Effects of phase explosion in pulsed laser deposition of nickel thin film and sub-micron droplets

Nickel (Ni) thin films were deposited on glass substrates in high vacuum and at room temperature with third-harmonic or 355-nm output from a nanosecond Nd:YAG laser. At low laser fluence of 1 J/cm², the deposition rate was about 0.0016 nm/shot which increased linearly until 4 J/cm². Above 4 J/cm², the onset of phase explosion in the ablation abruptly increased the optical emission intensity from laser-produced Ni plume as well as thin-film deposition rate by about 6×. The phase explosion also shifted the size distribution and number density of Ni droplets on its thin-film surface. On the other hand, the surface structures of the ablated Ni targets were compared between the scan-mode and the fixed-mode ablations, which may suggest that droplets observed on the thin-film surface were caused by direct laser-induced splashing of molten Ni rather than vapour-to-cluster condensation during the plume propagation.     

Strong emission of particulates towards the incident beam direction in pulsed-laser ablation experiments

Theoretical predictions suggested that particulates (large clusters and droplets) in pulsed-laser ablation deposition (PLD) move towards the surface normal and constitute a small fraction of the total plume mass. Contrary to expectations, here we report that, independently of the laser beam direction, large clusters are ejected towards the laser direction of incidence, which generally differs from the surface normal. Moreover, fragments and droplets constitute the major fraction of the ablated mass. Cross-sectional SEM investigations performed on the Si targets show that the direction of growth of the columns follows the laser beam direction. These observations have been explained by the change of the microscopic ablation mechanism from monomer evaporation at low local laser fluences to phase explosion at higher local fluences.     

Effects of laser fluence on the structural properties of pulsed laser deposited ruthenium thin films

Ruthenium (Ru) has received great interest in recent years for applications in microelectronics. Pulsed laser deposition (PLD) enables the growth of Ru thin films at low temperatures. In this paper, we report for the first time the characterization of pulsed laser deposited Ru thin films. The deposition processes were carried out at room temperature in vacuum environment for different durations with a pulsed Nd:YAG laser of 355-nm laser wavelength, employing various laser fluences ranging from 2 J/cm² to 8 J/cm². The effect of the laser fluence on the structural properties of the deposited Ru films was investigated using surface profilometry, scanning electron microscopy (SEM), and X-ray diffraction (XRD). Ru droplets, some spherical in shape and some flattened into round discs were found on the deposited Ru. The droplets were correlated to ripple formations on the target during the laser-induced ejection from the target. In addition, crystalline Ru with orientations of (100), (101), and (002) was observed in the XRD spectra and their intensities were found to increase with increasing laser fluence and film thickness. Grain sizes ranging from 20 nm to 35 nm were deduced using the Scherrer formula. Optical emission spectroscopy (OES) and energy-dispersive X-ray spectroscopy (EDS) show that the composition of the plume and the deposited Ru film was of high purity.     

Resonant infrared pulsed laser deposition of cyclic olefin copolymer films

Barrier materials on thin-film organic optoelectronic devices inhibit the uptake of water, oxygen, or environmental contaminants, and fabricating them is a major challenge. By definition, these barrier layers must be insoluble, so the usual routes to polymer- or organic-film deposition by spin coating are not problematic. In this paper, we report comparative studies of pulsed laser deposition of cyclic olefin copolymer (COC), an excellent moisture barrier and a model system for a larger class of protective materials that are potentially useful in organic electronic devices, such as organic light-emitting diodes (OLEDs). Thin films of COC were deposited by resonant and nonresonant infrared pulsed laser ablation of solid COC targets, using a free-electron laser tuned to the 3.43 μm C–H stretch of the COC, and a high-intensity nanosecond Q-switched laser operated at 1064 nm. The ablation craters and deposited films were characterized by scanning-electron microscopy, Fourier-transform infrared spectrometry, atomic-force microscopy, high-resolution optical microscopy, and surface profilometry. Thermal-diffusion calculations were performed to determine the temperature rise induced in the film at the C–H resonant wavelength. The results show that resonant infrared pulsed laser deposition (RIR-PLD) is an effective, low-temperature thin-film deposition technique that leads to evaporation and deposition of intact molecules in homogeneous, smooth films. Nonresonant PLD, on the other hand, leads to photothermal damage, degradation of the COC polymers, and to the deposition only of particulates.     

Short-pulse laser deposition of diamond-like carbon thin films

The high intensities present in and the non-thermal nature of ultrashort-pulse laser ablation provide a nearly ideal source for thin-film deposition. The high kinetic energies and high ion content in the ablation plume suggest that it would be useful for the creation of diamond thin films. We used a 120 fs, 3 W, 1 kHz laser to ablate a graphite target and characterized the resulting films. We were able to grow amorphous films of up to 18 7m thick and free from graphite particulates with no annealing necessary and at rates up to 25 7m/hr. The films had 40-50% sp³ bonds as measured by using EELS and had properties typical of PLD-generated diamond-like carbon films.     

Stoichiometry issues in pulsed-laser deposition of alloys grown from multicomponent targets

We have examined the degree of congruent transfer in pulsed-laser deposition (PLD) of alloy thin films in phases that are stable over a wide range of compositions. SiGe films were deposited by PLD onto high-purity glassy carbon substrates. We analyzed the average composition of these films using Rutherford backscattering spectrometry (RBS), and results show that the deposited films have a higher relative concentration of Ge than the initial targets. We infer that the noncongruent transfer is due to differential scattering in the plume itself. Additionally, the local composition of the particulates was measured by the use of microprobe analysis, and observations of a sintered target of Si and Ge powders and a solidified target of melted Si and Ge were compared. We found that the sintered target produces particulates with a wide range of compositions, whereas the solidified target produces five times fewer particulates with a tighter distribution of compositions. In contrast with the average composition of the films, the average composition of the particulates is the same as that of the targets. These results are discussed in terms of the microstructure of the targets and the melting process at the surface. The implications of these observations for composition determination by laser ablation are discussed.     

Dispersion of laser droplets using H+ ions and annealing effect on pulsed laser deposited nickel ferrite thin films

Nickel ferrite thin films were deposited by a pulsed laser deposition (PLD) technique on silicon substrate at room temperature in a vacuum of 5×10⁻⁵ mbar. The films were subjected to different annealing temperatures from 300–900°C and were also exposed to single shot energetic hydrogen ions using a Dense Plasma Focus (DPF) device. The changes induced in the films exposed at different distances from the top of the anode were investigated. The structural, morphological and magnetic properties of the annealed and exposed samples were investigated. X-ray diffraction (XRD) studies reveal the presence of a single phase of nickel ferrite after annealing. SEM micrographs indicate an increase in the grain size, both on annealing as well as on exposure to hydrogen ions. Annealing and hydrogen ion irradiation induced an enhancement in the magnetic moments. Laser droplets which are inherent in films deposited by laser ablation were found to be dispersed as a result of single shot hydrogen ion irradiation from the DPF.     

Double-peak droplet mass distribution observed during sub-ps laser ablation of Si targets

The angular distribution of the ablated material was studied during sub-ps Si laser ablation deposition using a special hemicylindrical substrate holder and different laser fluences ranging between 0.4 and 1.7 J/cm². Scanning electron microscopy analysis of the deposited films showed that, independent of the fluence, the distribution of the deposited droplets presents two maxima. The first maximum corresponds to the average plume deflection angle value due to the local surface orientation produced by the preferential etching process. The second maximum is observed approximately at 45° with respect to the normal of the target surface, and is related to the phase explosion products that expand along the incident laser beam direction. The investigation of the twofold distribution of the sub-μm size deposited droplets is important to improve the quality of the deposited coatings. PACS 81.15.Fg; 68.55.Jk; 79.20.Ds     

Interface kinetics during pulsed laser ablation

This work investigates evaporation kinetics -- the relation between the surface temperature and pressure during excimer laser ablation. Nickel targets are ablated by excimer laser pulses in a laser fluence range between 1 and 6 J/cm², with the upper limit exceeding the threshold of phase explosion (5 J/cm²). The surface pressure is determined with a polyvinylidene fluoride (PVDF) piezoelectric transducer. When phase explosion occurs, the surface temperature is known to be near the thermodynamic critical temperature, therefore, by measuring the surface pressure, the surface temperature-pressure relation is determined at the threshold fluence of phase explosion. The surface temperature and the threshold fluence of phase explosion are also estimated from the measured velocity of the vapor plume and gas dynamics calculations. It is shown that, during excimer laser ablation, the temperature and pressure relation deviates significantly from the equilibrium kinetic relation.     

Optical transmission and reflection of aluminum film irradiated by nanosecond laser beam and experimental studying of phase-explosion

In this paper we present evidence for a phase explosion during the laser-induced ablation process by studying the optical reflectivity of the ablated plume. The ablation was produced by irradiating thin film aluminum coated on a quartz substrate with a single pulse laser beam in ambient air. The laser pulse was provided by the second harmonic of a Q-switched Nd:YAG laser with ∼10 ns pulse duration. The transmission of a low power He–Ne laser beam through the hot ablated material plume and its reflection (from the front surface, and rear surface of aluminum film) were also monitored during the duration of the ablation event. The results show that the front surface reflectivity is enhanced at an early time of ablation which is described as strong evidence for the creation of a phase explosion in this process.     

纳秒脉冲激光沉积薄膜过程中的烧蚀特性研究

研究了高能短脉冲激光薄膜制备的整个烧蚀过程.首先建立了基于超热理论的烧蚀模型，然 后利用较为符合实际的高斯分布表示脉冲激光输入能量密度，给出了考虑蒸发效应不同阶段 的烧蚀状态方程.结合适当的边界条件，以Si靶材为例，利用有限差分法得到了靶材在各个 阶段温度随时间和烧蚀深度的演化分布规律及表面蒸发速度与烧蚀深度在不同激光辐照强度 下随时间的演化规律.结果表明，在脉冲激光辐照阶段，靶材表面的蒸发效应使得靶材表面 温度上升显著放缓；在激光辐照强度接近相爆炸能量阈值时，蒸发速度与蒸发厚度的变化由 于逆流现象将显著放缓.还得到了考虑了熔融弛豫时间及蒸发效应的固-液界面随时间的演化 方程，这一结论较先前工作更具有普适性. 关键词： 脉冲激光烧蚀 热流方程 温度演化 有限差分法     

TiCN thin films grown by reactive crossed beam pulsed laser deposition

In this work, we used a crossed plasma configuration where the ablation of two different targets in a reactive atmosphere was performed to prepare nanocrystalline thin films of ternary compounds. In order to assess this alternative deposition configuration, titanium carbonitride (TiCN) thin films were deposited. Two crossed plasmas were produced by simultaneously ablating titanium and graphite targets in an Ar/N₂ atmosphere. Films were deposited at room temperature onto Si (100) and AISI 4140 steel substrates whilst keeping the ablation conditions of the Ti target constant. By varying the laser fluence on the carbon target it was possible to study the effect of the carbon plasma on the characteristics of the deposited TiCN films. The structure and composition of the films were analyzed by X-ray Diffraction, Raman Spectroscopy and non-Rutherford Backscattering Spectroscopy. The hardness and elastic modulus of the films was also measured by nanoindentation. In general, the experimental results showed that the TiCN thin films were highly oriented in the (111) crystallographic direction with crystallite sizes as small as 6.0 nm. It was found that the hardness increased as the laser fluence was increased, reaching a maximum value of about 33 GPa and an elastic modulus of 244 GPa. With the proposed configuration, the carbon content could be easily varied from 42 to 5 at.% by changing the laser fluence on the carbon target.     

Study of pulsed laser deposition of RuO2 and SrRuO3 thin films

In this study, the pulsed laser ablation of RuO₂ and SrRuO₃ (SRO) is investigated by observing the fluorescence from excited atoms in the plume by using a framing streak camera. Vaporization, phase explosion and boiling are suggested to play the main roles in the processes for the interaction between the laser beam and target. Collisions and adiabatic expansion are also suggested before particles move forward with shifted Maxwellian spatial distribution. In O₂ pressure, numerous collisions between fast and slow atoms occur and result in the exchange of speeds. The structural and electrical (conductivity and work-function) properties of RuO₂ and SRO thin films are measured. Epitaxial SRO growth was obtained at growth temperatures down to 350 °C. Ferroelectric and high- dielectric thin-film capacitors with RuO₂ or SRO thin film electrode are also studied.     

Non-stoichiometry-induced metal-to-insulator transition in nickelate thin films grown by pulsed laser deposition

While controlling the cation contents in perovskite rare-earth nickelate thin films, a metal-to-insulator phase transition is reported. Systematic control of cation stoichiometry has been achieved by manipulating the irradiation of excimer laser in pulsed laser deposition. Two rare-earth nickelate bilayer thin-film heterostructures with the controlled cation stoichiometry (i.e. stoichiometric and Ni-excessive) have been fabricated. It is found that the Ni-excessive nickelate film is structurally less dense than the stoichiometric film, albeit both of them are epitaxial and coherent with respect to the underlying substrate. More interestingly, as a temperature decreases, a metal-to-insulator transition is only observed in the Ni-excessive nickelate films, which can be associated with the enhanced disproportionation of the Ni charge valence. Based on our theoretical results, possible origins (e.g. anti-site defects) of the low-temperature insulating state are discussed with the need of future work for deeper understanding. Our work can be utilized to realize unusual physical phenomena (e.g. metal-to-insulator phase transitions) in complex oxide films by manipulating the chemical stoichiometry in pulsed laser deposition.     

Patterning of CIGS thin films induced by rear-side laser ablation of polyimide carrier foil

Laser patterning of thin films is essential for the future development of flexible electronic devices. The damage-free scribing of thermally sensitive thin films such as copper–indium–gallium diselenide (CIGS) that is required for solar module fabrication by integrated interconnections is still challenging. In this study a new approach for non-thermal, damage-free scribing of CIGS films on polyimide foil is proposed and demonstrated. In contrast to the usually used direct laser ablation of the thin-film stack, laser ablation of the polyimide carrier foil at laser fluences higher than 3 J/cm² is utilized to achieve CIGS film delamination and thus the patterning of the thin film. The edges of the patterned CIGS films do not show typical laser-ablation-induced modifications like melting, debris contamination, or crack formation. The mechanism of the thin-film removal is of non-thermal origin and is probably due to stress formation at the CIGS/Mo interface resulting from secondary processes of polyimide laser ablation like shock-wave formation or local sample deformation.     

Particles in laser ablation of polytetrafluoroethylene

KrF-laser ablation of pressed polytetrafluoroethylene (PTFE) targets is accompanied by the ejection of submicron- to micron-sized particles. Collected ejecta consist of four basic particle morphologies ranging from small particles 50-200 nm in diameter to larger particles ~10 7m in diameter. Many particles carry electric charge as measured by using charged electrodes and by the Millikan technique. Thin PTFE films deposited by pulsed laser deposition (PLD) from the same targets onto heated Si substrates are highly crystalline and show only a minor but detectable increase of defects compared with the target material. The transferred particulates mainly consist of long PTFE molecule chains. The low molecular weight material that is also transferred to the substrate mainly either links with other low molecular weight material or evaporates during deposition.     

Indium and tin oxide polycrystalline thin films as NO gas sensors produced by reactive pulsed laser ablation and deposition

Pulsed laser ablation is a very interesting method of depositing thin films of several materials and compounds, such as oxides, nitrides, insulators, semiconductors, and superconductors. Indium and tin oxide polycrystalline thin films have been grown on silicon (100) substrates by reactive PLD from two metallic targets of indium and tin by multilayered deposition, in the presence of oxygen, using a frequency-doubled Nd-YAG laser (5=532 nm). The films produced have been studied to evaluate their use as NO gas sensors, and the best performance has been found by varying some important parameters, such as the substrate temperature and the pressure of oxygen in the deposition chamber. X-ray diffraction analysis of the deposited films shows that they are polycrystalline with a preferential (400) orientation. Electrical resistivity measurements, performed by using a four-point probe technique, show a sharp increase in resistivity when the films are exposed to NO. The electrical responses of tin oxide-indium oxide multilayered thin films are reported.     

Properties of pulsed laser deposited nanocomposite NiO:Au thin films for gas sensing applications

Nanocomposite thin films formed by gold nanoparticles embedded in a nickel oxide matrix have been synthesized by a new variation of the pulsed laser deposition technique. Two actively synchronized laser sources, a KrF excimer laser at 248 nm and an Nd:YAG laser at 355 nm, were used for the simultaneous ablation of nickel and gold targets in oxygen ambient. The structural, morphological, and electrical properties of the obtained nanocomposite films were investigated in relation to the fluence of the laser irradiating the gold target. The nanocomposite thin films were tested as electrochemical hydrogen sensors. It was found that the addition of the gold nanoparticles increased the sensor sensitivity significantly.     

Formation of TiN-Ir particle films using pulsed-laser deposition and their electrolytic properties in producing hypochlorous acid

Using sintered TiN and TiN-Ir (Ir contents: 5.9-14.2 at.%) targets, pulsed-laser deposition (PLD) was carried out to produce thin films composed of nanoparticles and particulates in the presence of nitrogen gas. The size (2-100 nm) of the produced crystalline TiN nanoparticles increased as nitrogen pressure was increased in the range from 1.33 to 1.33 × 10² Pa. At a pressure of 1.33 × 10³ Pa, amorphous TiN nanoparticles combined in the form of chains. Large Ir particulates with diameters of up to 2 μm were particularly prominent in TiN-Ir films. Size distributions of the Ir particulates were dependent on ablation laser wavelength; that is, the diameter decreased at laser wavelength shortened. The TiN-Ir films with different Ir contents and morphologies on Ti substrates were evaluated as electrolysis electrodes for water disinfection. The highest current efficiency was 0.45%, which is comparable to that of conventional Ti-Pt electrodes, for a chloride-ion concentration of 9 mg dm⁻³.     

Laser applications in thin-film photovoltaics

We review laser applications in thin-film photovoltaics (thin-film Si, CdTe, and Cu(In,Ga)Se₂ solar cells). Lasers are applied in this growing field to manufacture modules, to monitor Si deposition processes, and to characterize opto-electrical properties of thin films. Unlike traditional panels based on crystalline silicon wafers, the individual cells of a thin-film photovoltaic module can be serially interconnected by laser scribing during fabrication. Laser scribing applications are described in detail, while other laser-based fabrication processes, such as laser-induced crystallization and pulsed laser deposition, are briefly reviewed. Lasers are also integrated into various diagnostic tools to analyze the composition of chemical vapors during deposition of Si thin films. Silane (SiH₄), silane radicals (SiH₃, SiH₂, SiH, Si), and Si nanoparticles have all been monitored inside chemical vapor deposition systems. Finally, we review various thin-film characterization methods, in which lasers are implemented.