Growth of titanium oxynitride layers by short pulsed Nd:YAG laser treatment of Ti plates: Influence of the cumulated laser fluence

Titanium oxynitride layers were formed by surface laser treatment of Ti plates in air using a Nd:YAG laser source of short pulse duration about 5 ns. The cumulated laser fluence was varied in the 100-1200 J cm⁻² range and its influence on the composition and the structure of the formed layers was studied by different characterization techniques providing physico-chemical and structural information. It was shown that the laser treatment induces the insertion of light elements as O, N and C in the formed layer with the amount increasing with the laser fluence. The in-depth composition of the layers and the co-existence of different phases were also studied.The way in which the laser parameters such as fluence affect the insertion of nitrogen and oxygen was discussed in connection with the effects of the plasma plume formed above the target.     

X-ray photoelectron spectroscopic study on surface reaction on titanium by laser irradiation in nitrogen atmosphere

The surface reaction on titanium due to pulsed Nd:YAG laser irradiation in a nitrogen atmosphere was investigated using X-ray photoelectron spectroscopy (XPS). The laser, with a wavelength of 532 nm (SHG mode), was irradiated on a titanium substrate in an atmosphere-controlled chamber, and then the substrate was transported to an XPS analysis chamber without exposure to air. This in situ XPS technique makes it possible to clearly observe the intrinsic surface reaction. The characteristics of the surface layer strongly depend on the nitrogen gas pressure. When the pressure is 133 kPa, an oxynitride and a stoichiometric titanium nitride form the topmost and lower surface layers on the titanium substrate, respectively. However, only a nonstoichiometric titanium oxide layer containing a small amount of nitrogen is formed when the pressure is lower than 13.3 kPa. Repetition of laser shots promotes the formation of the oxide layer, but the formation is completed within a few laser shots. After the initial structure is formed, the chemical state of the surface layer is less influenced by the repetition of laser shots.     

Radiation effects and pulsed laser deposition of titanium by Nd:Yag laser

A study of Ti laser irradiation and thin film deposition produced by an Nd:Yag pulsed laser is presented. The laser pulse, 9?ns width, has a power density of the order of 10¹⁰?W/cm². The titanium etching rate is of the order of 1?µg/pulse, it increases with the laser fluence and shows a threshold value at about 30?J/cm² laser fluence. The angular distribution of ejected atoms (neutrals and ions) is peaked along the normal of the target surface. At high fluence, the fractional ionization of the plasma produced by the laser is of the order of 10%. Time-of-flight measurements demonstrate that the titanium ions, at high laser fluence, may reach kinetic energies of about 1?keV. Obtained results can be employed to produce energetic titanium ions, to produce coverage of thin films of titanium and to realize high adherent titanium-substrate interfaces. The obtained results can be employed to produce energetic titanium ions, to produce a coverage of thin titanium films on polymers, and to realize highly adherent titanium–substrate interfaces.     

Effects of green laser fluence on the characteristics of graphene nanosheets synthesized by laser ablation method in liquid nitrogen medium

We have studied the effects of laser fluence on the characteristics of graphene nanosheets produced by pulsed laser ablation technique. In this work, The second harmonic of a Q-switched Nd:YAG laser at 532 nm wavelength and 5 Hz repetition rate with different laser fluences in the range of 0.5–1.8 J/cm² was used to irradiate the graphite target in liquid nitrogen medium. The products of ablation were characterized using Fourier transform infrared spectroscopy, field emission scanning electron microscopy, X-ray diffraction pattern, UV–Vis absorption spectroscopy, Raman spectrum and transmission electron microscopy. The Raman spectroscopy indicates that the quality of the graphene nanosheets was decreased while their structure defects were increased as the laser fluence was increased from 0.5 to 1.4 J/cm². Our results suggest that the amount of defects and the number of layers in graphene nanosheets can be changed by adjusting the laser fluence. This study could be a useful guidance for producing of high quality of graphene nanosheets by laser ablation method.     

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.     

Wear resistance of ZrC/TiN and ZrC/ZrN thin multilayers grown by pulsed laser deposition

ZrC/TiN and ZrC/ZrN multilayers thinner than 350 nm were grown on (100) Si substrates at a temperature of 300 °C by the pulsed laser deposition (PLD) technique using a KrF excimer laser (λ=248 nm, pulse duration τ=25 ns, 8.0 J/cm² fluence and 40 Hz repetition rate). Cross-sectional transmission electron microscopy, Auger electron spectroscopy depth profiling and simulations of X-ray reflectivity curves indicated that there was intermixing between the deposited layers at the interfaces as well as between the first layer and the substrate. Nanoindentation investigations found hardness values between 35 and 38 GPa for the deposited multilayers. Linear unidirectional sliding wear tests were conducted using a ball-on-plate tribometer under 1 N normal force. Wear tracks were produced in a Hysitron nanoindenter with 1 μm radius diamond tip under a 500 μN load. High-resolution cross-sectional transmission electron microscopy studies of the wear tracks showed that the multilayers withstood these tests without significant damage. The results could be explained by the use of a high laser fluence during deposition that resulted in very dense and strongly adherent nanocrystalline layers.     

Characterization of polymer thin films obtained by pulsed laser deposition

The development of laser techniques for the deposition of polymer and biomaterial thin films on solid surfaces in a controlled manner has attracted great attention during the last few years. Here we report the deposition of thin polymer films, namely Polyepichlorhydrin by pulsed laser deposition. Polyepichlorhydrin polymer was deposited on flat substrate (i.e. silicon) using an NdYAG laser (266 nm, 5 ns pulse duration and 10 Hz repetition rate).The obtained thin films have been characterized by atomic force microscopy, scanning electron microscopy, Fourier transform infrared spectroscopy and spectroscopic ellipsometry.It was found that for laser fluences up to 1.5 J/cm² the chemical structure of the deposited polyepichlorhydrin polymer thin layers resembles to the native polymer, whilst by increasing the laser fluence above 1.5 J/cm² the polyepichlorohydrin films present deviations from the bulk polymer.Morphological investigations (atomic force microscopy and scanning electron microscopy) reveal continuous polyepichlorhydrin thin films for a relatively narrow range of fluences (1-1.5 J/cm²).The wavelength dependence of the refractive index and extinction coefficient was determined by ellipsometry studies which lead to new insights about the material.The obtained results indicate that pulsed laser deposition method is potentially useful for the fabrication of polymer thin films to be used in applications including electronics, microsensor or bioengineering industries.     

Excimer laser ablation of thin titanium oxide films on glass

Thin titanium dioxide films are deposited on glass substrates by magnetron sputter deposition. They are irradiated in air, by means of a KrF excimer laser. The ablation rate is measured as a function of the laser fluence per pulse, F, and of the number of pulses, N. Above a fluence threshold, the films are partially ablated. The ablated thickness does not vary linearly with N. This is the signature of a negative feedback between the film thickness and the ablation rate. The origin of this negative feedback is shown to be due to either thermal or electronic effects, or both. At high F, the film detachs from the substrate.     

Effect of laser annealing using high repetition rate pulsed laser on optical properties of phosphorus-ion-implanted ZnO nanorods

The effect of high repetition rate pulsed laser annealing with a KrF excimer laser on the optical properties of phosphorus-ion-implanted zinc oxide nanorods has been investigated. The recovery levels of phosphorus-ion-implanted zinc oxide nanorods have been measured by photoluminescence spectra and cathode luminescence images. Cathode luminescence disappeared over 300 nm below the surface due to the damage caused by ion implantation with an acceleration voltage of 25 kV. When the annealing was performed at a low repetition rate of the KrF excimer laser, cathode luminescence was recovered only in a shallow area below the surface. The depth of the annealed area was increased along with the repetition rate of the annealing laser. By optimizing the annealing conditions such as the repetition rate, the irradiation fluence and so on, we have succeeded in annealing the whole damaged area of over 300 nm in depth and in observing cathode luminescence. Thus, the effectiveness of high repetition rate pulsed laser annealing on phosphorus-ion-implanted zinc oxide nanorods was demonstrated.     

Femtosecond laser micromilling of Si wafers

Femtosecond laser micromilling of silicon is investigated using a regeneratively amplified 775 nm Ti:Sapphire laser with a pulse duration of 150 fs operating at 1 kHz repetition rate. The morphological observation and topological analysis of craters fabricated by single-shot laser irradiation indicated that the material removal is thermal in nature and there are two distinct ablation regimes of low fluence and higher fluence with logarithmical relations between the ablation depth and the laser fluence. Crater patterns were categorized into four characteristic groups and their formation mechanisms were investigated. Femtosecond laser micromilling of pockets in silicon was performed. The effect of process parameters such as pulse energy, translation speed, and the number of passes on the material removal rate and the formation of cone-shaped microstructures were investigated. The results indicate that the microstructuring mechanism has a strong dependence on the polarization, the number of passes and laser fluence. The optimal laser fluence range for Si micromilling was found to be 2-8 J/cm² and the milling efficiency attains its maximum between 10 and 20 J/cm².     

具有窄光致发光谱的纳米Si晶薄膜的激光烧蚀制备

采用XeCl脉冲准分子激光器，在10Pa的Ar气环境下，烧蚀高阻单晶Si靶，分别在距靶3cm的玻璃和单晶Si衬底上制备了纳米Si薄膜. 相应的Raman谱和x射线衍射谱均证实了薄膜中纳米Si晶粒的形成. 扫描电子显微镜图像显示，所形成的薄膜呈均匀的纳米Si晶粒镶嵌结构. 相应的光致发光峰位出现在599nm，峰值半高宽为56nm，与相同参数下以He气为缓冲气体的结果相比，具有较窄的光致发光谱，并显示出谱峰蓝移现象. 关键词： 纳米Si晶粒 脉冲激光烧蚀 薄膜形貌 光致发光     

Picosecond pulsed laser ablation and micromachining of 4H-SiC wafers

Ultra-short pulsed laser ablation and micromachining of n-type, 4H-SiC wafer was performed using a 1552 nm wavelength, 2 ps pulse, 5 μJ pulse energy erbium-doped fiber laser with an objective of rapid etching of diaphragms for pressure sensors. Ablation rate, studied as a function of energy fluence, reached a maximum of 20 nm per pulse at 10 mJ/cm², which is much higher than that achievable by the femtosecond laser for the equivalent energy fluence. Ablation threshold was determined as 2 mJ/cm². Scanning electron microscope images supported the Coulomb explosion (CE) mechanism by revealing very fine particulates, smooth surfaces and absence of thermal effects including melt layer formation. It is hypothesized that defect-activated absorption and multiphoton absorption mechanisms gave rise to a charge density in the surface layers required for CE and enabled material expulsion in the form of nanoparticles. Trenches and holes micromachined by the picosecond laser exhibited clean and smooth edges and non-thermal ablation mode for pulse repetition rates less than 250 kHz. However carbonaceous material and recast layer were noted in the machined region when the pulse repetition rate was increased 500 kHz that could be attributed to the interaction between air plasma and micro/nanoparticles. A comparison with femtosecond pulsed lasers shows the promise that picosecond lasers are more efficient and cost effective tools for creating sensor diaphragms and via holes in 4H-SiC.     

Removal of doped poly(methylmetacrylate) from tungsten and titanium substrates by femto- and nanosecond laser cleaning

The influence of different laser pulse lengths on the removal of a polymer layer from metal substrates was investigated. As model systems, doped poly(methylmetacrylate) (PMMA) on titanium and tungsten substrates were selected.The ablation threshold and irradiation spot morphology of titanium and tungsten were compared for femtosecond (fs) and nanosecond (ns) laser irradiation and different pulse numbers. Nanosecond laser treatment resulted in a non-homogeneous surface morphology for both titanium and tungsten substrates. Femtosecond irradiation of tungsten revealed a homogeneous ablation spot with little changes in the surface morphology. For titanium, the formation of columnar structures within the irradiation spot was observed.Two different dopant concentrations were used for PMMA to achieve an equal linear absorption coefficient for the femto- and nanosecond laser wavelengths of 790 and 1064 nm. The best results were achieved for the removal of doped PMMA by femtosecond laser irradiation, where only a minimal modification of the metal surface was detected. In the case of nanosecond laser exposure, a pronounced change of the structure was observed, suggesting that damage-free cleaning of the selected metal may only be possible using femtosecond laser pulses. Different experimental parameters, such as laser fluence, pulse repetition rate and sample speed were also investigated to optimize the cleaning quality of doped PMMA from tungsten substrates with femtosecond laser pulses.     

High repetition rate femtosecond laser nano-machining of thin films

Thin film laser micromachining has been utilized for repairing semiconductor masks, creating solar cells and fabricating MEMS devices. A unique high repetition rate femtosecond fiber laser system capable of variable repetition rates from 200 KHz to 25 MHz along with helium gas assist was used to study the effect of pulse repetition rate and pulse energy on femtosecond laser machining of gold-coated silicon wafer. It was seen that high repetition rates lead to smaller craters with uniform line width. Craters created at 13 MHz pulse repetition rate with 2.042 J/cm² beam energy fluence measured 110 nm in width and had a heat affected zone of 0.79 μm. It was found that pulse repetition rate only played a significant role in the size of the heat affected zone in the lower pulse energy ranges. In the future, a 1 W laser system will be acquired to find the optimal repetition rate that would create the minimal feature size with the least heat affected zone. Using this kind of setup along with techniques such as radial polarization and a different gas assist may enable us to create sub 100 nm feature size with good quality.     

基于石墨烯可饱和吸收体的纳秒锁模掺铥光纤激光器

报道了一种基于石墨烯可饱和吸收体的纳秒锁模掺铥光纤激光器.该激光器采用环形腔结构,利用自制的三层石墨烯薄膜作为可饱和吸收体实现锁模.同时在腔内插入一个窄带光纤光栅,约束腔内起振的纵模数,适当调节抽运功率和偏振控制器的角度,得到了重复频率为3.8 MHz、脉宽在3.8—94.3 ns之间灵活可调的2μm纳秒锁模脉冲输出,整个脉宽调节范围超过90 ns.此外,由于获得的兆赫兹纳秒锁模脉冲时间带宽积在49—1119范围内,即存在强烈的啁啾,因而可作为2μm波段啁啾脉冲放大系统中的种子源使用.     

XeCl laser controlled chemical etching of aluminum in chlorine gas

The 308 nm XeCl laser assisted etching process of thin Al metal films on Si substrate in Cl₂ gas was investigated. Etch rates were measured versus the laser fluence on the sample, the laser repetition rate, the Cl₂ pressure and the sample temperature. Irradiation experiments under vacuum of films which were previously exposed to Cl₂, and laser assisted etching in rare gases, nitrogen and air mixtures with Cl₂ were also performed to elucidate the mechanism of the etching process. The surface morphology was investigated by scanning electron microscopy. The results show that a) Etch rates of up to about 1.5 m per pulse are obtained which are strongly dependent on the Cl₂ pressure and sample temperature. b) The etching mechanism is essentially a chemical chlorination of the Al in between the laser pulses which is followed by photo-ablation of the reaction products, c) AlCl₃ evaporation and redeposition processes can explain the observed results. d) The Al films can be etched fully and cleanly without damage to the smooth Si substrate. e) Etching through adjacent or imaged mask on the Al film yielded relatively smooth and well defined Al walls with structures of the order of 1 m.     

Projection ablation of glass-based single and arrayed microstructures using excimer laser

Ablation of single and arrayed microstructures using an excimer laser is studied. The single feature microstructures are fabricated for evaluating the ablation mechanism, threshold fluence, and associated material removing (ablation) rate. The morphology changes during ablation are investigated with the focus on the formation of the ablation defects, debris or recast. The possibility of removing these defects is also evaluated and demonstrated. The present study concentrates on the borosilicate glass, although ablation of polyimide and silicon are performed and discussed for comparison. Polyimide and silicon are the most popular polymer or semiconductor material used in the electronics industry. The arrayed microstructures are ablated to demonstrate the fact that, by repetition of a simple-patterned mask associated with synchronized laser pulses and substrate movement, arrayed and more complex structures can be cost-effectively manufactured. The potential applications of these arrayed microstructures are discussed and illustrated. A low-cost replication technique that uses the arrayed microstructure presently machined as the forming mold for making electroforming nickel microneedles is specifically presented. Finally, the potential areas of using excimer laser in micromachining of glass-based structures for future research are also briefly covered.     

Low-temperature growth of SnO2 film prepared by XeCl excimer laser MOD process

A SnO₂ film has been prepared by an excimer laser metal organic deposition (ELMOD) process using an XeCl laser. The effects of the laser fluence, shot number, and the pretreatment temperature of the Sn acetylacetonate (Sn-acac) on the crystallization of the SnO₂ film were investigated by X-ray diffraction and infrared spectroscopy. When the MO spin-coated film preheated at room temperature on a Si substrate was irradiated by the laser at a fluence of 100 mJ/cm² and at a repetition rate of 10 Hz for 5 min, a crystallized SnO₂ film was successfully obtained without heat treatment. At a fluence of 260 mJ/cm², the highest crystalline film was formed. On the other hand, when the amorphous SnO₂ film was irradiated by the laser at 260 mJ/cm², the crystallinity of the SnO₂ film was improved. SnO₂ films were also prepared by conventional thermal MOD in a temperature range from 300 to 900 °C. The crystallinity of the SnO₂ films prepared by the ELMOD process at room temperature was higher than that of the films prepared by heating at 900 °C for 60 min. PACS 81.15.Fg; 81.15.-z; 81.16.Mk; 82.50.Hp; 73.61.Le     

Structural characterization of AlN films synthesized by pulsed laser deposition

We obtained AlN thin films by pulsed laser deposition (PLD) from a polycrystalline AlN target using a pulsed KrF* excimer laser source (248 nm, 25 ns, intensity of ∼4 × 10⁸ W/cm², repetition rate 3 Hz, 10 J/cm² laser fluence). The target-Si substrate distance was 5 cm. Films were grown either in vacuum (10⁻⁴ Pa residual pressure) or in nitrogen at a dynamic pressure of 0.1 and 10 Pa, using a total of 20,000 subsequent pulses. The films structure was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and spectral ellipsometry (SE). Our TEM and XRD studies showed a strong dependence of the film structure on the nitrogen content in the ambient gas. The films deposited in vacuum exhibited a high quality polycrystalline structure with a hexagonal phase. The crystallite growth proceeds along the c-axis, perpendicular to the substrate surface, resulting in a columnar and strongly textured structure. The films grown at low nitrogen pressure (0.1 Pa) were amorphous as seen by TEM and XRD, but SE data analysis revealed ∼1.7 vol.% crystallites embedded in the amorphous AlN matrix. Increasing the nitrogen pressure to 10 Pa promotes the formation of cubic (≤10 nm) crystallites as seen by TEM but their density was still low to be detected by XRD. SE data analysis confirmed the results obtained from the TEM and XRD observations.     

Femtosecond pulsed laser ablation of 3CSiC thin film on silicon

A femtosecond pulsed Ti:sapphire laser (pulse width=120 fs, wavelength=800 nm, repetition rate=1 kHz) was employed to perform laser ablation of 1-m-thick silicon carbide (3CSiC) films grown on silicon substrates. The threshold fluence and ablation rate, useful for the micromachining of the 3CSiC films, were experimentally determined. The material removal mechanisms vary depending on the applied energy fluence. At high laser fluence, a thermally dominated process such as melting, boiling and vaporizing of single-crystal SiC occurs. At low laser fluence, the ablation is a defect-activation process via incubation, defect accumulation, formation of nanoparticles and final vaporization of boundaries. The defect-activation process reduces the ablation threshold fluence and enhances lateral and vertical precision as compared to the thermally dominated mechanism. Helium, as an assistant gas, plays a major role in improving the processing quality and ablation rate of SiC thin films due to its inertness and high first ionization energy. PACS 79.20.Ds; 42.62.Cf; 42.70.Qs; 61.72; 61.46