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Paper des Monats
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Ti:sapphire laser pulses of 130 fs and 800 nm were focused on 3.2-7m-thick TiN films by a 60-mm focal length lens in air. The morphology of the ablated areas generated by laser pulses at a fluence slightly above the ablation threshold was characterized in dependence on the pulse number by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The cavity profiles, depths, diameters, and volumes were quantitatively evaluated by AFM. The polarization state of the laser light is discussed as a further parameter, in addition to fluence and pulse number, that influences and controls the ablation precision of these materials. It was observed that circularly polarized radiation enhances the average ablation rates and reduces the roughness in the cavities by a factor of 2-3 as compared to linearly polarized radiation of the same incident laser fluence. Special attention was paid to the interfacial region between the coating and substrate. Ultrashort-pulse laser drilling into the Si substrate revealed the generation of columnar features which even may surmount the original coating under laser conditions.
Some applications of polymer films require the microstructuring of partly uneven substrates. This cannot be achieved by conventional photolithography, usually performed with ultraviolet short-pulse lasers (excimer, fourth harmonic Nd:YAG). When processing thermally sensitive or undoped polymers with low optical absorption, the use of femtosecond laser pulses can improve the ablation precision, also reducing the heat-affected zone. Therefore, a Ti:sapphire laser system was employed to perform ablation experiments on polyimide (PI). The irradiated areas were evaluated by means of optical and scanning electron microscopy. Highly oriented ripple structures, which are related to the polarization state of the laser pulses, were observed in the cavities. The relationship between the ablation threshold fluence and the number of laser pulses applied to the same spot is described in accordance with an incubation model.
Laser ablation with femtosecond pulses (130 fs, wavelength 800 nm, repetition rate 2 Hz) was compared with nanosecond-pulse ablation (10 ns, wavelength 266 nm, repetition rate 2.5 Hz) of bariumalumoborosilicate glass in air using the direct focusing technique. Different ablation thresholds and heat-affected zones were observed. The lateral and vertical machining precision was evaluated. Single nanosecond laser pulses in the far UV resulted in a bubble or a circular hole in the centre of the illuminated spot, depending on the applied fluence. The ablation behaviour in the case of near-IR femtosecond pulses contrasted to this. Bubble formation was not detected. It needed repeated pulses at the same spot to modify the surface until material removal could be observed (incubation). Cavity dimensions of less than the beam diameter were achieved in this case.
Chemical, morphological and accumulation phenomena in ultrashort-pulse laser ablation of TiN in air
(2000)
Ultrashort-pulse laser ablation (F=130 fs, 5=800 nm, repetition rate 2-20 Hz) of titanium nitride was investigated for laser fluences between 0.3 and 4.5 J/cm2 using the direct focusing technique in air. The influence of the laser pulse number and the peak fluence was investigated by means of several surface analytical techniques (optical microscopy, dynamic friction atomic force microscopy, scanning Auger electron microscopy and small-spot electron spectroscopy for chemical analysis). The correlation of the results about optical, physical and chemical properties of the irradiated areas allows us to propose a simple oxidation model, which explains different observed phenomena associated with surface damage such as mound formation and crater widening and clarifies the incubation behavior reported earlier for this material.
Ultrashort pulse laser microstructuring (pulse duration 130 fs, wavelength 800 nm, repetition rate 2 Hz) of titanium nitride (TiN) films on silicon substrates was performed in air using the direct focusing technique. The lateral and vertical precision of laser ablation was evaluated. The TiN ablation threshold changed with the number of pulses applied to the surface due to an incubation effect. An ablation depth per pulse below the penetration depth of light was observed. Columnar structures were formed in the silicon substrate after drilling through the TiN layer.
Ablation experiments with ultrashort laser pulses (pulse duration 150 fs, wavelength 800 nm) on polymers (PC, PMMA) relevant for biomedical technology have been performed in air. The lateral and vertical machining precision was evaluated by optical, atomic force and scanning electron microscopy. The ablation threshold reaches values in the range of 0.52.5 J/cm2 and depends significantly on the number of laser pulses applied to the same spot. The hole diameters are influenced by the laser fluence and the number of laser pulses. The relation between the ablation threshold and the number of laser pulses applied to the same spot is described in accordance with an incubation model.
Ablation of indium phosphide wafers in air was performed with low repetition rate ultrashort laser pulses (130 fs, 10 Hz) of 800 nm wavelength. The relationships between the dimensions of the craters and the ablation parameters were analyzed. The ablation threshold fluence depends on the number of pulses applied to the same spot. The single-pulse ablation threshold value was estimated to be fth(1)=0.16 J/cm2. The dependence of the threshold fluence on the number of laser pulses indicates an incubation effect. Morphological and chemical changes of the ablated regions were characterized by means of scanning electron microscopy and Auger electron spectroscopy.
Physical and chemical phenomena resulting from irradiation of silicon and indium phosphide with ultrashort laser pulses (~100fs) were investigated
with respect to the difference between single- and multiple-pulse treatment. In the single-pulse case, several processes were identified: modification,
recrystallization and ablation. All processes exhibit a distinct treshold behaviour. A two photon-absorption coefficient can be determined from a single
spatial ablation profile. Accumulation effects were observed for multi-pulse illumination. Different morphological features like bubbles, rippels and
microcolumns were found.
We investigated the initial modification and ablation of crystalline silicon with single and multiple Ti:sapphire laser pulses of 5 to 400 fs duration. In accordance with earlier established models, we found the phenomena amorphization, melting, re-crystallization, nucleated vaporization, and ablation to occur with increasing laser fluence down to the shortest pulse durations. We noticed new morphological features (bubbles) as well as familiar ones (ripples, columns). A nearly constant ablation threshold fluence on the order of 0.2 J/cm2 for all pulse durations and multiple-pulse irradiation was observed. For a duration of ,100 fs, significant incubation can be observed, whereas for 5 fs pulses, the ablation threshold does not depend on the pulse number within the experimental error. For micromachining of silicon, a pulse duration of less than 500 fs is not advantageous.
The ultrafast laser ablation of silicon has been investigated experimentally and theoretically. The theoretical description is based on molecular dynamics (MD) simulations combined with a microscopic electronic model. We determine the thresholds of melting and ablation for two different pulse durations =20 and 500 fs. Experiments have been performed using 100 Ti:Sap-phire laser pulses per spot in air environment. The ablation thresholds were determined for pulses with a duration of 25 and 400 fs, respectively. Good agreement is obtained between theory and experiment.
Multiple pulse investigations of 130-fs Ti:sapphire laser-induced damage of a high reflecting mirror consisting of alternating ?/4-layers of Ta2O5 and SiO2 and a single 500-nm Ta2O5 film were performed. In both cases, fused silica served as the substrate. For a fixed number of 1000 laser pulses per spot, a decrease in the damage threshold fluence of the mirror by a factor of two was observed by changing the repetition rate from 10 Hz to 1 kHz. A single 500-nm Ta2O5 film shows higher damage resistance compared to the mirror. The mirror and the Ta2O5 film samples were partially coated with a 300-nm-thick aluminium layer. The aluminium coating does not influence the damage threshold of the dielectrics underneath.
The surface modification of single-crystalline silicon induced by single 130 femtosecond (fs) Ti:sapphire laser pulses (wavelength 800 nm) in air is investigated by means of micro Raman spectroscopy (?-RS), atomic force microscopy and scanning laser microscopy. Depending on the laser fluence, in some regions the studies indicate a thin amorphous top-layer as well as ablated and recrystallized zones. The single-pulse threshold fluences for melting, ablation and polycrystalline recrystallization are determined quantitatively. Several different topographical surface structures (rims and protrusions) are found. Their formation is discussed in the context of recent studies of the laser irradiation of silicon. In combination with a thin-film optical model, the thickness of the amorphous layer is determined by two independent and nondestructive optical methods to be in the order of several 10 nm.
Laser ablation of single-crystalline indium phosphide (InP) was performed in air by means of linearly polarized Ti : sapphire femtosecond pulses (800 nm, 130 fs, 10 Hz). As a result of the irradiation with a variable number of laser pulses per spot (N /spl les/ 5), several morphological changes (crater formation, rim formation, ripple structures, and cones) were observed. These effects were explored using force modulation microscopy (FMM), a technique based on scanning force microscopy, allowing the simultaneous imaging of both topography and local stiffness at a high lateral resolution. The first laser pulse induces the formation of a protruding rim (height < 20 nm, width /spl ap/ 300 nm) bordering the ablated crater. A Fourier analysis of the multipulse generated topographies reveals the formation of wavelength-sized periodic ripples (modulation depth < 100 nm) with an orientation perpendicular to that of the electric field vector of the laser radiation. Besides these morphological alterations, material modifications were also observed in the irradiated regions by means of the FMM technique. Within the ablated craters, local stiffness variations were found revealing an inhomogeneous material composition/structure as a consequence of the femtosecond pulse laser treatment.
Structure formation on the surface of indium phosphide irradiated by femtosecond laser pulses
(2005)
Laser-induced periodic surface structures (LIPSS; ripples) with different spatial characteristics have been observed after irradiation of single-crystalline indium phosphide (c-InP) with multiple linearly polarized femtosecond pulses (130 fs, 800 nm) in air. With an increasing number of pulses per spot, N, up to 100, a characteristic evolution of two different types of ripples has been observed, i.e., (i) the growth of a grating perpendicular to the polarization vector consisting of nearly wavelength-sized periodic lines and (ii), in a specific pulse number regime (N = 5-30), the additional formation of equally oriented ripples with a spatial period close to half of the laser wavelength. For pulse numbers higher than 50, the formation of micrometer-spaced grooves has been found, which are oriented perpendicular to the ripples. These topographical surface alterations are discussed in the frame of existing LIPSS theories.
Femtosecond time-resolved microscopy has been used to analyze the structural transformation dynamics (melting, ablation, and solidification phenomena) induced by single intense 130 fs laser pulses in single-crystalline (100)-indium phosphide wafers in air on a time scale from ~100 fs up to 8 ns. In the ablative regime close to the ablation threshold, transient surface reflectivity patterns are observed by fs microscopy on a ps to ns time scale as a consequence of the complex spatial density structure of the ablating material (dynamic Newton fringes). At higher fluences, exceeding six times the ablation threshold, optical breakdown causes another, more violent ablation regime, which reduces the energy deposition depth along with the time of significant material removal. As a consequence, ablation lasts longer in a ring-shaped region around the region of optical breakdown. This leads to the formation of a crater profile with a central protrusion. In the melting regime below the ablation threshold, the melting dynamics of indium phosphide has been quantified and subsequent superficial amorphization has been observed upon solidification on the ns time scale leading to amorphous layer thicknesses of the order of a few tens of nanometers.
Ablation of single-crystalline (100) indium phosphide wafer surfaces with single 10 fs Ti:sapphire laser pulses in air has been studied by means of complementary cross-sectional transmission electron microscopy, scanning force microscopy, and optical microscopy. A local protrusion of ~70 nm height is generated within the ablation craters for fluences exceeding 0.78 J/cm². This morphological feature has been studied in detail, revealing the material structure of the laser-affected zone and its spatial extent. The resolidified layer (60-200 nm thick) consists of polycrystalline grains (5-15 nm diameter) and is covered by an ~10 nm thick amorphous top layer. Interestingly, the sharp boundary of the solidified layer to the unaffected crystal underneath exhibits a Gaussian-like shape and does not follow the shape of the surface topography. Evidence is presented that the central crater protrusion is formed by near-surface optical breakdown, and that the absorption in the material transiently changes during the femtosecond-laser pulse.
The formation of nearly wavelength-sized laser-induced periodic surface structures (LIPSSs) on single-crystalline silicon upon irradiation with single or multiple femtosecond-laser pulses (pulse duration τ=130 fs and central wavelength λ=800 nm) in air is studied experimentally and theoretically. In our theoretical approach, we model the LIPSS formation by combining the generally accepted first-principles theory of Sipe and co-workers with a Drude model in order to account for transient intrapulse changes in the optical properties of the material due to the excitation of a dense electron-hole plasma. Our results are capable to explain quantitatively the spatial periods of the LIPSSs being somewhat smaller than the laser wavelength, their orientation perpendicular to the laser beam polarization, and their characteristic fluence dependence. Moreover, evidence is presented that surface plasmon polaritons play a dominant role during the initial stage of near-wavelength-sized periodic surface structures in femtosecond-laser irradiated silicon, and it is demonstrated that these LIPSSs can be formed in silicon upon irradiation by single femtosecond-laser pulses.
Near-IR femtosecond ( τ = 150 fs, λ = 775 nm, repetition rate 1 kHz) and VUV nanosecond (τ = 20 ns, λ = 157 nm, repetition rate 1 to 5 Hz) laser pulse ablation of single-crystalline TeO2 (c-TeO2, grown by the balance controlled Czochalski growth method) surfaces was performed in air using the direct focusing technique. The multi-method characterization using optical microscopy, atomic force microscopy and scanning electron microscopy revealed the surface morphology of the ablated craters. This allowed us to characterize precisely the lateral and vertical dimensions of the laser-ablated craters for different laser pulse energies and pulse numbers at each spot. Based on the obtained information, we quantitatively determined the ablation threshold fluence for the fs laser irradiation when different pulse numbers were applied to the same spot by using two independent extrapolation techniques. We found that in case of NIR femtosecond laser pulse irradiation, the ablation threshold significantly depends on the number of laser pulses applied to the same spot indicating that incubation effects play an important role in this material. In case of VUV ns laser pulses, the ablation rate is significantly higher due to the high photon energy and the predominantly linear absorption in the material. These results are discussed on the basis of recent models of the interaction of laser pulses with dielectrics.
We have studied plasma formation and relaxation dynamics along with the corresponding topography modifications in fused silica and sapphire induced by single femtosecond laser pulses (800 nm and 120 fs). These materials, representative of high bandgap amorphous and crystalline dielectrics, respectively, require nonlinear mechanisms to absorb the laser light. The study employed a femtosecond time-resolved microscopy technique that allows obtaining reflectivity and transmission images of the material surface at well-defined temporal delays after the arrival of the pump pulse which excites the dielectric material. The transient evolution of the free-electron plasma formed can be followed by combining the time-resolved optical data with a Drude model to estimate transient electron densities and skin depths. The temporal evolution of the optical properties is very similar in both materials within the first few hundred picoseconds, including the formation of a high reflectivity ring at about 7 ps. In contrast, at longer delays (100 ps20 ns) the behavior of both materials differs significantly, revealing a longer lasting ablation process in sapphire. Moreover, transient images of sapphire show a concentric ring pattern surrounding the ablation crater, which is not observed in fused silica. We attribute this phenomenon to optical diffraction at a transient elevation of the ejected molten material at the crater border. On the other hand, the final topography of the ablation crater is radically different for each material. While in fused silica a relatively smooth crater with two distinct regimes is observed, sapphire shows much steeper crater walls, surrounded by a weak depression along with cracks in the material surface. These differences are explained in terms of the most relevant thermal and mechanical properties of the material. Despite these differences the maximum crater depth is comparable in both material at the highest fluences used (16J/cm2). The evolution of the crater depth as a function of fluence can be described taking into account the individual bandgap of each material.
A new approach is presented to quantify the so-called "heat affected zone" (HAZ) during
femtosecond laser pulse processing. Ablation of titanium nitride (TiN) thin films (~3 μm
thickness) by multiple femtosecond laser pulses (τ=130 fs, λ=800 nm) in air environment was
studied by means of two different surface analytical methods both being sensitive to chemical
alterations at the surface. Scanning Auger electron microscopy was applied for a visualization of the
spatial distribution of specific elements (Ti, O) within the laser-modified areas. The chemical state
of the irradiated surface was revealed by complementary x-ray photoelectron spectroscopy. Both
methods were used for a depth-profiling chemical analysis (tracking the elements Ti, N, O, and C)
using an Ar-ion beam for surface sputtering. In a narrow laser fluence range slightly below the
ablation threshold of TiN significant superficial oxidation can be observed leading to the formation
of substoichiometric TiO2-x. At fluences above the ablation threshold, an increased titanium
concentration is observed within the entire ablation craters. Following upon sputter removal the
elemental distribution into the depth of the nonablated material, the results allow an estimation of
the heat-affected zone for femtosecond laser ablation in air environment. According to our analyses,
the HAZ extends up to a few hundreds of nanometers into the nonablated material.
Femtosecond (fs) laser pulse ablation (pulse duration of 150 fs, wavelength of 775 nm, repetition rate of 1 kHz) of single-crystalline TeO2 surfaces was performed in air using the direct focusing technique. The lateral and vertical dimensions of laser ablated craters as well as the laser damage thresholds were evaluated for different pulse numbers applied to the same spot. The joint observation using optical microscopy, atomic force microscopy and scanning electron microscopy revealed the surface morphology of the ablated craters and also showed that the ablation threshold depends significantly on the number of laser pulses applied to the same spot due to incubation effects. The incubation effects change the absorption processes involved in fs-laser ablation of the transparent material from multiphoton absorption to a single-photon absorption. These results are discussed on the basis of recent models of the interaction of fs-laser pulses with dielectrics.
The irradiation of single-crystalline indium phosphide (c-InP) by Ti:sapphire femtosecond laser pulses (130 fs, 800 nm) in air is studied by means of in-situ time resolved reflectivity measurements [fs-time-resolved microscopy (100 fs-10 ns) and point probing analysis (ns - µs)] and by complementary ex-situ surface analytical methods (Micro Raman Spectroscopy, Scanning Force, and Optical Microscopy). The dynamics of melting, ablation, and optical breakdown as well as structural changes resulting from rapid solidification are investigated in detail. Different laser-induced surface morphologies are characterized and discussed on the basis of recent ablation and optical breakdown models.
The formation of nearly wavelength-sized laser-induced periodic surface structures (LIPSS) on
single-crystalline silicon upon irradiation with single (N = 1) and multiple (N ≤ 1000) linearly
polarized femtosecond (fs) laser pulses (pulse duration τ = 130 fs, central wavelength λ = 800 nm)
in air is studied experimentally. Scanning electron microscopy (SEM) and optical microscopy are
used for imaging of the ablated surface morphologies, both revealing LIPSS with periodicities close
to the laser wavelength and an orientation always perpendicular to the polarization of the fs-laser
beam. It is experimentally demonstrated that these LIPSS can be formed in silicon upon irradiation
by single fs-laser pulses—a result that is additionally supported by a recent theoretical model.
Two-dimensional Fourier transforms of the SEM images allow the detailed analysis of the
distribution of the spatial frequencies of the LIPSS and indicate, at a fixed peak fluence, a
monotonous decrease in their mean spatial period between ~770 nm (N = 1) and 560 nm (N
= 1000). The characteristic decrease in the LIPSS period is caused by a feedback-mechanism acting
upon excitation of surface plasmon polaritons at the rough silicon surface which is developing under
the action of multiple pulses into a periodically corrugated surface.
One wavelength fits all
(2011)
Structuring of Thin-film Solar Cells with a Single Laser Wavelength Structuring of a PV module into a number of cells is necessary to lower the current and to increase the voltage, and is typically accomplished with nanosecond laser pulses of different wavelengths. Duetothe many available laser sources, complex and expensive scribing Setups are necessary. To overcome this a concept for laser structuring of thin-film PV modules using a single wavelength allows prediction ofthe ablation behaviourfor a given laser pulse energy.
The formation of laser-induced periodic surface structures (LIPSS) upon irradiation of fused silica with multiple irradiation sequences consisting of five Ti:sapphire femtosecond (fs) laser pulse pairs (150 fs, 800 nm) is studied experimentally. A Michelson interferometer is used to generate near-equal-energy double-pulse sequences with a temporal pulse delay from -20 to +20 ps between the cross-polarized individual fs-laser pulses (~0.2 ps resolution). The results of multiple double-pulse irradiation sequences are characterized by means of Scanning Electron and Scanning Force Microscopy. Specifically in the sub-ps delay domain striking differences in the surface morphologies can be observed, indicating the importance of the laser-induced free-electron plasma in the conduction band of the solids for the formation of LIPSS.
We describe a method to visualize ultrafast laser-induced refractive index changes in transparent materials with a 310 fs impulse response and a submicrometer spatial resolution. The temporal profile of the laser excitation sequence can be arbitrarily set on the subpicosecond and picosecond time scales with a pulse shaping unit, allowing for complex laser excitation. Time-resolved phase contrast microscopy reveals the real part of the refractive index change and complementary time-resolved optical transmission microscopy measurements give access to the imaginary part of the refractive index in the irradiated region. A femtosecond laser source probes the complex refractive index changes from the excitation time up to 1 ns, and a frequency-doubled Nd:YAG laser emitting 1 ns duration pulses is employed for collecting data at longer time delays, when the evolution is slow. We demonstrate the performance of our setup by studying the energy relaxation in a fused silica sample after irradiation with a double pulse sequence. The excitation pulses are separated by 3 ps. Our results show two dimensional refractive index maps at different times from 200 fs to 100 µs after the laser excitation. On the subpicosecond time scale we have access to the spatial characteristics of the energy deposition into the sample. At longer times (800 ps), time-resolved phase contrast microscopy shows the appearance of a strong compression wave emitted from the excited region. On the microsecond time scale, we observe energy transfer outside the irradiated region.
The formation of laser-induced periodic surface structures (LIPSS) upon irradiation of silicon wafer surfaces by linearly polarized Ti:sapphire femtosecond laser pulses (pulse duration 130 fs, central wavelength 800 nm) is studied experimentally and theoretically. In the experiments, so-called low-spatial frequency LIPSS (LSFL) were found with periods smaller than the laser wavelength and an orientation perpendicular to the polarization. The experimental results are analyzed by means of a new theoretical approach, which combines the widely accepted LIPSS theory of Sipe et al. with a Drude model, in order to account for transient (intra-pulse) changes of the optical properties of the irradiated materials. It is found that the LSFL formation is caused by the excitation of surface plasmon polaritons, SPPs, once the initially semiconducting material turns to a metallic state upon formation of a dense free-electron-plasma in the material and the subsequent interference between its electrical field with that of the incident laser beam resulting in a spatially modulated energy deposition at the surface. Moreover, the influence of the laser-excited carrier density and the role of the feedback upon the multi-pulse irradiation and its relation to the excitation of SPP in a grating-like surface structure is discussed.
Single-pulse femtosecond (fs) (pulse duration ~200 fs, wavelength 398 nm) and nanosecond (ns) (pulse duration 4 ns, wavelength 355 nm) laser ablation have been applied in combination with time-of-flight mass spectrometer (TOFMS) to analyze the elemental composition of the plasma plume of single-crystalline telluria (c-TeO2, grown by the balance controlled Czochralski growth method). Due to the three-order difference of the peak intensities of the ns and fs-laser pulses, significant differences were observed regarding the laser-induced species in the plasma plume. Positive singly, doubly and triply charged Te ions (Te+, Te2+, Te3+) in the form of their isotopes were observed in case of both irradiations. In case of the ns-laser ablation the TeO+ formation was negligible compared to the fs case and there was no Te trimer (Te3+) formation observed. It was found that the amplitude of Te ion signals strongly depended on the applied laser pulse energy. Singly charged oxygen ions (O+) are always present as a byproduct in both kinds of laser ablation.
The formation of laser-induced periodic surface structures (LIPSS) upon irradiation of fused silica with multiple irradiation sequences of parallel polarized Ti:sapphire femtosecond laser pulse pairs (160 fs pulse duration, 800 nm central wavelength) was studied experimentally. For that purpose, a Michelson interferometer was used to generate near-equal-energy double-pulse sequences allowing the temporal pulse delay between the parallel-polarized individual fs-laser pulses to be varied between 0 and 40 ps with ~0.2 ps temporal resolution. The surface morphologies of the irradiated surface areas were characterized by means of scanning electron and scanning force microscopy. In the sub-ps delay range a strong decrease of the LIPSS periods and the ablation crater depths with the double-pulse delay was observed indicating the importance of the laser-induced free-electron plasma in the conduction band of the solids for the formation of LIPSS.
The effects of femtosecond laser pulse irradiation on the glass structure of alkaline silicate glasses were investigated by x-ray absorption near edge structure spectroscopy using the beamline of the Physikalisch-Technische Bundesanstalt at the electron synchrotron BESSY II in Berlin (Germany) by analyzing the magnesium Κ-edge absorption peak for different laser fluences. The application of fluences above the material modification threshold (2.1 J/cm²) leads to a characteristic shift of ~1.0 eV in the Κ-edge revealing a reduced (~3%) mean magnesium bond length to the ligated oxygen ions (Mg-O) along with a reduced average coordination number of the Mg ions.
The formation of laser-induced periodic surface structures (LIPSS) in different materials (metals, semiconductors, and dielectrics) upon irradiation with linearly polarized fs-laser pulses (τ~30–150 fs, λ~800 nm) in air environment is studied experimentally and theoretically. In metals, predominantly low-spatial-frequency-LIPSS with periods close to the laser wavelength λ are observed perpendicular to the polarization. Under specific irradiation conditions, high-spatial-frequency-LIPSS with sub-100-nm spatial periods (~λ/10) can be generated. For semiconductors, the impact of transient changes of the optical properties to the LIPSS periods is analyzed theoretically and experimentally. In dielectrics, the importance of transient excitation stages in the LIPSS formation is demonstrated experimentally using (multiple) double-fs-laser-pulse irradiation sequences. A characteristic decrease of the LIPSS periods is observed for double-pulse delays of less than 2 ps.
The formation of laser-induced periodic surface structures (LIPSS) on two different silica polymorphs (single-crystalline synthetic quartz and commercial fused silica glass) upon irradiation in air with multiple linearly polarized single- and double-fs-laser pulse sequences (τ = 150 fs pulse duration, λ = 800nm center wavelength, temporal pulse separation Δt < 40 ps) is studied experimentally and theoretically. Two distinct types of fs-LIPSS [so-called low-spatial-frequency LIPSS (LSFL) and high-spatial-frequency LIPSS (HSFL)] with different spatial periods and orientations were identified. Their appearance was characterized with respect to the experimental parameters peak laser fluence and number of laser pulses per spot. Additionally, the 'dynamics' of the LIPSS formation was addressed in complementary double-fs-pulse experiments with varying delays, revealing a characteristic change of the LSFL periods. The experimental results are interpreted on the basis of a Sipe-Drude model considering the carrier dependence of the optical properties of fs-laser excited silica. This new approach provides an explanation of the LSFL orientation parallel to the laser beam polarisation in silica—as opposed to the behaviour of most other materials.
Femtosecond diffraction dynamics of laser-induced periodic surface structures on fused silica
(2013)
The formation of laser-induced periodic surface structures (LIPSS) on fused silica upon irradiation with linearly polarized fs-laser pulses (50 fs pulse duration, 800?nm center wavelength) is studied experimentally using a transillumination femtosecond time-resolved (0.1 ps-1 ns) pump-probe diffraction approach. This allows to reveal the generation dynamics of near-wavelength-sized LIPSS showing a transient diffraction at specific spatial frequencies even before a corresponding permanent surface relief was observed. The results confirm that the ultrafast energy deposition to the materials surface plays a key role and triggers subsequent physical mechanisms such as carrier scattering into self-trapped excitons.
We report self-assembly of periodic surface structures in a commercial block copolymer (BCP) (Filofocon A) upon irradiation with a few tens of excimer laser pulses (20 ns, 193 nm) at fluences above the ablation threshold. This new type of structures is characterized by much larger periods than those characteristic for Laser-Induced Periodic Surface Structures (LIPSS) and features nanochains instead of ripples. We find a period of 790?nm at 400 mJ/cm², scaling linearly with laser fluence up to a maximum of 1.0 µm. While an entangled random network of nanochains is produced for normal-incidence and non-polarized light, nanochain alignment can be achieved either by irradiation at an angle or by using linearly polarized light, forming a lamella-like structure. In both cases, the nanochains are aligned parallel to the penetrating polarization orientation and their period does not show a dependence on the angle of incidence, as opposed to the general behavior of standard LIPSS. Also, our results show that the chains are not formed by frozen capillary waves. In contrast, we show analogies of the nanochains produced to lamellar structures fabricated on a smaller scale in other BCP. We discuss the origin of the self-assembly process in terms of a combination of chemical (BCP), optical (surface scattering), and thermal (melting, coarsening, and ablation) effects.
The formation of near-wavelength laser-induced periodic surface structures (LIPSS) on silicon upon irradiation with sequences of Ti:sapphire femtosecond laser pulse pairs (pulse duration 150 fs, central wavelength 800 nm) is studied theoretically. For this purpose, the nonlinear generation of conduction band electrons in silicon and their relaxation is numerically calculated using a two-temperature model approach including intrapulse changes of optical properties, transport, diffusion and recombination effects. Following the idea that surface plasmon polaritons (SPP) can be excited when the material turns from semiconducting to metallic state, the 'SPP active area' is calculated as function of fluence and double-pulse delay up to several picoseconds and compared to the experimentally observed rippled surface areas. Evidence is presented that multi-photon absorption explains the large increase of the rippled area for temporally overlapping pulses. For longer double-pulse delays, relevant relaxation processes are identified. The results demonstrate that femtosecond LIPSS on silicon are caused by the excitation of SPP and can be controlled by temporal pulse shaping.
Nonlinear optical properties such as the nonlinear refractive index and nonlinear absorption are characterized by z-scan measurements for a series of silicate glasses upon irradiation with laser pulses of 130 fs duration and 800 nm center wavelength. The stoichiometry of the silicate glasses is varied systematically to reveal the influence of the glass composition on the nonlinear optical properties. Additionally, the thermal properties such as glass–transformation temperature and thermal expansion coefficient are obtained from dilatometric measurements. It is found that the nonlinear refractive index is mainly related to the silica matrix. The nonlinear absorption is increased with the addition of network–forming ions.
The removal of a 75- to 90-nm-thick passivating silicon nitride antireflection coating from standard textured multicrystalline silicon photovoltaic wafers with a typical diffused 90-Ω/sq-emitter upon irradiation with near-infrared femtosecond laser pulses (790 nm central wavelength, 30 fs pulse duration) is studied experimentally. The laser irradiation areas are subsequently characterized by complementary optical microscopy, scanning electron microscopy and depth profiling chemical analyses using secondary ion mass spectrometry. The results clarify the thin-film femtosecond laser ablation scenario and outline the process windows for selective antireflection coating removal.
The formation of laser-induced periodic surface structures (LIPSS) upon irradiation of fused silica and silicon with multiple (NDPS) irradiation sequences consisting of linearly polarized femtosecond laser pulse pairs (pulse duration ~150 fs, central wavelength ~800 nm) is studied experimentally. Nearly equal-energy double-pulse sequences are generated allowing the temporal pulse delay Δt between the cross-polarized individual fs-laser pulses to be varied from -40 ps to +40 ps with a resolution of ~0.2 ps. The surface morphologies of the irradiated surface areas are characterized by means of scanning electron and scanning force microscopy. Particularly for dielectrics in the sub-ps delay range striking differences in the orientation and spatial characteristics of the LIPSS can be observed. For fused silica, a significant decrease of the LIPSS spatial periods from ~790 nm towards ~550 nm is demonstrated for delay changes of less than ~2 ps. In contrast, for silicon under similar irradiation conditions, the LIPSS periods remain constant (~760 nm) for delays up to 40 ps. The results prove the impact of laser-induced electrons in the conduction band of the solid and associated transient changes of the optical properties on fs-LIPSS formation.
The formation of laser-induced periodic surface structures (LIPSS) on titanium upon irradiation with linearly polarized femtosecond (fs) laser pulses (τ = 30 fs, λ = 790 nm) in an air environment is studied experimentally and theoretically. In the experiments, the dependence on the laser fluence and the number of laser pulses per irradiation spot has been analyzed. For a moderate number of laser pulses (N < 1000) and at fluences between ~0.09 and ~0.35 J/cm², predominantly low-spatial-frequency-LIPSS with periods between 400 nm and 800 nm are observed perpendicular to the polarization. In a narrow fluence range between 0.05 and 0.09 J/cm², high-spatial-frequency-LIPSS with sub-100-nm spatial periods (~λ/10) can be generated with an orientation parallel to the polarization (N = 50). These experimental results are complemented by calculations based on a theoretical LIPSS model and compared to the present literature.
The formation of laser-induced periodic surface structures (LIPSS) upon irradiation of fused silica with multiple irradiation sequences consisting of laser pulse pairs (50 fs single-pulse duration) of two different wavelengths (400 and 800 nm) is studied experimentally. Parallel polarized double-pulse sequences with a variable delay Δt between -10 and +10 ps and between the individual fs-laser pulses were used to investigate the LIPSS periods versus Δt. These two-color experiments reveal the importance of the ultrafast energy deposition to the silica surface by the first laser pulse for LIPSS formation. The second laser pulse subsequently reinforces the previously seeded spatial LIPSS frequencies.
The effects of single femtosecond laser pulse irradiation (130 fs pulse duration, 800 nm center wavelength) on the structure of binary lithium silicate glasses of varying chemical compositions were investigated by micro-Raman spectroscopy. Permanent modifications were generated at the surface of the glass samples with varying laser fluences in the ablative regime and evaluated for changes in the corresponding Raman band positions and bandwidths. For increasing laser fluences, the position of certain Raman bands changed, indicating an increase in the mass density of the glass inside the irradiated area. Simultaneously, the widths of all investigated bands increased, indicating a higher degree of disorder in the glass structure with respect to bond-angle and bond-length variations.
The formation of laser-induced periodic surface structures upon irradiation of titanium, silicon, and fused silica with multiple irradiation sequences consisting of parallel polarized Ti:sapphire femtosecond laser pulse pairs (pulse duration 50–150 fs, central wavelength ~800 nm) is studied experimentally. The temporal delay between the individual near-equal energy fs-laser pulses was varied between 0 and 5 ps with a temporal resolution of better than 0.2 ps. The surface morphology of the irradiated surface areas is characterized by means of scanning electron microscopy (SEM). In all materials a decrease of the rippled surface area is observed for increasing delays. The characteristic delay decay scale is quantified and related to material dependent excitation and energy relaxation processes.
The irradiation of ~0.9-µm-thick hydrogenated amorphous carbon (a-C:H) layers deposited on silicon substrates with single femtosecond (fs) laser pulses (35 fs pulse duration, 790 nm centre wavelength) in air is studied experimentally. Irradiation spots have been generated with different peak fluences and subsequently investigated by optical topometry, micro Raman spectroscopy and microscale mechanical indentation in order to evaluate their microscopic, topographical, structural and mechanical properties (e.g. elastic modulus). By this multi-method approach, a clear separation of different effects (delamination and graphitisation) becomes possible. The joint application of mechanical and spectroscopic techniques provides unique insights into the effects of the fs-laser radiation on the carbon layer.
The relation between ablation threshold fluence upon femtosecond laser pulse irradiation and the average dissociation energy density of silicate based multicomponent glass is studied. A simple model based on multiphoton absorption quantifies the absorbed energy density at the ablation threshold fluence. This energy density is compared to a calculated energy density which is necessary to decompose the glass compound into its atomic constituents. The results confirm that this energy density is a crucial intrinsic material parameter for the description of the femtosecond laser ablation threshold fluence of dielectrics.
The redeposited material (debris) resulting from ablation of a potassium–magnesium silicate glass upon scanning femtosecond laser pulse irradiation (130 fs, 800 nm) in air environment is investigated by means of three complementary surface analytical methods. Changes in the electronic band structure of the glass constituent Magnesium (Mg) were identified by X-ray Absorption Near Edge Structure spectroscopy (XANES) using synchrotron radiation. An up-shift of ≈0.8 eV of a specific Magnesium Κ-edge absorption peak in the spectrum of the redeposited material along with a significant change in its leading edge position was detected. In contrast, the surface left after laser ablation exhibits a downshift of the peak position by ≈0.9 eV. Both observations may be related to a change of the Mg coordinative state of the laser modified/redeposited glass material. The presence of carbon in the debris is revealed by micro Raman spectroscopy (µ-RS) and was confirmed by energy dispersive X-ray spectroscopy (EDX). These observations are attributed to structural changes and chemical reactions taking place during the ablation process.
Laser-induced periodic surface structures (LIPSS, ripples) were generated on stainless steel (100Cr6) and titanium alloy (Ti6Al4V) surfaces upon irradiation with multiple femtosecond laser pulses (pulse duration 30 fs, central wavelength 790 nm). The experimental conditions (laser fluence, spatial spot overlap) were optimized in a sample-scanning geometry for the processing of large surface areas (5 × 5 mm²) covered homogeneously by the nanostructures. The irradiated surface regions were subjected to white light interference microscopy and scanning electron microscopy revealing spatial periods around 600 nm. The tribological performance of the nanostructured surface was characterized by reciprocal sliding against a ball of hardened steel in paraffin oil and in commercial engine oil as lubricants, followed by subsequent inspection of the wear tracks. For specific conditions, on the titanium alloy a significant reduction of the friction coefficient by a factor of more than two was observed on the laser-irradiated (LIPSS-covered) surface when compared to the non-irradiated one, indicating the potential benefit of laser surface structuring for tribological applications.
The formation of laser-induced periodic surface structures (LIPSS, ripples) upon irradiation of silicon with multiple irradiation sequences consisting of femtosecond laser pulse pairs (pulse duration 150 fs, central wavelength 800 nm) is studied numerically using a rate equation system along with a two-temperature model accounting for one- and two-photon absorption and subsequent carrier diffusion and Auger recombination processes. The temporal delay between the individual equal-energy fs-laser pulses was varied between 0 and ~4 ps for quantification of the transient carrier densities in the conduction band of the laser-excited silicon. The results of the numerical analysis reveal the importance of carrier generation and relaxation processes in fs-LIPSS formation on silicon and quantitatively explain the two time constants of the delay-dependent decrease of the low spatial frequency LIPSS (LSFL) area observed experimentally. The role of carrier generation, diffusion and recombination is quantified individually.
The formation of laser-induced periodic surface structures (LIPSS) upon irradiation of silicon by multiple (N = 100) linearly polarized Ti:sapphire femtosecond laser pulses (duration τ = 30 fs, center wavelength λ0 ~ 790 nm) is studied experimentally in air and water environment. The LIPSS surface morphologies are characterized by scanning electron microscopy and their spatial periods are quantified by two-dimensional Fourier analyses. It is demonstrated that the irradiation environment significantly influences the periodicity of the LIPSS. In air, so-called low-spatial frequency LIPSS (LSFL) were found with periods somewhat smaller than the laser wavelength (ΛLSFL ~ 0.7 × λ0) and an orientation perpendicular to the laser polarization. In contrast, for laser processing in water a reduced ablation threshold and LIPSS with approximately five times smaller periods ΛLIPSS ~ 0.15 × λ0 were observed in the same direction as in air. The results are discussed within the frame of recent LIPSS theories and complemented by a thin film based surface plasmon polariton model, which successfully describes the tremendously reduced LIPSS periods in water.
Single-pulse (532 nm, 8 ns) micropatterning of silicon with nanometric surface modulation is demonstrated by irradiating through a diffracting pinhole. The irradiation results obtained at fluences above the melting threshold are characterized by scanning electron and scanning force microscopy and reveal a good agreement with Fresnel diffraction theory. The physical mechanism is identified and discussed on basis of both thermocapillary and chemicapillary induced material transport during the molten state of the surface.
The dynamics of the formation of laser-induced periodic surface structures (LIPSS) on fused silica upon irradiation with linearly polarized fs-laser pulses (50 fs pulse duration) is studied by cross-polarized two-color double-fs-pulse experiments. In order to analyze the relevance of temporally distributed energy deposition in the early stage of LIPSS formation, a Mach-Zehnder interferometer was used for generating multiple double-pulse sequences at two different wavelengths (400 and 800 nm). The inter-pulse delay between the individual cross-polarized pulses of each sequence was systematically varied in the sub-ps range and the resulting LIPSS morphologies were characterized by scanning electron microscopy. It is found that the polarization of the first laser pulse arriving to the surface determines the orientation and the periodicity of the LIPSS. These two-color experiments further confirm the importance of the ultrafast energy deposition to the silica surface for LIPSS formation, particularly by the first laser pulse of each sequence. The second laser pulse subsequently reinforces the previously seeded spatial LIPSS characteristics (period, orientation).
Laser-induced periodic surface structures (LIPSS, ripples) were processed on steel (X30CrMoN15-1) and titanium (Ti) surfaces by irradiation in air with linear polarized femtosecond laser pulses with a pulse duration of 30 fs at 790 nm wavelength. For the processing of large LIPSS covered surface areas (5 mm × 5 mm), the laser fluence and the spatial spot overlap were optimized in a sample-scanning geometry. The laser-processed surfaces were characterized by optical microscopy (OM), white light interference microscopy (WLIM) and scanning electron microscopy (SEM). Spatial LIPSS periods between 450 and 600 nm were determined. The nanostructured surface regions were tribologically tested under reciprocal sliding conditions against a 10-mm diameter ball of hardened 100Cr6 steel. Paraffin oil and engine oil were used as lubricants for 1000 sliding cycles at 1 Hz with a normal load of 1.0 N. The corresponding wear tracks were analyzed by OM and SEM. In particular cases, the laser-generated nanostructures endured the tribological treatment. Simultaneously, a significant reduction of the friction coefficient and the wear was observed in the laser-irradiated (LIPSS-covered) areas when compared to the non-irradiated surface. The experiments reveal the potential benefit of laser surface structuring for tribological applications.
Two-color double-fs-pulse experiments were performed on silicon wafers to study the temporally distributed energy deposition in the formation of laser-induced periodic surface structures (LIPSS). A Mach-Zehnder interferometer generated parallel or cross-polarized double-pulse sequences at 400 and 800 nm wavelength, with inter-pulse delays up to a few picoseconds between the sub-ablation 50-fs-pulses. Multiple two-color double-pulse sequences were collinearly focused by a spherical mirror to the sample. The resulting LIPSS characteristics (periods, areas) were analyzed by scanning electron microscopy. A wavelength-dependent plasmonic mechanism is proposed to explain the delay-dependence of the LIPSS. These two-color experiments extend previous single-color studies and prove the importance of the ultrafast energy deposition for LIPSS formation.
Single- and two-color double-fs-pulse experiments were performed on titanium to study the dynamics of the formation of laser-induced periodic surface structures (LIPSS). A Mach-Zehnder inter-ferometer generated polarization controlled (parallel or cross-polarized) double-pulse sequences in two configurations – either at 800 nm only, or at 400 and 800 nm wavelengths. The inter-pulse delays of the individual 50-fs pulses ranged up to some tens of picoseconds. Multiple of these single- or two-color double-fs-pulse sequences were collinearly focused by a spherical mirror to the sample surface. In both experimental configurations, the peak fluence of each individual pulse was kept below its respective ablation threshold and only the joint action of both pulses lead to the formation of LIPSS. Their resulting characteristics were analyzed by scanning electron microscopy and the periods were quantified by Fourier analyses. The LIPSS periods along with the orientation allow a clear identification of the pulse which dominates the energy coupling to the material. A plasmonic model successfully explains the delay-dependence of the LIPSS on titanium and confirms the importance of the ultrafast energy deposition stage for LIPSS formation.
Ultrafast laser processing can be used to realize various morphological surface transformations, ranging from direct contour shaping to large-area-surface functionalization via the generation of “self-ordered” micro- and nanostructures as well as their hierarchical hybrids. Irradiation with high-intensity laser pulses excites materials into extreme conditions, which then return to equilibrium through these unique surface transformations. In combination with suitable top-down or bottom-up manufacturing strategies, such laser-tailored surface morphologies open up new avenues toward the control of optical, chemical, and mechanical surface properties, featuring various technical applications especially in the fields of photovoltaics, tribology, and medicine. This article reviews recent efforts in the fundamental understanding of the formation of laser-induced surface micro- and nanostructures and discusses some of their emerging capabilities.
We discuss the dynamics of ultrashort pulsed laser excitation in bulk optical silica-based glasses (fused silica and borosilicate BK7) well-above the permanent modification threshold. We indicate subsequent structural and thermomechanical energy relaxation paths that translate into positive and negative refractive index changes, compression and rarefaction zones. If fast electronic decay occurs at low excitation levels in fused silica via self-trapping of excitons, for carrier densities in the vicinity of the critical value at the incident wavelength, persistent long-living absorptive states indicate the achievement of low viscosity matter states manifesting pressure relaxation, rarefaction, void opening and compaction in the neighboring domains. An intermediate ps-long excited carrier dynamics is observed for BK7 in the range corresponding to structural expansion and rarefaction. The amount of excitation and the strength of the subsequent hydrodynamic evolution is critically dependent on the pulse time envelope, indicative of potential optimization schemes.
A bottom-up approach is presented for the production of arrays of indium islands on a molybdenum layer on glass, which can serve as micro-sized precursors for indium compounds such as copper-indium-gallium-diselenide used in photovoltaics. Femtosecond laser ablation of glass and a subsequent deposition of a molybdenum film or direct laser processing of the molybdenum film both allow the preferential nucleation and growth of indium islands at the predefined locations in a following indium-based physical vapor deposition (PVD) process. A proper choice of laser and deposition parameters ensures the controlled growth of indium islands exclusively at the laser ablated spots. Based on a statistical analysis, these results are compared to the non-structured molybdenum surface, leading to randomly grown indium islands after PVD.
The possibility to excite surface plasmon polaritons (SPPs) at the interface between two media depends on the optical properties of both media and geometrical aspects. Specific conditions allowing the coupling of light with a plasmon-active interface must be satisfied. Plasmonic effects are well described in noble metals where the imaginary part of the dielectric permittivity is often neglected ('perfect medium approximation (PMA)'). However, some systems exist for which such approximation cannot be applied, hence requiring a refinement of the common SPP theory. In this context, several properties of SPPs such as excitation conditions, period of the electromagnetic field modulation and SPP lifetime then may strongly deviate from that of the PMA. In this paper, calculations taking into account the imaginary part of the dielectric permittivities are presented. The model identifies analytical terms which should not be neglected in the mathematical description of SPPs on lossy materials. These calculations are applied to numerous material combinations resulting in a prediction of the corresponding SPP features. A list of plasmon-active interfaces is provided along with a quantification of the above mentioned SPP properties in the regime where the PMA is not applicable.
Sub-100-nm laser-induced periodic surface structures (LIPSS) were processed on bulk titanium (Ti) surfaces by femtosecond laser pulse irradiation in air (30 fs pulse duration, 790 nm wavelength). The laser peak fluence, the spatial spot overlap, and the number of overscans were optimized in a sample-scanning geometry in order to obtain large surface areas (5 mm × 5 mm) covered homogeneously by the LIPSS. The laser-processed regions were characterized by optical microscopy (OM), white light interference microscopy (WLIM) and scanning electron microscopy (SEM). The friction coefficient of the nanostructured surfaces was tested during 1000 cycles under reciprocal sliding conditions (1 Hz, 1.0 N normal load) against a 10-mm diameter ball of hardened 100Cr6 steel, both in paraffin oil and in engine oil used as lubricants. Subsequently, the corresponding wear tracks were qualified by OM, SEM, and energy dispersive X-ray analyses (EDX). The results of the tribological tests are discussed and compared to that obtained for near wavelength-sized fs-LIPSS, processed under somewhat different irradiation conditions. Some constraints for a beneficial effect of LIPSS on the tribological performance are provided.
In order to address the dynamics and physical mechanisms of LIPSS formation for three different classes of materials (metals, semiconductors, and dielectrics), two-color double-fs-pulse experiments were performed on Titanium, Silicon and Fused Silica. For that purpose a Mach–Zehnder interferometer generated polarization controlled (parallel or cross-polarized) double-pulse sequences at 400 nm and 800 nm wavelength, with inter-pulse delays up to a few picoseconds. Multiple of these two-color double-pulse sequences were collinearly focused by a spherical mirror to the sample surfaces. The fluence of each individual pulse (400 nm and 800 nm) was always kept below its respective ablation threshold and only the joint action of both pulses lead to the formation of LIPSS. Their resulting characteristics (periods, areas) were analyzed by scanning electron microscopy. The periods along with the LIPSS orientation allow a clear identification of the pulse which dominates the energy coupling to the material. For strong absorbing materials (Silicon, Titanium), a wavelength-dependent plasmonic mechanism can explain the delay-dependence of the LIPSS. In contrast, for dielectrics (Fused Silica) the first pulse always dominates the energy deposition and LIPSS orientation, supporting a non-plasmonic formation scenario. For all materials, these two-color experiments confirm the importance of the ultrafast energy deposition stage for LIPSS formation.
This article represents the editorial preface for the proceedings of the Symposium CC “Laser and plasma processing for advanced applications in material science” held from May 11th to 15th 2015 in the Lille Grand Palais, France, during the annual Spring Meeting of the European Materials Research Society (E-MRS).
Laser-induced periodic surface structures (LIPSS, ripples) are a universal phenomenon and can be generated on almost any material upon irradiation with linearly polarized radiation. With the availability of ultrashort laser pulses, LIPSS have gained an increasing attraction during the past decade, since these structures can be generated in a simple single-step process, which allows a surface nanostructuring for tailoring optical, mechanical, and chemical surface properties. In this study, the current state in the field of LIPSS is reviewed. Their formation mechanisms are analyzed in ultrafast time-resolved scattering, diffraction, and polarization constrained double-pulse experiments. These experiments allow us to address the question whether the LIPSS are seeded via ultrafast energy deposition mechanisms acting during the absorption of optical radiation or via self-organization after the irradiation process. Relevant control parameters of LIPSS are identified, and technological applications featuring surface functionalization in the fields of optics, fluidics, medicine, and tribology are discussed.
Structural relaxation phenomena in binary and multicomponent lithium silicate glasses were studied upon irradiation with femtosecond (fs) laser pulses (800 nm central wavelength, 130 fs pulse duration) and subsequent thermal annealing experiments. Depending on the annealing temperature, micro-Raman spectroscopy analyses evidenced different relaxation behaviours, associated to bridging and non-bridging oxygen structures present in the glass network. The results indicate that the mobility of lithium ions is an important factor during the glass modification with fs-laser pulses. Quantitative phase contrast imaging (spatial light interference microscopy) revealed that these fs-laser induced structural modifications are closely related to local changes in the refractive index of the material. The results establish a promising strategy for tailoring fs-laser sensitivity of glasses through structural mobility.
In order to study the temporally distributed energy deposition in the formation of laser-induced periodic surface structures (LIPSS) on single-crystalline zinc oxide (ZnO), two-colour double-fs-pulse experiments were performed. Parallel or cross-polarised double-pulse sequences at 400 and 800 nm wavelength were generated by a Mach–Zehnder interferometer, exhibiting inter-pulse delays up to a few picoseconds between the sub-ablation 50-fs-pulses. Twenty two-colour double-pulse sequences were collinearly focused by a spherical mirror to the sample surface. The resulting LIPSS periods and areas were analysed by scanning electron microscopy. The delay-dependence of these LIPSS characteristics shows a dissimilar behaviour when compared to the semiconductor silicon, the dielectric fused silica, or the metal titanium. A wavelength-dependent plasmonic mechanism is proposed to explain the delay-dependence of the LIPSS on ZnO when considering multi-photon excitation processes. Our results support the involvement of nonlinear processes for temporally overlapping pulses. These experiments extend previous two-colour studies on the indirect semiconductor silicon towards the direct wide band-gap semiconductor ZnO and further manifest the relevance of the ultrafast energy deposition for LIPSS formation.
The chemical characteristics of two different types of laser-induced periodic surface structures (LIPSS), so-called high and low spatial frequency LIPSS (HSFL and LSFL), formed upon irradiation of titanium surfaces by multiple femtosecond laser pulses in air (30 fs, 790 nm, 1 kHz), are analyzed by various optical and electron beam based surface analytical techniques, including micro-Raman spectroscopy, energy dispersive X-ray analysis, X-ray photoelectron spectroscopy, and Auger electron spectroscopy. The latter method was employed in a high-resolution mode being capable of spatially resolving even the smallest HSFL structures featuring spatial periods below 100 nm. In combination with an ion sputtering technique, depths-resolved chemical information of superficial oxidation processes was obtained, revealing characteristic differences between the two different types of LIPSS. Our results indicate that a few tens of nanometer shallow HSFL are formed on top of a ∼150 nm thick graded superficial oxide layer without sharp interfaces, consisting of amorphous TiO2 and partially crystallized Ti2O3. The larger LSFL structures with periods close to the irradiation wavelength originate from the laser-interaction with metallic titanium. They are covered by a ∼200 nm thick amorphous oxide layer, which consists mainly of TiO2 (at the surface) and other titanium oxide species of lower oxidation states underneath.
Single-pulse femtosecond laser-induced forward transfer (LIFT, 30 fs, 790 nm) is used to deposit micron-sized dots of copper and/or indium onto a molybdenum layer on glass. Such systems can serve as precursors for the bottom-up manufacturing of micro-concentrator solar cells based on copper-indium-gallium-diselenide. The influence of the thickness of the copper, indium and combined copper-indium donor layers on the quality of the transferred dots was qualified by scanning electron microscopy, energy-dispersive X-ray analysis, and optical microscopy. The potential for manufacturing of a spatial arrangement adapted to the geometry of micro-lens arrays needed for micro-concentrator solar cells is demonstrated.
Periodic self-organization of matter beyond the diffraction limit is a puzzling phenomenon, typical both for surface and bulk ultrashort laser processing. Here we compare the mechanisms of periodic nanostructure formation on the surface and in the bulk of fused silica. We show that volume nanogratings and surface nanoripples having subwavelength periodicity and oriented perpendicular to the laser polarization share the same electromagnetic origin. The nanostructure orientation is defined by the near-field local enhancement in the vicinity of the inhomogeneous scattering centers. The periodicity is attributed to the coherent superposition of the waves scattered at inhomogeneities. Numerical calculations also support the multipulse accumulation nature of nanogratings formation on the surface and inside fused silica. Laser surface processing by multiple laser pulses promotes the transition from the high spatial frequency perpendicularly oriented nanoripples to the low spatial frequency ripples, parallel or perpendicular to the laser polarization. The latter structures also share the electromagnetic origin, but are related to the incident field interference with the scattered far-field of rough non-metallic or transiently metallic surfaces. The characteristic ripple appearances are predicted by combined electromagnetic and thermo-mechanical approaches and supported by SEM images of the final surface morphology and by time-resolved pump-probe diffraction measurements.
Ultrashort laser pulses with durations in the fs-to-ps range were used for large area surface processing of steel aimed at mimicking the morphology and extraordinary wetting behaviour of bark bugs (Aradidae) found in nature. The processing was performed by scanning the laser beam over the surface of polished flat sample surfaces. A systematic variation of the laser processing parameters (peak fluence and effective number of pulses per spot diameter) allowed the identification of different regimes associated with characteristic surface morphologies (laser-induced periodic surface structures, i.e., LIPSS, grooves, spikes, etc.). Moreover, different laser processing strategies, varying laser wavelength, pulse duration, angle of incidence, irradiation atmosphere, and repetition rates, allowed to achieve a range of morphologies that resemble specific structures found on bark bugs. For identifying the ideal combination of parameters for mimicking bug-like structures, the surfaces were inspected by scanning electron microscopy. In particular, tilted micrometre-sized spikes are the best match for the structure found on bark bugs. Complementary to the morphology study, the wetting behaviour of the surface structures for water and oil was examined in terms of philic/ phobic nature and fluid transport. These results point out a route towards reproducing complex surface structures inspired by nature and their functional response in technologically relevant materials.
Miniaturized pacemakers with a surface consisting of a Ti alloy may have to be removed after several years from their implantation site in the heart and shall, therefore, not be completely overgrown by cells or tissue. A method to avoid this may be to create at the surface by laser-ablation self-organized sharp conical spikes, which provide too little surface for cells (i.e., fibroblasts) to grow on. For this purpose, Ti-alloy substrates were irradiated in the air by 790 nm Ti:sapphire femtosecond laser pulses at fluences above the ablation threshold. The laser irradiation resulted in pronounced microstructure formation with hierarchical surface morphologies. Murine fibroblasts were seeded onto the laser-patterned surface and the coverage by cells was evaluated after 3–21 days of cultivation by means of scanning electron microscopy. Compared to flat surfaces, the cell density on the microstructures was significantly lower, the coverage was incomplete, and the cells had a clearly different morphology. The best results regarding suppression of cell growth were obtained on spike structures which were additionally electrochemically oxidized under acidic conditions. Cell cultivation with additional shear stress could reduce further the number of adherent cells.
A procedure to fabricate CuInSe2 (CISe) micro-absorbers and solar cells for concentrator applications is presented. The micro-absorbers are developed from indium precursor islands, which are deposited on a molybdenum coated glass substrate (back contact), followed by deposition of copper on top and subsequent selenization as well as selective etching of copper selenides. In order to compare the properties of the locally grown absorbers to those of conventional large area CISe films, we systematically examine the compositional and morphological homogeneity of the micro absorbers and carry out photoluminescence measurements. Preliminary devices for micro-concentrator solar cell applications are fabricated by optimizing the copper to indium ratio and the size of the indium precursor islands. The resulting micro solar cells provide a characteristic I–V curve under standard illumination conditions (1 sun).
Titanium nitride (TiN) was coated on different substrate materials, namely pure titanium (Ti), titanium alloy (Ti6Al4V) and steel (100Cr6), generating 2.5 μm thick TiN layers. Using femtosecond laser pulses (30 fs, 790 nm, 1 kHz pulse repetition rate), large surface areas (5 mm × 5 mm) of laser-induced periodic surface structures (LIPSS) with sub-wavelength periods ranging between 470 nm and 600 nm were generated and characterized by optical microscopy (OM), white light interference microscopy (WLIM) and scanning electron microscopy (SEM). In tribological tests, coefficients of friction (COF) of the nanostructured surfaces were determined under reciprocating sliding conditions (1 Hz, 1.0 N normal load) against a 10-mm diameter ball of hardened 100Cr6 steel during 1000 cycles using two different lubricants, namely paraffin oil and engine oil. It turned out that the substrate material, the laser fluence and the lubricant are crucial for the tribological performance. However, friction and wear could not be significantly reduced by LIPSS on TiN layers in comparison to unstructured TiN surfaces. Finally, the resulting wear tracks on the nanostructured surfaces were investigated with respect to their morphology (OM, SEM), depth (WLIM) and chemical composition by energy dispersive X-ray spectroscopy (EDX) and, on one hand, compared with each other, on the other hand, with non-structured TiN surfaces.
Inorganic materials, such as steel, were functionalized by ultrashort laser pulse irradiation (fs- to ps-range) to modify the surface’s wetting behavior. The laser processing was performed by scanning the laser beam across the surface of initially polished flat sample material. A systematic experimental study of the laser processing parameters (peak fluence, scan velocity, line overlap) allowed the identification of different regimes associated with characteristic surface morphologies (laser-induced periodic surface structures, grooves, spikes, etc.). Analyses of the surface using optical as well as scanning electron microscopy revealed morphologies providing the optimum similarity to the natural skin of lizards. For mimicking skin structures of moisture-harvesting lizards towards an optimization of the surface wetting behavior, additionally a two-step laser processing strategy was established for realizing hierarchical microstructures. In this approach, micrometer-scaled capillaries (step 1) were superimposed by a laser-generated regular array of small dimples (step 2). Optical focus variation imaging measurements finally disclosed the three dimensional topography of the laser processed surfaces derived from lizard skin structures. The functionality of these surfaces was analyzed in view of wetting properties.
Biofilm formation poses high risks in multiple industrial and medical settings. However, the robust nature of biofilms makes them also attractive for industrial applications where cell biocatalysts are increasingly in use. Since tailoring material properties that affect bacterial growth or its inhibition is gaining attention, here we focus on the effects of femtosecond laser produced nanostructures on bacterial adhesion. Large area periodic surface structures were generated on steel surfaces using 30-fs laser pulses at 790 nm wavelength. Two types of steel exhibiting a different corrosion resistance were used, i.e., a plain structural steel (corrodible) and a stainless steel (resistant to corrosion). Homogeneous fields of laser-induced periodic surface structures (LIPSS) were realized utilizing laser fluences close to the ablation threshold while scanning the sample under the focused laser beam in a multi-pulse regime. The nanostructures were characterized with optical and scanning electron microscopy. For each type of steel, more than ten identical samples were laser-processed. Subsequently, the samples were subjected to microbial adhesion tests. Bacteria of different shape and adhesion behavior (Escherichia coli and Staphylococcus aureus) were exposed to laser structures and to polished reference surfaces. Our results indicate that E. coli preferentially avoids adhesion to the LIPSS-covered areas, whereas S. aureus favors these areas for colonization.
Indium islands on molybdenum coated glass can be grown in ordered arrays by surface structuring using a femtosecond laser. The effect of varying the molybdenum coated glass substrate temperature and the indium deposition rate on island areal density, volume and geometry is investigated and evaluated in a physical vapor deposition (PVD) process. The joined impact of growth conditions and spacing of the femtosecond laser structured spots on the arrangement and morphology of indium islands is demonstrated. The results yield a deeper understanding of the island growth and its precise adjustment to industrial requirements, which is indispensable for a technological application of such structures at a high throughput, for instance as precursors for the preparation of Cu(In,Ga)Se2 micro concentrator solar cells.
Scattering on scattering
(2017)
The formation and properties of laser-induced periodic surface structures (LIPSS) were investigated on carbon fibers under irradiation of fs-laser pulses characterized by a pulse duration τ = 300 fs and a laser wavelength λ = 1025 nm. The LIPSS were fabricated in an air environment at normal incidence with different values of the laser peak fluence and number of pulses per spot. The morphology of the generated structures was characterized by using scanning electron microscopy, atomic force microscopy and Fast-Fourier transform analyses. Moreover, the material structure and the surface chemistry of the carbon fibers before and after laser irradiation was analyzed by micro Raman spectroscopy and X-ray photoelectron spectroscopy. Large areas in the cm2 range of carbon fiber arrangements were successfully processed with homogenously distributed high- and low-spatial frequency LIPSS. Beyond those distinct nanostructures, hybrid structures were realized for the very first time by a superposition of both types of LIPSS in a two-step process. The findings facilitate the fabrication of tailored LIPSS-based surface structures on carbon fibers that could be of particular interest for e.g. fiber reinforced polymers and concretes.
A laser-based bottom-up technique for the fabrication of Cu(In,Ga)Se2 (CIGSe) micro solar cells is presented.
We use femtosecond laser-induced forward transfer (LIFT) to transport a metallic precursor composed of copper, indium, and gallium onto a molybdenum back contact layer on a glass substrate. A CIGSe absorber forms by subsequent selenization. An array of micro absorbers with defined spacing is fabricated to solar cells and characterized under concentrated light illumination. The solar cell array exhibited a conversion efficiency of 1.4‰ at 1 sun as well as a significant efficiency enhancement of 68% rel. under 20-fold concentration. This work demonstrates the possibility of directly grown micrometer-sized solar cells based on chalcogenide absorber layers, enabling effective material usage.
Laser texturing is an emerging technology for generating surface functionalities on basis of optical, mechanical, or chemical properties. Taking benefit of laser sources with ultrashort (fs) pulse durations features outstanding precision of machining and negligible rims or burrs surrounding the laser-irradiation zone. Consequently, additional mechanical or chemical post-processing steps are usually not required for fs-laser surface texturing (fs-LST). This work aimed to provide a bridge between research in the field of tribology and laser materials processing. The paper reviews the current state-of-the-art in fs-LST, with a focus on the tribological performance (friction and wear) of specific self-organized surface structures (so-called ripples, grooves, and spikes) on steel and titanium alloys. On the titanium alloy, specific sickle-shaped hybrid micro-nanostructures were also observed and tribologically tested. Care is taken to identify accompanying effects affecting the materials hardness, superficial oxidation, nano- and microscale topographies, and the role of additives contained in lubricants, such as commercial engine oil.
In laser machining with ultrashort laser pulses unwanted X-ray radiation in the keV range can be generated when a critical laser intensity is exceeded. Even if the emitted X-ray dose per pulse is low, high laser repetition rates can lead to an accumulation of X-ray doses beyond exposure safety limits. For 925 fs pulse duration at a center wavelength of 1030 nm, the X-ray emission was investigated up to an intensity of 2.6 × 10^14 W/cm2. The experiments were performed in air with a thin disk laser at a repetition rate of 400 kHz. X-ray spectra and doses were measured for various planar target materials covering a wide range of the periodic table from aluminum to tungsten. Without radiation shielding, the measured radiation doses at this high repetition rate clearly exceed the regulatory limits. Estimations for an adequate radiation shielding are provided.
We investigate the periodic structure formation upon intense femtosecond pulsed irradiation of chrome steel (100Cr6) for linearly polarised laser beams. The underlying physical mechanism of the laser-induced periodic structures is explored, their spatial frequency is calculated and theoretical results are compared with experimental observations. The proposed theoretical model comprises estimations of electron excitation, heat transfer, relaxation processes, and hydrodynamics-related mass transport. Simulations describe the sequential formation of sub-wavelength ripples and supra-wavelength grooves. In addition, the influence of the laser wavelength on the periodicity of the structures is discussed. The proposed theoretical investigation offers a systematic methodology towards laser processing of steel surfaces with important applications.
Commercial grade-1 titanium samples (Ti, 99.6%) were treated using three alternative methods, (i) femtosecond laser processing, (ii) thermal heat treatment, and (iii) electrochemical anodization, respectively, resulting in the formation of differently conditioned superficial titanium oxide layers. The laser processing (i) was carried out by a Ti:sapphire laser (pulse duration 30 fs, central wavelength 790 nm, pulse repetition rate 1 kHz) in a regime of generating laser-induced periodic surface structures (LIPSS). The experimental conditions (laser fluence, spatial spot overlap) were optimized in a sample-scanning setup for the processing of several square-millimeters large surface areas covered homogeneously by these nanostructures. The differently oxidized titanium surfaces were characterized by optical microscopy, micro Raman spectroscopy, variable angle spectroscopic ellipsometry, and instrumented indentation testing. The tribological performance was characterized in the regime of mixed friction by reciprocating sliding tests against a sphere of hardened steel in fully formulated engine oil as lubricant. The specific tribological performance of the differently treated surfaces is discussed with respect to possible physical and chemical mechanisms.
Micro-concentrator solar cells offer an attractive way to further enhance the efficiency of planar-cell technologies while saving absorber material. Here, two laser-based bottom-up processes for the fabrication of regular arrays of CuInSe2 and Cu(In,Ga)Se2 microabsorber islands are presented, namely one approach based on nucleation and one based on laser-induced forward transfer.
Additionally, a procedure for processing these microabsorbers to functioning micro solar cells connected in parallel is demonstrated. The resulting cells show up to 2.9% efficiency and a significant efficiency enhancement under concentrated Illumination.
Time-resolved phase-contrast microscopy is employed to visualize spatio-temporal thermal transients induced by tight focusing of a single Ti:sapphire fs-laser pulse into a solid dielectric sample. This method relies on the coupling of the refractive index change and the sample temperature through the thermo-optic coefficient dn/dT. The thermal transients are studied on a timescale ranging from 10 ns up to 0.1 ms after laser excitation. Beyond providing direct insights into the laser–matter interaction, analyzing the results obtained also enables quantifying the local thermal diffusivity of the sample on a micrometer scale. Studies conducted in different solid dielectrics, namely amorphous fused silica (a-SiO2), a commercial borosilicate glass (BO33, Schott), and a custom alkaline earth silicate glass (NaSi66), illustrate the applicability of this approach to the investigation of various glassy materials.
The formation of gratings on the surface of a silicon wafer by nanosecond laser irradiation through a phase mask using an ArF laser emitting at 193 nm is studied. The phase mask along with some focusing optics is capable to generate via interference a periodic intensity distribution, which can be used for surface patterning. The surface patterning strongly depends on the laser energy density and on the number of pulses, as revealed by atomic force microscopy (AFM). The results show that irradiation even with a single laser pulse produces periodic depth modulations on the surface. The spatial surface modulation is in the micrometer (1.7 µm) range while the depth modulation is in the nanometer regime (1–20 nm). With an increasing number of pulses (1–100), the depth modulation amplitude increases smoothly. Increasing the number of pulses further results in the progressive destruction of the grating, vanishing completely after ~5000 pulses. This evolution is also monitored in situ by measuring the intensity of the first order-diffracted probe beam and the behavior is in accordance with what is observed by AFM. Finally, we qualitatively explain the results invoking thermally induced effects in the melted Si: these physical processes involved are probably thermocapillary and/or Marangoni effects inducing material displacement as the surface melts.
Modeling of silicon surface topographies induced by single nanosecond laser pulse induced melt-flows
(2019)
Irradiation with a single nanosecond laser pulse in the melting regime can result in a characteristic change in the surface morphology of crystalline silicon. This has been verified experimentally in a variety of situations, where dimple-shaped surface topographies are produced. In this work, the dimple height, depth, and width are modeled following and extending in a more rigorous manner the approach of Wood and Giles [Phys. Rev. B 23, 2923–2942 (1981)] and that of Schwarz-Selinger and coworkers [Phys. Rev. B 64, 155323 (2001)], upon varying the laser irradiation parameters such as peak energy density, pulse duration, and wavelength. This is achieved with numerical simulations of one-dimensional heat flow as input to the analytical fluid-flow equations.
Laser-induced periodic surface structures (LIPSS, ripples) with ~500–700 nm period were produced on titanium alloy (Ti6Al4V) surfaces upon scan processing in air by a Ti:sapphire femtosecond laser. The tribological performance of the surfaces were qualified in linear reciprocating sliding tribological tests against balls made of different materials using different oilbased lubricants. Extending our previous work, we studied the admixture of the additive 2-ethylhexyl-zinc-dithiophosphate to a base oil containing only anti-oxidants and temperature stabilizers. The presence of this additive along with the variation of the chemical composition of the counterbodies allows us to explore the synergy of the additive with the laseroxidized nanostructures.
The influence of processing parameters on X‑ray emission during ultra‑short pulse laser machining
(2019)
During ultra-short laser material processing at high laser pulse repetition rates unwanted X-ray radiation can be generated in a quantity that may constitute a potential risk for health. An adequate X-ray radiation protection requires a thoroughly understanding of the influence of the laser processing parameters on the generation of X-ray radiation. In the present work, the generated X-ray dose during laser machining was investigated in air for varying beam scanning conditions at a pulse duration of 925 fs, a center wavelength of 1030 nm and a laser peak intensity of 2.6 × 10^14 W/cm^2. The X-ray radiation dose and the corresponding spectral X-ray emission were investigated in dependence on the laser’s pulse repetition rate and on the beam scanning speed. The results show a strong dependence of the X-ray emission on these laser processing parameters.
In this study, femtosecond laser-induced sub-micrometer structures are generated to modify polyethylene (PE) surface topographies. These surfaces were subjected to bacterial colonization studies with Escherichia coli and Staphylococcus aureus as test strains. The results reveal that the nanostructures do not influence S. aureus coverage, while the adhesion of E. coli is reduced.
In this paper, the influence of the bulk temperature (BT) of Polycarbonate (PC) on the occurrence and growth of Laser-induced Periodic Surface Structures (LIPSS) is studied. Ultrashort UV laser pulses with various laser peak fluence levels F_0 and various numbers of overscans (N_OS) were applied on the surface of pre-heated Polycarbonate at different bulk temperatures. Increased BT leads to a stronger absorption of laser energy by the Polycarbonate. For N_OS < 1000 High Spatial Frequency LIPSS (HSFL), Low Spatial Frequency LIPSS perpendicular (LSFL-I) and parallel (LSFL-II) to the laser polarization were only observed on the rim of the ablated tracks on the surface but not in the center of the tracks. For N_OS ≥ 1000 , it was found that when pre-heating the polymer to a BT close its glass transition temperature (T_g), the laser fluence to achieve similar LIPSS as when processed at room temperature decreases by a factor of two. LSFL types I and II were obtained on PC at a BT close to T_g and their periods and amplitudes were similar to typical values found in the literature. To the best of the author’s knowledge, it is the first time both LSFL types developed simultaneously and consistently on the same sample under equal laser processing parameters. The evolution of LIPSS from HSFL, over LSFL-II to LSFL I, is described, depending on laser peak fluence levels, number of pulses processing the spot and bulk temperature.
The impact of femtosecond (fs) laser-induced periodic surface structures (LIPSS) on tribological properties was investigated for metal-reinforced ceramic composites (Al2O3-ZrO2-Nb). For this purpose, the metallic niobium (Nb) phase was selectively structured with LIPSS in an air environment with different values of the fs-laser peak fluence by near-infrared fs-laser radiation (λ = 1025 nm, τ = 300 fs, frep = 1 kHz), taking advantage of the different light absorption behavior of ceramic and metal. The tribological performance was evaluated by reciprocating sliding tests in a ball-on-disc configuration using Ringer's solution as lubricant. The surfaces were characterized before and after laser irradiation by optical microscopy, scanning electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy, energy dispersive X-ray spectroscopy and by measuring the contact angle with Ringer's solution. The LIPSS formation resulted in an increased wetting of the surface with the lubricant. Moreover, the selectively structured composite surfaces revealed a coefficient of friction significantly reduced by a factor of ~3 when compared to the non-irradiated surface. Furthermore, the formation of a laser-induced oxidation layer was detected with NbO as the most prominent oxidation state. Selectively structured composites with outstanding mechanical properties and enhanced tribological performance are of particular interest for biomedical applications.
In recent years, the improved understanding of the formation of laser-induced periodic surface structures (LIPSS) has led to an emerging variety of applications that modify the optical, mechanical, and chemical properties of many materials. Such structures strongly depend on the laser beam polarization and are formed usually after irradiation with ultrashort linearly polarized laser pulses. The most accepted explanation for the origin of the structures is based on the interference of the incident laser radiation with electromagnetic surface waves that propagate or scatter at the surface of the irradiated materials. This leads to an intensity modulation that is finally responsible for the selective ablation in the form of parallel structures with periods ranging from hundreds of nanometers up to some micrometers. The versatility when forming such structures is based on the high reproducibility with different wavelengths, pulse durations and repetition rate laser sources, customized micro- and nanometric spatial resolutions, and compatibility with industrially relevant processing speeds when combined with fast scanning devices. In this contribution, we review the latest applications in the rapidly emerging field of surface functionalization through LIPSS, including biomimetic functionalities on fluid transport, control of the wetting properties, specific optical responses in technical materials, improvement of tribological performance on metallic surfaces, and bacterial and cell growth for medical devices, among many others.
Irradiation with a single spatially Gaussian-shaped nanosecond laser pulse in the melting regime can result in a characteristic annular change in the surface morphology of crystalline silicon. This has been verified experimentally in a variety of situations, where dimple-shaped surface topographies are produced. In a recent work we have investigated the induced changes in the surface topography upon exposure to wavelengths in the visible and near infrared spectral region. Irradiation in the UV requires a more detailed analysis due to the enhanced absorption of the material. In the present analysis, we determine under which conditions our previous model can be used and the corresponding results are presented.
Herein, Ti6Al4V alloy is surface modified by femtosecond laser ablation. The microstructure image obtained by secondary electron microscopy reveals a combination of micrometer spikes or cones superimposed by nanoripples (laser‐induced periodic surface structures). To make the surface hydrophilic, anodization is performed resulting in further smoothness of microstructure and a final thickness of 35 ± 4 nm is estimated for oxide produced after anodization at 10 V (scan rate = 0.1 V s−1) versus standard hydrogen electrode. The obtained electrochemically active surface area (ECSA) is approximately 8 times larger compared with flat mirror polished Ti6Al4V surface. Combined chemical analysis by Pourbaix diagram and X‐ray photoelectron spectroscopy (XPS) analyses reveal that titanium and aluminum are passivating into TiO2 and Al2O3, but the dissolution of aluminum in the form of solvated ion is inevitable. Finally, cell seeding experiments on anodized and laser‐treated titanium alloy samples show that the growth of murine fibroblast cells is significantly suppressed due to unique surface texture of the laser‐treated and anodized titanium alloy sample.
The invention of new miniaturized and smart medical implants continues in all medical fields, including miniaturized heart pacemakers. These implants often come with a titanium (Ti) casing, which may have to be removed after several months or years and shall therefore not be completely overgrown by cells or scar tissue after implantation. Scar tissue is mainly formed by fibroblast cells and extracellular matrix proteins like collagen produced by them. Suppression of fibroblast growth at Ti surfaces could be achieved by 800 nm femtosecond laser-ablation creating self-organized sharp spikes with dimensions in the 10 μm-range which are superposed by fine sub-μm parallel ripples. On flat Ti control samples, the best results regarding suppression of cell growth were obtained on spike-structures which were additionally electrochemically anodized under acidic conditions. When Ti cylinders with a diameter of 8 mm (similar as the pacemakers) were placed upright in a culture of murine fibroblasts, a multi-layer cell growth up to a height of at least 1.5 mm occurred within 19–22 days. We have demonstrated that a laser-structured and anodized ring around the Ti cylinder surface is an effective way to create a barrier that murine fibroblasts were not able to overgrow within this time.
The exciting properties of micro- and nano-patterned surfaces found in natural species hide a virtually endless potential of technological ideas, opening new opportunities for innovation and exploitation in materials science and engineering. Due to the diversity of biomimetic surface functionalities, inspirations from natural surfaces are interesting for a broad range of applications in engineering, including phenomena of adhesion, friction, wear, lubrication, wetting phenomena, self-cleaning, antifouling, antibacterial phenomena, thermoregulation and optics. Lasers are increasingly proving to be promising tools for the precise and controlled structuring of materials at micro- and nano-scales. When ultrashort-pulsed lasers are used, the optimal interplay between laser and material parameters enables structuring down to the nanometer scale. Besides this, a unique aspect of laser processing technology is the possibility for material modifications at multiple (hierarchical) length scales, leading to the complex biomimetic micro- and nano-scale patterns, while adding a new dimension to structure optimization. This article reviews the current state of the art of laser processing methodologies, which are being used for the fabrication of bioinspired artificial surfaces to realize extraordinary wetting, optical, mechanical, and biological-active properties for numerous applications. The innovative aspect of laser functionalized biomimetic surfaces for a wide variety of current and future applications is particularly demonstrated and discussed. The article concludes with illustrating the wealth of arising possibilities and the number of new laser micro/nano fabrication approaches for obtaining complex high-resolution features, which prescribe a future where control of structures and subsequent functionalities are beyond our current imagination.
Hierarchical micro/-nanostructures were produced on polycarbonate polymer surfaces by employing a two-step UV-laser processing strategy based on the combination of Direct Laser Interference Patterning (DLIP) of gratings and pillars on the microscale (3 ns, 266 nm, 2 kHz) and subsequently superimposing Laser-induced Periodic Surface Structures (LIPSS; 7–10 ps, 350 nm, 100 kHz) which adds nanoscale surface features. Particular emphasis was laid on the influence of the direction of the laser beam polarization on the morphology of resulting hierarchical surfaces. Scanning electron and atomic force microscopy methods were used for the characterization of the hybrid surface structures. Finite-difference time-domain (FDTD) calculations of the laser intensity distribution on the DLIP structures allowed to address the specific polarization dependence of the LIPSS formation observed in the second processing step. Complementary chemical analyzes by micro-Raman spectroscopy and attenuated total reflection Fourier-transform infrared spectroscopy provided in-depth information on the chemical and structural material modifications and material degradation imposed by the laser processing. It was found that when the linear laser polarization was set perpendicular to the DLIP ridges, LIPSS could be formed on top of various DLIP structures. FDTD calculations showed enhanced optical intensity at the topographic maxima, which can explain the dependency of the morphology of LIPSS on the polarization with respect to the orientation of the DLIP structures. It was also found that the degradation of the polymer was enhanced for increasing accumulated fluence levels.