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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.
A promising technology in photovoltaics is based on micro-concentrator solar cells, where the photovoltaic active area is realized as an array of sub-millimeter sized cells onto which the incident light is focused via microlenses. This approach allows to increase the cell efficiency and to realize much more compact modules compared to macroscopic concentrator devices. At the same time, expensive raw materials can be saved, which is of interest, for example, with respect to indium in the case of copper-indium-gallium-diselenide (CIGSe) thin film solar cells. Two methods to produce micro-sized precursors of CIGSe absorbers on molybdenum are presented using 30-fs laser pulses at 790 nm wavelength. On the one hand, a multi pulse surface structuring of the molybdenum film or the underlying glass substrate and a subsequent physical vapor deposition were used for a site-selective aggregation of indium droplets. On the other hand, a single pulse laser-induced forward transfer was utilized to selectively deposit combined copper-indium precursor pixels on the molybdenum back contact of the solar cell. Post-processing (selenization, isolation, contacting) of the laser-generated micro-sized precursors results in functional CIGSe solar cells.
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.
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.
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.
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.
Micromachining experiments were performed with Ti:sapphire laser pulses (130 fs - 150 fs, 800 nm, approximately 10 Hz) in air. Employing the direct focusing technique, highly absorbing titanium nitride (TiN) and weakly absorbing polyimide (PI) and polymethylmethacrylate (PMMA) served as target materials. The lateral and vertical precision of the laser ablation and morphological features were characterized by scanning force (SFM), scanning electron (SEM) and optical microscopy. For TiN, incubation can be observed, i.e. the single-pulse surface damage threshold (0.26 J/cm2) is by a factor of two greater than the threshold for 100 pulses. Ablation rates below 10 nm per pulse can be achieved. The evolution of sub-wavelength ripples is presented in dependence on pulse number and laser fluence, respectively. The incubation behavior of the polymers can be described by an accumulation model as for TiN. Experiments on PI with varying focal lengths result in the same modification thresholds. Different polarization states of light (linear, circular) lead to a variation of the ablation rate and to various morphological patterns in the ablation craters (wavelength ripples, cones). Swelling of PMMA occurred at fluences below the ablation threshold.
Multi-shot investigations of Ti:sapphire laser (wavelength (lambda) approximately equals 800 nm) induced damage were performed in three different laboratories (BAM, Berlin; LZH, Hannover; UNM, Albuquerque). The ablation behavior of a high reflecting mirror consisting of alternating (lambda) /4- layers of Ta2O5 and SiO2 was studied. Fused silica served as substrate. The influence of the pulse duration ((tau) equals 13 - 130 fs), the pulse number (30 - (infinity) ) and the repetition rate (10 Hz - 100 MHz) on the damage threshold will be discussed.
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 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.