paper, we report the direct synthesis of small-sized nanoparticles even when no ambient gas was used, with the experiments being done in higher vacuum of about 10^?5 mbar in PLD chamber. The deposition rate under vacuum condition is significantly higher than the deposition rate at high ambient pressure. The study of inplane and outplane magnetic properties, along with XRD results, confirmed that the as-deposited CoPt nanoparticles thin film has oriented growth. The as-deposited CoPt nanoparticles are in magnetically soft fcc phase and a post deposition annealing at 600°C resulted in phase transition to magnetically hard fct phase.     

脉冲激光气相沉积法制备钴纳米薄膜实验研究

 采用脉冲激光沉积技术制备了钴纳米薄膜，分析和讨论了不同背景气压和脉冲频率对钴纳米薄膜表面形貌的影响及纳米微粒的形成机理。实验结果表明：在低背景气压下，等离子体羽辉自身粒子之间的碰撞占主导作用，容易形成液滴；在较高背景气压下，等离子体羽辉边缘粒子和背景气体粒子之间的碰撞占主导作用，容易形成小岛并凝聚成微颗粒；在4Hz的脉冲重复频率和5Pa背景气压下生长出单分散性良好的钴纳米颗粒。     

Effect of gas pressure on the growth and structure of carbon nanotubes by chemical vapor deposition

The effect of gas pressure on the structure of carbon nanotubes (CNTs) has been systematically investigated in the chemical vapor deposition process. The yield of CNTs (defined as the weight ratio of CNTs vs. catalyst) increases significantly with the gas pressure, reaches 600% at 600 Torr, then decreases with further increase of gas pressure. At low reacting gas pressure the CNTs have completely hollow cores, whereas at high pressure the CNTs have a bamboo structure. The density of the compartments in the bamboo-structured CNTs increases dramatically with the increase of the gas pressure. This result shows that the structure and yield of carbon nanotubes are strongly affected by the growth gas pressure. Received: 10 May 2001 / Accepted: 10 May 2001 / Published online: 20 June 2001     

Suppression of Ag deposition by Ar gas in mtorr range and its implication to mitigation of impurity deposition on first mirrors

We observe that Ar gas confined in a tube maintained at a pressure higher than 10 mtorr by a baffled duct is very effective in minimizing the deposition of incoming Ag particles onto the surface of quartz crystal microbalance (QCM) in the tube. Ar gas is introduced into the tube and the gas flow to the main chamber is minimized by a baffled duct. In this way, the tube pressure of 10 mTorr or higher is achieved. The pressure is found to be enough to suppress the deposition of nearly 97% Ag particles onto the QCM in the tube. The suppression of the Ag deposition is successfully explained by reduced mean-free path at the high pressure in the tube. We propose that the present approach can be very promising in the mitigation of impurity particles on first mirrors in thermonuclear reactors.     

Growth of stoichiometric and textured LiNbO3 films on Si by pulsed laser deposition

Laser ablation of single-crystal LiNbO₃ in a gas environment is used to grow films on (100) Si substrates heated to 650 °C. The film composition and crystallinity are studied as a function of the nature (reactive, O₂, or inert, Ar) and pressure of the gas environment applied during deposition and cooling-down processes, the laser energy density and the target–substrate distance. Experimental results show that a gas pressure close to 1 mbar is required to produce stoichiometric films in either O₂ or Ar. The modification of the laser energy density and the target–substrate distance allows us to improve the crystallinity of the films that become textured along the (006) direction. The influence of the experimental parameters on the film properties is discussed in the frame of the formation of a blast wave, that leads to the focusing of the expanding Li species and thus, to the increase of the Li content in the films. Received: 8 February 2001 / Accepted: 9 February 2001 / Published online: 3 May 2001     

Kinetics of chemical vapor deposition of SiC from methyltrichlorosilane and hydrogen

In this study, the dependence of the deposition rate on processing parameters, such as temperature, and partial pressure is studied by chemical vapor deposition from mixture of methyltrichlorosilane (CH₃SiCl₃, MTS) and hydrogen. The kinetics investigation is carried out in a tubular, hot-wall reactor coupled to a sensitive magnetic suspension microbalance. The results show that the active energy limited by surface reactions is 188 kJ/mol. In the case, the deposition rate is linear to the partial pressure of MTS and the square of partial pressure of hydrogen. SiCl₂ and CH₃ are proposed as the effective precursor for SiC. A reaction model was proposed concluding gas phase reactions and surface reactions. The theoretical relation between deposition rate and partial pressures of MTS and H₂ was in a good accordance with experimental results.     

Critical parameters influencing the material distribution produced by pulsed laser deposition

The parameters that control the thickness distribution of thin films produced by pulsed laser deposition are investigated. It is found that highly asymmetric material distribution profiles can be obtained in vacuum when high energy densities are used and the target surface is positioned at the lens focus. The asymmetries are due to asymmetries in the spatial distribution of the beam. Under Ar gas pressure, the profile becomes symmetric and the distribution narrows as a consequence of collisions between the ejected species and the gas. In vacuum, decreasing the energy density, by decreasing the laser energy output or by moving the lens to defocus the beam, leads to symmetric distribution profiles. Nevertheless, in the first case a quite broad distribution and a low deposition rate are obtained, whereas in the second case the distribution is narrow and the deposition rate increases.     

Prediction of particle sticking efficiency for fly ash deposition at high temperatures

The tendency of ash particles to stick under high temperatures is dictated by the ash chemistry, particle physical properties, deposit surface properties and furnace operation conditions. A model has been developed in order to predict the particle sticking efficiency for fly ash deposition at high temperatures. The model incorporates the particle properties relevant to the ash chemistry, particle kinetic energy and furnace operation conditions and takes into consideration the partial sticking behaviour and the deposit layer. To test the model, the sticking behaviours of synthetic ash in a drop tube furnace are evaluated and the slagging formation from coal combustion in a down-fired furnace is modelled. Compared with the measurements, the proposed model presents reasonable prediction performance on the particle sticking behaviour and the ash deposition formation. Through a sensitivity analysis, furnace operation conditions (velocity and temperature), contact angle and particle size have been found to be the significant factors in controlling the sticking behaviours for the synthetic ash particles. The ash chemistry and furnace temperature dictate the wetting potential of the ash particles and the melting ability of the deposit surface; particle size and density not only control the particle kinetic energy, but also affect the particle temperature. The furnace velocity condition has been identified as being able to influence the selective deposition behaviour, where the maximum deposition efficiency moves to smaller particles when increasing the gas velocity. In addition, the thermophoresis effect on the arrival rate of the particles reduces with increasing the gas velocity. Further, increasing the melting degree of the deposit layer could greatly enhance the predicted deposition formation, in particular for the high furnace velocity condition.     

Indomethacin nanoparticles directly deposited on the fluidized particulate excipient by pulsed laser deposition

Nanoparticles of indomethacin (IM), a sparingly soluble drug in water, were prepared by pulsed laser deposition with Nd: YAG laser at 1064 nm. Variation of the deposition rate (DR) with various experimental conditions, such as species and pressure of the background gas, and laser fluence, was discussed. We obtained highest DR, 2.7 g/cm²min, under He at 100 Pa with the laser fluence of 25 J/cm². In the deposited solid product, no trace of drug decomposition was observed by HPLC. Deposition of IM nanoparticles was achieved on the fluidized excipient, potato starch particles of 20 m regime. By TEM observation and zeta potential distribution measurement, we confirmed that surface of excipient particles was fully covered by nanoparticles of IM. Thus, the present method enables us a new method of one-step preparation of drug-excipient nanocomposites to eliminate tedious problems associated with nanoparticles handling.     

Effect of deposition parameters on morphology and size of FeCo nanoparticles synthesized by pulsed laser ablation deposition

The experimental parameters that control the surface morphology and size of iron cobalt nanoparticles synthesized at room temperature by pulsed laser ablation deposition (PLAD) technique have been systematically investigated. The nanoparticle synthesis has been achieved at higher operating gas pressures of argon. It was found that nanoparticles upon deposition formed small clusters, the size of which increases with decreasing pressure, increasing laser-energy density, and decreasing target-to-substrate distance. This trend could be attributed to change in the kinetic energy of deposited nanoparticles with varying argon pressure, laser-energy, and target-to-substrate distance. The nanoparticles size and size distribution showed strong dependence on argon pressure and weak dependence on laser-energy density and target-to-substrate distance.     

螺旋波等离子体增强化学气相沉积氮化硅薄膜

利用螺旋波等离子体增强化学气相沉积(HWP-CVD)技术，以SiH4和N2为反应气体进行了氮化硅(SiN)薄膜沉积，并研究了实验参量对薄膜特性的影响.利用傅里叶变换红外光谱、紫外—可见光谱和椭偏光检测等技术对薄膜的结构、厚度和折射率等参量进行了测量.结果表明，采用HWP-CVD技术能在低衬底温度条件下以较高的沉积速率制备低H含量的SiN薄膜，所沉积的薄膜主要表现为Si—N键合结构.采用较低的反应气体压强将提高薄膜沉积速率，并使薄膜的致密性增加.适当提高N2/SiH4比例有利于薄膜中H含量的降低. 关键词： 螺旋波等离子体 化学气相沉积 氮化硅薄膜     

Systematic investigation of the reactive ion beam sputter deposition process of SiO<Subscript>2</Subscript>

Ion beam sputter deposition (IBSD) is an established physical vapour deposition technique that offers the opportunity to tailor the properties of film-forming particles and, consequently, film properties. This is because of two reasons: (i) ion generation and acceleration (ion source), sputtering (target) and film deposition (substrate) are locally separated. (ii) The angular and energy distribution of sputtered target atoms and scattered primary particles depend on ion incidence angle, ion energy, and ion species. Ion beam sputtering of a Si target in a reactive oxygen atmosphere was used to grow SiO₂ films on silicon substrates. The sputtering geometry, ion energy and ion species were varied systematically and their influence on film properties was investigated. The SiO₂ films are amorphous. The growth rate increases with increasing ion energy and ion incidence angle. Thickness, index of refraction, stoichiometry, mass density and surface roughness show a strong correlation with the sputtering geometry. A considerable amount of primary inert gas particles is found in the deposited films. The primary ion species also has an impact on the film properties, whereas the influence of the ion energy is rather small.