Femtosecond laser surface processing (FLSP) is a material processing technique used to produce self-organized micro/nanostructures on metals. The hierarchal structures can improve the surface properties of materials when applied to specific applications such as enhancing heat transfer. In this paper, we demonstrate a recently developed technique termed multi-material, multi-layer FLSP (3ML-FLSP). With 3ML-FLSP, micro/nanoscale features can be produced that are composed of multiple materials by processing surfaces using traditional FLSP techniques that are layered with thin foils of different materials. We demonstrate results with three layers of different metals (304 stainless steel, copper, and aluminum) clamped together during laser processing to create structures composed of all three metals. Ion beam milling is used to cross-section structures for subsurface analysis of the microstructure. The three metals did not mix within the bulk of the microstructures indicating that the microstructures were produced primarily through preferential removal of material around the structures. However, there was mixing of all three materials within the nanoparticle layer that covers the microstructures.
We have shown recently that unique optical signatures can be observed with the measurement of ultrashort middle infrared laser pulses that have been transmitted through molecular vapors. Here, we report on an increased signal-to-noise ratio of the pulse measurements by using a cross-correlation technique with a lockin amplifier. Carbon tetrafluoride and dimethyl methylphosphonate (DMMP) cross-correlation signatures are highly discriminated using principal component analysis. A squared exponential Gaussian process regression model is used to quantitatively predict the concentration of DMMP.
Femtosecond laser surface processing (FLSP) is a unique material processing technique that can produce self-organized micro/nanostructures on most materials including metals, semiconductors, and dielectrics. These structures have demonstrated the enhancement of surface properties such as heat transfer and broadband light absorption. The chemical composition and morphology of FLSP structures is highly dependent on processing parameters including background gas composition, pressure, laser fluence, and number of laser pulses. When the laser processing is carried out in open atmosphere, a thick oxide layer forms on the FLSP surface structures due to the high reactivity of the surface with the environmental constituents immediately after laser processing. In this work, N2 and forming gas are used during laser processing in an effort to form a metal nitride on the surface of aluminum. Aluminum nitride is a promising material for enhancing the heat transfer performance of surfaces because of its thermal conductivity, which can be as high as 285 W/m-K, whereas aluminum oxide has a low thermal conductivity (30 W/m-K). Aluminum nitride incorporation into FLSP surfaces has the potential to act as a passivation layer to decrease the oxygen content and increase the thermal conductivity of the surface. Nitrogen incorporation is studied by applying FLSP in air, N2, and a 95% N2/5% H2 mixture. The chemical composition of the FLSP surfaces is determined by X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray spectroscopy (EDS). Cross-sectional analysis of the FLSP microstructures is performed using ion beam milling.
The capability to produce femtosecond laser pulses with wavelengths in the atmospheric absorption window requires a new understanding of pulse propagation effects. In this work, we characterize the changes in temporal propagation of middle infrared femtosecond laser pulses by cross-correlation frequency resolved optical gating (XFROG). The temporally distorted infrared pulses are cross-correlated with 800 nm pulses by a four-wave mixing process in air. For the first time, we investigate these propagation effects through gas molecules that are not present in the atmosphere. Each molecule is shown to have a unique effect on the temporal propagation of the pulse that is wavelength dependent. We verify our experimental data with simulations based on a KramersKronig transformation of spectral data from the HITRAN database. The propagation effects are similar to optical free induction decay. Multiple vibrational and rovibrational absorption lines are excited by the middle infrared pulse and constructive interference occurs at various delay times relative to the initial pulse. The constructive interference impresses a unique fingerprint onto the pulse because the spectral lines of each molecule are unique. The fingerprint behaves as a nonlinear function related to the molecular concentration. To account for this, a regression model is developed to predict the concentration of unknown gas species. The middle infrared beam is the only laser beam sensitive to the analytes. Thus, standoff detection is a possibility since the XFROG can be performed locally.
The use of self-organized micro/nanostructured surfaces formed using femtosecond laser surface processing (FLSP) techniques has become a promising area of research for enhancing surface properties of metals, with many applications including enhancing heat transfer. In this work, we demonstrate advantages of the use of dual-pulse versus single-pulse FLSP techniques to produce self-organized micro/nanostructures on copper. With the dual-pulse technique, the femtosecond pulses out of the laser (spaced 1 ms apart) are split into pulse pairs spaced < 1 ns apart and are focused collinear on the sample surface. Single-pulse FLSP techniques have been widely used to produce self-organized “mound-like” structures on a wide range of metals including a number of stainless steel alloys, aluminum, nickel, titanium, and recently on copper. Due to its high thermal conductivity, copper is used in many critical heat transfer applications and micro/nanostructured copper surfaces are desired to further improve heat transfer characteristics. Using single-pulse (pulses spaced 1 ms apart) FLSP techniques, self-organized microstructure formation on copper requires much higher pulse fluence than is commonly used for producing microstructures on other metals, which results in instabilities during laser processing (non-uniform surfaces), low processing efficiency, and limitations on the control of the types of structures produced. In this paper, we report results that demonstrate that the dual-pulse FLSP technique can be used to produce microstructures on copper more efficiently than using single-pulse FLSP, with better control of the surface structures produced. Cross-sectional subsurface microstructure analysis is also presented for single-pulse versus dual-pulse FLSP functionalized copper surfaces.
Femtosecond Laser Surface Processing (FLSP) is a versatile technique for the fabrication of a wide variety of micro/nanostructured surfaces with tailored physical and chemical properties. Through control over processing conditions such as laser fluence, incident pulse count, polarization, and incident angle, the size and density of both micrometer and nanometer-scale surface features can be tailored. Furthermore, the composition and pressure of the environment both during and after laser processing have a substantial impact on the final surface chemistry of the target material. FLSP is therefore a powerful tool for optimizing interfacial phenomena such as wetting, wicking, and phasetransitions associated with a vapor/liquid/solid interface. In the present study, we utilize a series of multiscale FLSPgenerated surfaces to improve the efficiency of vapor generation on a structured surface. Specifically, we demonstrate that FLSP of stainless steel 316 electrode surfaces in an alkaline electrolysis cell results in increased efficiency of the water-splitting reaction used to generate hydrogen. The electrodes are fabricated to be superhydrophilic (the contact angle of a water droplet on the surface is less than 5 degrees). The overpotential of the hydrogen evolution reaction (HER) is measured using a 3-electrode configuration with a structured electrode as the working electrode. The enhancement is attributed to several factors including increased surface area, increased wettability, and the impact of micro/nanostructures on the bubble formation and release. Special emphasis is placed on identifying and isolating the relative impacts of the various contributions.
Femtosecond laser surface processing (FLSP) is a powerful technique used to create self-organized microstructures with nanoscale features on metallic surfaces. By combining FLSP surface texturing with surface chemistry changes, either induced by the femtosecond laser during processing or introduced through post processing techniques, the wetting properties of metals can be altered. In this work, FLSP is demonstrated as a technique to create superhydrophobic surfaces on grade 2 titanium and 304 stainless steel that can retain an air film (plastron) between the surface and a surrounding liquid when completely submerged. It is shown that the plastron lifetime when submerged in distilled water or synthetic stomach acid is critically dependent on the specific degree of surface micro- and nano-roughness, which can be tuned by controlling various FLSP parameters. The longest plastron lifetime was on a 304 stainless steel sample that was submerged in distilled water and maintained a plastron for 41 days, the length of time of the study, with no signs of degradation. Also demonstrated for the first time is the precise control of pulse fluence and pulse count to produce three unique classes of surface micron/nano-structuring on titanium.
Femtosecond Laser Surface Processing (FLSP) is a powerful technique for the fabrication of self-organized multiscale
surface structures on metals that are critical for advanced control over energy transfer at a liquid/solid interface in
applications such as electrolysis. The efficiency of the hydrogen evolution reaction on stainless steel 316 electrodes in a
1 molar potassium hydroxide solution is used to analyze the role of surface geometry to facilitate the phase conversion of
the liquid to a gaseous state in the vicinity of the interface. It is found that the efficiency of the electrolysis process is
directly related to the separation of micro-scale features on an electrode surface. The enhancement is attributed to the
size of the valleys between microstructures controlling the contact between an evolving vapor bubble and the electrode
surface. The results suggest an alternative pathway for the tailoring of interfacial energy transfer on structured surfaces
separate from traditional benchmarks such as surface area and contact angle.
There are a growing number of unique self-organized micro/nanostructures created using femtosecond laser surface
processing that have been demonstrated. Although researchers have provided insight into the formation processes for
distinctive morphologies on specific materials, there is a need for a broader understanding of the physics behind the
formation of a wide range of morphologies and what parameters affect their formation. In this work, the formation
processes for mound structures on 316 stainless steel (SS) with growth above the original sample surface are studied.
The formation process for the structures on 316 SS is compared to similar structures formed on nickel using the same
technique. The structures are formed using 800 nm, 50 fs laser pulses, and are self-organized, meaning the structure
dimensions are much smaller than the spot size of the pulses used to create them. The formation dynamics were studied
using a stop-motion scanning electron microscope (SEM) technique, where the same location of an irradiated sample
was imaged in the SEM at various pulse counts. The result is a series of images showing the developmental progress
with increasing pulse counts. The structures form through a combination of fluid flow of the surface melt that results
after irradiation, preferential ablation of the center of the pits between structures, and material/nanoparticle redeposition.
We describe the evolution of laser damage spots on bulk nickel generated by multipulse femtosecond laser irradiation
with a 100 μm x 100 μm square flat-top beam profile as a function of the laser fluence and the number of pulses incident
on the target. This large-area irradiation simulates conditions associated with the interaction of femtosecond laser pulses
on a remote target. The larger area laser damage sites are characterized either by a series of self-organized surface
structures with micro- and nanoscale features or a deep circular pit rather than a crater that mirrors the beam profile.
Furthermore, the ablation rate of the deepest feature sharply increases above a laser fluence of 2 J/cm2; this increase is
associated with the creation of a deep circular ablation pit generated during ablation with the first few pulses on the
sample that continuously grows upon multipulse irradiation due to the focusing of incident laser energy into the pit by
the sloped pit surfaces.
We demonstrate a fiber-optic Raman probe based on single-crystal sapphire fibers to overcome the large background signal of Raman probes based on standard glass fibers. Using 514.5 nm and 785 nm excitation lasers, Raman spectroscopy was performed on samples of calcite, aqueous sodium carbonate solution, and silicon wafer using a single crystal sapphire fiber and a silica fiber of similar lengths and numerical apertures. The single-crystal sapphire fiber exhibits narrow Raman peaks and low background signal, allowing for the detection of weaker Raman signals or Raman signals located in the lower wavenumber region, while the traditional silica fiber has a strong broadband Raman spectrum of its own.
Free space optical communications using 9-10 fs pulses was investigated through aerosol clouds
approaching 104 to 105 particles per cm3 in a 15 cm long tube containing aerosol particles 4-5 μm in
diameter. This small size is representative of the most difficult situation for the transmission of light
through the atmosphere. The ultra fast pulse transmission were compared to continuous wave (cw)
transmission through the exact same aerosols clouds and compared to the ultra short pulses. Results
indicate that there was increased transmission for the ultra short laser pulses, but was not as high as
expected. The results now can be explained by a recent paper demonstrating that deviation from the Beer
Lambert law does not occur until the ultra short pulse transverses a longer path length in water. Results
will be presented on the pulse dispersion in water and glass.
Inspired by previous theoretical work, experiments on diffraction of 10 femtosecond ultrashort pulses passing through a single slit have been performed. Fringes are dramatically reduced or even eliminated in the diffraction of 10 fs ultrashort pulsed laser in the near field compared with that of the continuous-wave laser. This can be explained in the frequency domain as a result of the broadband spectrum contained in ultrashort pulses. Simulations are performed for Fresnel diffraction for both 10 fs ultrashort pulsed and continuous-wave lasers and the results agree with the experimental observation. The results of this work have important implication in biomedical imaging and remote imaging applications to name only a few.
Steam laser cleaning of alumina and titanium carbide nanoparticles from silicon substrates is presented. A KrF excimer laser with a wavelength of 248 nm was used to irradiate the substrates in laser cleaning. A water layer of micrometer thickness was deposited on silicon substrates to improve the cleaning process. Cleaning efficiency was measured for different laser fluences ranging from 50 to 250 mJ/cm2 and pulse numbers from 1 to 100. Research work was carried out to address the factors governing steam laser cleaning, during which thickness of water thin film and lift-off velocities of water films from Si substrate surfaces were monitored. In addition, one-dimensional simulations were employed to estimate the temperature increase on the material surfaces upon laser irradiation. Water layer thickness was measured using Fourier Transform Infrared Spectroscopy. Monitoring of both lift-off velocities and water thin film removal time were carried out by optical probing approaches using He-Ne laser of 632.8 nm wavelength.
There is a need in many scientific and manufacturing processes to drill to small diameter holes with high aspect ratios in both brittle materials as well as metals. Femtosecond lasers operating at 795 nm or frequency doubled to 400 nm provide a unique tool for carrying out these processes. In this work, the femtosecond laser nanomachining facilities at the University of Nebraska is discussed to drill 1 micrometers holes in Si/SiO2 with aspect rations > 8. The quality of the cut and the small nanoparticles are discussed.
Microfabrication of sub-micron holes on 30 nm thick aluminum films on fused silica was investigated using pulse durations form 300 fs to 6 ns at 400 nm wavelength. Micromachined areas were investigate using atomic force microscopy for quality and size of features produced. Ablation diameters less than 400 nm was achieved with all pulse widths. Pulses less than 5 ps removed the films cleanly and left a flat- bottomed crater with no evidence of substrate melting over a wide fluence range.
In this work we examine the feasibility of active thermal sensing of buried objects. A 1.5 kW carbon dioxide laser is used to provide a thermal impulse to the surface of a sand test bed containing simulated metallic landmines. Time- dependent thermal images of the induced surface temperature differentials are obtained using an infrared focal plane array imaging system. Experimental results are reported for two target sizes and four thermal pulse conditions. Quantitative evaluation of the induced surface temperature differentials as a function of time are presented.
Many chemical warfare agents are dispersed as small aerosol particles. In the past, most electro-optical excitation and detection schemes have used continuous or pulsed lasers with pulse lengths ranging from nanoseconds to microseconds. In this paper, we present interesting ongoing new results on femtosecond imaging and on the time dependent solutions to the scattering problem of a femtosecond laser pulse interacting with a single small aerosol particle. Results are presented for various incident pulse lengths. Experimental imaging results using femtosecond pulses indicate that the diffraction rings present when using nanosecond laser pulses for imaging are greatly reduced when femtosecond laser pulses are used. Results are presented in terms of the internal fields as a function of time and the optical size parameter.
Complex index-of-refraction values of RP-1 liquid rocket fuel are reported at laser wavelengths of 0.193 μm (ArF excimer), 0.4765 μm (argon ion), 0.488 μm (argon ion), 0.5145 μm (argon ion), 0.532 μm (Nd-YAG, frequency doubled), 0.6328 μm (He-Ne), 1.064 μm (Nd-YAG), and 10.5915 μm (CO2). The imaginary part of the index of refraction (k) is determined by traditional transmission methods. The real part (nr) at the specific laser lines is determined using reflectance measurements, critical-angle measurements, Mueller matrix elements, and Michelson interferometric measurements. Reflectance measurements are used to obtain nr at a wavelength of 0.193 μm. The critical-angle method is used to determine nr at 0.4765, 0.488, 0.5145, and 0.532 μm: the real part of the refractive index is obtained from Snell's law by measuring the critical angle. The real part of the refractive index at 0.6328 and 1.064 μm is derived from elements of the Mueller matrix, which are obtained using a TMA Technologies scatterometer. A Michelson interferometer is used to obtain phase shifts in a wedge cell, which are then used to calculate nr at 10.5915 μm. The need for many methods to measure the complex index of refraction is a result of the large changes in k over the wavelengths of interest.
Complex index of refraction values of RP-1 liquid rocket fuel are reported at laser wavelengths of 0.193 micrometers (ArF excimer), 0.5145 micrometers (argon-ion), 0.532 micrometers (Nd-YAG, frequency doubled), 1.064 micrometers (Nd-YAG), and 10.5915 micrometers (CO2). The imaginary part of the index of refraction (k) was determined by the traditional transmission method. The real part (n-r)) is determined by reflectance measurements, critical angle, Mueller matrix, and Michelson interferometer techniques. Reflectance measurements are used to obtain nr at a wavelength of 0.193 micrometers . Critical angle method is used to determine nr at 0.5145 micrometers and 0.532 micrometers . The real part of the refractive index is obtained from Snell's law by measuring the critical angle. The real part of the refractive index at 1.064 micrometers is derived based on elements of the Mueller matrix. Specular measurements were performed using a TMA scatterometer to obtain the Mueller matrix. A Michelson interferometer is used to determine nr at 10.5915 micrometers .
A computer program is being developed for the theoretical analysis of the propagation of a laser pulse optically focused within an aerosol spray. The computer program can be applied, for example, to analyze laser ignition arrangements where a focused laser pulse would be used to ignite a liquid aerosol fuel spray. Laser light scattering and absorption of the individual aerosol droplets are evaluated using electromagnetic Lorenz-Mie theory. Initially, beam propagation is being modeled using a simple modified paraxial theory. Arbitrary input parameters to the computer program describing the optical/laser/aerosol spray arrangement include the liquid volume fraction, average droplet size, droplet size distribution, laser wavelength, laser pulse energy, laser pulse duration, lens focal length, beam diameter incident on the lens, and the choice of aerosol liquid and surrounding gaseous medium (through arbitrary inputted values of the thermodynamic and optical properties of the aerosol liquid and the gaseous medium). The output of the computer program includes, as a function of spatial position along the laser propagation axis within the spray, the laser pulse intensity and energy, the overall volumetric absorption of laser energy by the aerosol liquid and by the gaseous medium, and the overall average temperature rise of the aerosol liquid and of the gaseous medium.
It is well known that CO2 laser reflectances of natural surfaces containing certain minerals, notably quartz, feldspar and kaolinite, exhibit differential reflectance features in the 9 - 11 micrometers mid-infrared spectral range. The use of off-normal reflectance ratios using measurements at four CO2 laser wavelengths to differentiate between various types of soil surfaces has been established. Off-normal reflectance ratios are observed to be relatively independent of incidence angle compared to ratios computed at normal incidence, which makes them suitable for field remote sensing applications. Road surface materials, such as concrete and asphalt, contain large quantities of quartz, and as such exhibit reflectance characteristics similar to soils. Our measurements indicate that it is, nevertheless, possible to discriminate between road and soil surfaces using off-normal reflectance ratios. Discrimination from soil surfaces is better for concrete compared to asphalt.
Systematic theoretical calculations are presented investigating (a) the external excitation of resonances within a spherical droplet using a focused laser beam, (b) the internal excitation of resonances within a spherical droplet due to an embedded source, and (c) the effect of droplet nonsphericity on resonance excitation.
Intensity ratios of the resonant Na((lambda) equals 589 nm) to H(alpha ) ((lambda) equals 656 nm) emission lines have been measured for 10 GW/cm2 KrF laser radiation ((lambda) = 248 nm, tpulse equals 17 ns) interacting with 50 micrometers diameter saltwater droplets as a function of position in the breakdown region parallel to the incident laser beam. Results indicate the H(alpha ) emission intensity is highly non-uniform through the plasma plume and is highest in the plume ejected back toward the laser beam. In contrast, the Na emission line intensity shows a much weaker spatial dependence as a function of position within the plasma plume. Calibration data are also reported for the ratio of Na to H(alpha ) emission intensities as a function of Na concentration (0-2000 ppm) for approximately equals 20 micrometers diameter monodisperse droplets located at a fixed observation point in the plasma plume. Future research will extend the ratioing technique to remotely measure droplet salt concentrations in polydisperse saltwater sprays.
Active mid-infrared backscatter characteristics of various agricultural crop leaves were measured at different wavelengths in the 9-11 m spectral range at varied angles of incidence under both co-polarized and cross-polarized conditions. Measurements indicate that differences exist in the backscatter signatures between crop species and also among different strains of the same species. Backscatter is also seen to depend on the leaf moisture. Our preliminary studies demonstrate the potential of using active mid-infrared backscatter characteristics to remotely identify certain crop fypes and monitor their leaf moisture content. 1.
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