Fixation of bioactive calcium alkali phosphate on Ti6Al4V implant material with femtosecond laser pulses

Bone implants made of metal, often titanium or the titanium alloy Ti6Al4V, need to be surface treated to become bioactive. This enables the formation of a firm and durable connection of the prosthesis with the living bone. We present a new method to uniformly cover Ti6Al4V with a thin layer of ceramics that imitates bone material. These calcium alkali phosphates, called GB14 and Ca10, are applied to the metal by dip coating of metal plates into an aqueous slurry containing the fine ceramic powder. The dried samples are illuminated with the 790 nm radiation of a pulsed femtosecond laser. If the laser fluence is set to a value just below the ablation threshold of the ceramic (ca. 0.4 J/cm²) the 30 fs laser pulses penetrate the partly transparent ceramic layer of 20-40 μm thickness. The remaining laser fluence at the ceramic-metal interface is still high enough to generate a thin metal melt layer leading to the ceramic fixation on the metal. The laser processing step is only possible because Ti6Al4V has a lower ablation threshold (between 0.1 and 0.15 J/cm²) than the ceramic material. After laser treatment in a fluence range between 0.1 and 0.4 J/cm², only the particles in contact with the metal withstand a post-laser treatment (ultrasonic cleaning). The non-irradiated rest of the layer is washed off. In this work, we present results of a successful ceramic fixation extending over larger areas. This is fundamental for future applications of arbitrarily shaped implants.     

Particulate assisted growth of ZnO nanorods and microrods by pulsed laser deposition

Zinc oxide (ZnO) thin films were deposited on the gallium nitride (GaN) and sapphire (Al₂O₃) substrates by pulsed laser deposition (PLD) without using any metal catalyst. The experiment was carried out at three different laser wavelengths of Nd:YAG laser (λ = 1064 nm, λ = 532 nm) and KrF excimer laser (λ = 248 nm). The ZnO films grown at λ = 532 nm revealed the presence of ZnO nanorods and microrods. The diameter of the rods varies from 250 nm to 2 μm and the length varies between 9 and 22 μm. The scanning electron microscopy (SEM) images of the rods revealed the absence of frozen balls at the tip of the ZnO rods. The growth of ZnO rods has been explained by vapor-solid (V-S) mechanism. The origin of growth of ZnO rods has been attributed to the ejection of micrometric and sub-micrometric sized particulates from the ZnO target. The ZnO films grown at λ = 1064 nm and λ = 248 nm do not show the rod like morphology. X-ray photoelectron spectroscopy (XPS) has not shown the presence of any impurity except zinc and oxygen.     

Analysis of materials modifications caused by UV laser micro drilling of via holes in AlGaN/GaN transistors on SiC

Pulsed UV laser drilling can be applied to fabricate vertical electrical interconnects (vias) for AlGaN/GaN high electron mobility transistor devices on single-crystalline silicon carbide (SiC) substrate. Through-wafer micro holes with a diameter of 50-100 μm were formed in 400 μm thick bulk 4H-SiC by a frequency-tripled solid-state laser (355 nm) with a pulse width of ≤30 ns and a focal spot size of ∼15 μm. The impact of laser machining on the material system in the vicinity of micro holes was investigated by means of micro-Raman spectroscopy and transmission electron microscopy. After removing the loosely deposited debris by etching in buffered hydrofluoric acid, a layer of <4 μm resolidified material remains at the side walls of the holes. The thickness of the resolidified layer depends on the vertical distance to the hole entry as observed by scanning electron microscopy. Micro-Raman spectra indicate a change of internal strain due to laser drilling and evidence the formation of nanocrystalline silicon (Si). Microstructure analysis of the vias’ side walls using cross sectional TEM reveals altered degree of crystallinity in SiC. Layers of heavily disturbed SiC, and nanocrystalline Si are formed by laser irradiation. The layers are separated by 50-100 nm thick interface regions. No evidence of extended defects, micro cracking or crystal damage was found beneath the resolidified layer. The precision of UV laser micro ablation of SiC using nanosecond pulses is not limited by laser-induced extended crystal defects.     

Patterning of indium-tin oxide on glass with picosecond lasers

The results of patterning of the indium-tin oxide (ITO) film on the glass substrate with high repetition rate picosecond lasers at various wavelengths are presented. Laser radiation initiated the ablation of the material, forming grooves in ITO. Profile of the grooves was analyzed with a phase contrast optical microscope, a stylus type profiler, scanning electron microscope (SEM) and atomic force microscope (AFM). Clean removal of the ITO film was achieved with the 266 nm radiation when laser fluence was above the threshold at 0.20 J/cm², while for the 355 nm radiation, the threshold was higher, above 0.46 J/cm². The glass substrate was damaged in the area where the fluence was higher than 1.55 J/cm². The 532 nm radiation allowed getting well defined grooves, but a lot of residues in the form of dust were generated on the surface. UV radiation with the 266 nm wavelength provided the widest working window for ITO ablation without damage of the substrate. Use of UV laser radiation with fluences close to the ablation threshold made it possible to minimize surface contamination and the recast ridge formation during the process.     

A study on UV laser drilling of PEEK reinforced with carbon fibers

This paper deals with the application of Nd-YAG laser emitting at 355 nm to the drilling process of Carbon Fiber Reinforced Polyetheretherkethone (PEEK-CF) laminates. The combination of a modern UV-laser source with a scanning technology enabling speeds up to 4 m/s, suppresses heat affected zones (HAZ) and consequently detachment of fibers from the polymer matrix. A removal technique based on the ablation of superimposed layers of composite material is proposed and analyzed in detail as a function of energy density delivered to the surface, hatch strategy and thickness of the laminate to be drilled. The hatching technique discussed in the paper is compared with conventional laser trepanning and percussion drilling through holes for the realization of 2 mm and 0.1 mm diameter, respectively. In both the cases benefits were noticed in terms of extension of HAZ and quality of the cut edges.     

Surface modifications of AISI 1045 steel created by high intensity 1064 and 532 nm picosecond Nd:YAG laser pulses

Interaction of Nd:YAG laser, operating at 1064 or 532 nm wavelength and a pulse duration of 40 ps, with AISI 1045 steel was studied. Surface damage thresholds were estimated to be 0.30 and 0.16 J/cm² at the wavelengths of 1064 and 532 nm, respectively. The steel surface modification was studied at the laser energy density of 10.3 J/cm² (at 1064 nm) and 5.4 J/cm² (at 532 nm). The energy absorbed from Nd:YAG laser beam is partially converted to thermal energy, which generates a series of effects, such as melting, vaporization of the molten material, shock waves, etc. The following AISI 1045 steel surface morphological changes and processes were observed: (i) both laser wavelengths cause damage of the steel in the central zone of irradiated area; (ii) appearance of a hydrodynamic feature in the form of resolidified droplets of the material in the surrounding outer zone with 1064 nm laser wavelength; (iii) appearance of periodic surface structures, at micro- and nano-level, with the 532 nm wavelength and, (iv) development of plasma in front of the target. Generally, interaction of laser beam with the AISI 1045 steel (at 1064 and 532 nm) results in a near-instantaneous creation of damage, meaning that large steel surfaces can be processed in short time.     

Micro-ablation on silicon by femtosecond laser pulses focused with an axicon assisted with a lens

Micro-ablation of crystalline silicon was performed by irradiating a silicon substrate with femtosecond laser pulses of wavelengths 786 nm or 393 nm focused using a conical axicon assisted with a convex lens. Focusing the laser beam close to the tip of the axicon by means of the lens significantly improved the efficiency of concentration of laser pulse energy at the central spot of the resulting Bessel-Gaussian intensity distribution. As a result, micron-sized holes were formed with the diameter determined by the ablation threshold in the calculated fluence profile. It is possible to predict hole size from the laser pulse energy and the wavelength. Crystalline particles, a few tens of nanometers in size, were formed near the ablated zone.     

Surface modifications of a titanium implant by a picosecond Nd:YAG laser operating at 1064 and 532 nm

Interaction of an Nd:YAG laser, operating at 1064 or 532 nm wavelength and pulse duration of 40 ps, with titanium implant was studied. Surface damage thresholds were estimated to 0.9 and 0.6 J/cm² at wavelengths 1064 and 532 nm, respectively. The titanium implant surface modification was studied by the laser beam of energy density of 4.0 and 23.8 J/cm² (at 1064 nm) and 13.6 J/cm² (at 532 nm). The energy absorbed from the Nd:YAG laser beam is partially converted to thermal energy, which generates a series of effects, such as melting, vaporization of the molten material, shock waves, etc. The following titanium/implant surface morphological changes were observed: (i) both laser wavelengths cause damage of the titanium in the central zone of the irradiated area, (ii) appearance of a hydrodynamic feature in the form of resolidified droplets of the material in the surrounding outer zone with the 1064 nm laser wavelength and (iii) appearance of wave-like microstructures with the 532 nm wavelength. Generally, both laser wavelengths and the corresponding laser energy densities can efficiently enhance the titanium/implant roughness. This implant roughness is expected to improve its bio-integration. The process of the laser interaction with titanium implant was accompanied by formation of plasma.     

Laser through-hole drilling and laser cutting in teflon

We report a novel technique for laser high-speed drilling and cutting in teflon films. The new laser drilling surpasses the conventional techniques in simplicity, throughput and spatial resolution. The laser cutting and drilling process consists of three simple steps. First, a thin absorbing layer (in this case 300 Å of gold) is deposited on the teflon to allow for laser absorption. Second, the drilling is performed by pulsed-laser irradiation at the rate of one hole per pulse. The irradiation process does not completely open the holes in which debris still remain. Third, the ultrasonic cleaning in water is used to remove the modified and weakly bound material inside the drilled holes, leaving behind 50 m diameter through holes in 25 m thick teflon sheets. The drilling process-window is well mapped. The cutting process is obtained by fast scanning the laser beam at laser powers above a threshold value. This new technique is desirable for packaging because of its drilling speed as high as 60 000 holes per minute, its fast cutting and its low laser equipment cost.     

Application of the laser ablation for conservation of historical paper documents

Laser ablation was applied for surface cleaning and spectroscopic diagnostics of historical paper documents and model samples in the framework of the conservation projects. During cleaning the spectra of ablation products were recorded by means of the LIBS technique which allowed for nearly non-destructive identification of surface layers such as contaminants, substrate and pigments. For consecutive laser pulses a strong decrease of band intensities of the emission lines of Ca, Na, K, Al and Fe ascribed to contaminants were observed. The effect was used for monitoring of the cleaning progress of stained paper. For surface cleaning and spectra excitation the Q-switched Nd:YAG laser of 6 ns pulsewidth operating at wavelengths of 266, 355, 532, and 1064 nm and of fluence selected from the range 0.3-0.9 J/cm² was applied. The ablation parameters were optimized in agreement with the literature and the results were confirmed by surface studies and testing of the mechanical and chemical properties, and also by the response to the ageing process of the paper substrate. In case of the model paper irradiated in the UV range at 266 and 355 nm a visual inspection revealed local damages of the cellulose fibers accompanied by a decrease of the mechanical strength of the substrate. The effect was more pronounced after artificial ageing. The best results were obtained for samples irradiated at 532 nm and at laser fluence below the damage threshold of 0.6 J/cm², which is in agreement with literature.     

Highly efficient frequency doubling of high-energy Nd:YAG laser using a CsB3O5 crystal

We have demonstrated efficient frequency doubling of high-energy fundamental Nd:YAG laser pulse energy of the multi-joule (J) level at a high repetition rate using high optical-quality top-seeded solution growth CsB₃O₅(TSSG-CBO) crystal for the first time. Second-harmonic (532 nm) generation (SHG) output energy of 1.2 J at 10 Hz is obtained with a conversion efficiency of 60%. This result has been obtained at the multi-J level by the growth of high optical-quality TSSG-CBO crystal with the large effective nonlinear coefficient and high damage threshold. These results indicate that TSSG-CBO is a good candidate material for high-energy SHG of Nd-doped lasers at the several J level or more with high repetition rate.     

Enhanced near field mediated nanohole fabrication on silicon substrate by femtosecond laser pulse

Investigation of the process of nanohole formation on silicon surface mediated with near electromagnetic field enhancement in vicinity of gold particles is described. Gold nanospheres with diameters of 40, 80 and 200 nm are used. Irradiation of the samples with laser pulse at fluences below the ablation threshold for native Si surface, results in a nanosized surface modification. The nanostructure formation is investigated for the fundamental (λ = 800 nm, 100 fs) and the second harmonic (λ = 400 nm, 250 fs) of the laser radiation generated by ultrashort Ti:sapphire laser system. The near electric field distribution is analyzed by an Finite Difference Time Domain (FDTD) simulation code. The properties of the produced morphological changes on the Si surface are found to depend strongly on the polarization and the wavelength of the laser irradiation. When the laser pulse is linearly polarized the produced nanohole shape is elongated in the E-direction of the polarization. The shape of the hole becomes symmetrical when the laser radiation is circularly polarized. The size of the ablated holes depends on the size of the gold particles, as the smallest holes are produced with the smallest particles. The variation of the laser fluence and the particle size gives possibility of fabricating structures with lateral dimensions ranging from 200 nm to below 40 nm. Explanation of the obtained results is given on the basis simulations of the near field properties using FDTD model and Mie's theory.     

Carbon dendrite formation induced by pulsed laser irradiation

Porous carbon dendrite has been prepared by irradiating graphite targets with 532 nm, 10 ns laser pulses. The prepared samples were characterized by means of scanning electron microscopy, transmission electron microscopy and Raman spectroscopy. The measurement results show that carbon dendrite structures with cluster diameter of 10 nm were obtained on the irradiated target surface in an inert gas atmosphere. The evolution of target surface morphology induced by different laser intensities was investigated. The formation mechanism of the dendrite structure has been discussed in detail. The laser intensity plays an important role in the formation of the nanostructures and there exists an optimum intensity to prepare the carbon dendrite.     

Lasing from single, stationary, dye-doped glycerol/water microdroplets located on a superhydrophobic surface

We report laser emission from single, stationary, Rhodamine B-doped glycerol/water microdroplets located on a superhydrophobic surface. In the experiments, a pulsed, frequency-doubled Nd:YAG laser operating at 532 nm was used as the excitation source. The microdroplets ranged in diameter from a few to 20 μm. Lasing was achieved in the red-shifted portion of the dye emission spectrum with threshold fluences as low as 750 J/cm². Photobleaching was observed when the microdroplets were pumped above threshold. In certain cases, multimode lasing was also observed and attributed to the simultaneous lasing of two modes belonging to different sets of whispering gallery modes.     

Comparison of surface films formed on titanium by pulsed Nd:YAG laser irradiation at different powers and wavelengths in nitrogen atmosphere

The nitridation of titanium (Ti) caused by a Q-switched Nd:YAG laser under nitrogen gas atmosphere was investigated in situ using X-ray photoelectron spectroscopy (XPS). A laser having a wavelength of 1064 nm and 532 nm (SHG mode) was irradiated on a titanium substrate in an atmosphere-controlled chamber, and the substrate was then transported to an XPS analysis chamber without exposing it to air. The characteristics of the surface layer strongly depend on the laser power. When the power is relatively low, a titanium dioxide layer containing a small amount of nitrogen is formed on the substrate. Laser irradiation beyond a certain laser power is required to obtain a stoichiometric titanium nitride (TiN) layer. A TiN layer and an oxynitride layer with a TiO_xN_y-like structure are formed as the topmost and the lower surface layer, respectively, when the laser power exceeds this threshold value. The threshold laser power strongly depends on the wavelength of the laser, and this threshold value for the 532-nm laser is quite lower than that for the 1064-nm laser.     

Investigation of Nd:YVO4/YVO4 composite crystal and its laser performance pumped by a fiber coupled diode laser

Thermal effect control is critical to scale the output power of diode end-pumping solid lasers to several watts up and beyond. Diffusion bonding crystal has been demonstrated to be an effective method to relieve the thermal lens for the end-pumping laser crystal. The temperature distribution and thermal lens in Nd:YVO₄/YVO₄ composite crystal was numerically analyzed and compared with that of Nd:YVO4 crystal in this paper. The end-pumping Nd:YVO₄/YVO₄ composite crystal laser was set up and tested with z cavity. The maximum output power of 9.87 W at 1064 nm and 6.14 W at 532 nm were obtained at the pumping power of 16.5 W. The highest optical-optical conversion efficiencies were up to 60% at 1064 nm and 40% at 532 nm, respectively.     

Laser Shock Processing of 6061-T6 Al alloy with 1064 nm and 532 nm wavelengths

Laser Shock Processing (LSP) has been proposed as a competitive alternative technology to classical treatments for improving fatigue and wear resistance of metals. We present a configuration and results in the LSP concept for metal surface treatments in underwater laser irradiation at 532 nm and 1064 nm. The purpose of the work is to compare the effect of both wavelengths on the same material. A convergent lens is used to deliver 1.2 J/pulse (1064 nm) and 0.9 J/pulse (532 nm) in a 8 ns laser FWHM pulse produced by 10 Hz Q-switched Nd:YAG laser with spots of a 1.5 mm in diameter moving forward along the work piece. A LSP configuration with experimental results using a pulse density of 2500 pulses/cm² and 5000 pulses/cm² in 6061-T6 aluminum samples are presented. High level compressive residual stresses are produced using both wavelengths. It has been shown that surface residual stress level is comparable to that achieved by conventional shot peening, but with greater depths. This method can be applied to surface treatment of final metal products.     

Position-controlled synthesis of single-walled carbon nanotubes on a transparent substrate by laser-induced chemical vapor deposition

The synthesis of single-walled carbon nanotubes (SWCNTs) on a transparent substrate with multiple-catalyst layer (Fe/Al/Cr: 0.5/15/500 nm) using laser-induced chemical vapor deposition is reported. Ethylene (C₂H₄) mixed with hydrogen (H₂) and a continuous wave Nd:YVO₄ laser (532 nm) were used as the precursor gas and the irradiation source, respectively. It was found that the density and quality of the SWCNT dots varied sensitively to laser irradiance and chamber pressure. From subsequent micro-Raman analyses at different excitation sources (488, 514, 633, and 785 nm), the diameters of the SWCNTs were estimated to be within the range of 0.8-2 nm and that the SWCNT dots were composed of both semiconducting and metallic SWCNTs. It is demonstrated that an array of SWCNT dots can be fabricated at precisely controlled positions of a transparent substrate at room temperature with no need of catalysis patterning.     

Correction of small imperfections on white glazed china surfaces by laser radiation

A laser-assisted technique has been developed for correction of small diameter (1 mm) and shallow (0.5 mm) imperfections on the surface of gloss fired porcelain. To study the physics and establish the important parameters, artificially made holes in a porcelain sample have been first filled with correction material, then covered with raw glaze and treated by a pulsed, 7 kHz repetition rate CO₂ laser at 10.6 μm. The modification of the surface and the surrounding area have been quantified and studied with a large range of parameters of incident laser power (1-10 W), width of the laser pulses (10-125 μs) and duration of laser heating (60-480 s). Although the shine of the treated area, defined as the distribution of micro-droplets on the surface, is very similar to the untreated surfaces, the surroundings of the treated area usually show cracks. The measurement of both the spatial temperature distribution and the temporal cooling rate of the treated surface has revealed that a simple melting process always results in high gradient temperature distribution within the irradiated zone. Its inhomogeneous and fast cooling always generate at least micro-cracks on the surface within a few seconds after the laser was turned off. The duration and intensity of the laser irradiation have been then optimized in order to achieve the fastest possible melting of the surface, but without producing such high temperature gradients. To eliminate the cracks, more elaborated pre-heating and slowed-cooling-rate processes have been tried with prosperous results. These achievements complete our previous study, making possible to repair the most common surface imperfections and holes of gloss fired china samples.     

Nanosecond laser damage resistance of differently prepared semi-finished parts of optical multimode fibers

Optical multimode fibers are applied in materials processing (e.g. automotive industry), defense, aviation technology, medicine and biotechnology. One challenging task concerning the production of multimode fibers is the enhancement of laser-induced damage thresholds. A higher damage threshold enables a higher transmitted average power at a given fiber diameter or the same power inside a thinner fiber to obtain smaller focus spots.In principle, different material parameters affect the damage threshold. Besides the quality of the preform bulk material itself, the drawing process during the production of the fiber and the preparation of the fiber end surfaces influence the resistance. Therefore, the change of the laser-induced damage threshold of preform materials was investigated in dependence on a varying thermal treatment and preparation procedure.Single and multi-pulse laser-induced damage thresholds of preforms (F300, Heraeus) were measured using a Q-switched Nd:YAG laser at 1064 nm wavelength emitting pulses with a duration of 15 ns, a pulse energy of 12 mJ and a repetition rate of 10 Hz. The temporal and spatial shape of the laser pulses were controlled accurately.Laser-induced damage thresholds in a range from 150 J cm⁻² to 350 J cm⁻² were determined depending on the number of pulses applied to the same spot, the thermal history and the polishing quality of the samples, respectively.