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- Laser-induced periodic surface structures (LIPSS) (5)
- Femtosecond laser ablation (4)
- Laser processing (4)
- Surface functionalization (4)
- Cleaning (3)
- Femtosecond laser (3)
- Laser (3)
- Laser cleaning (3)
- Laser-induced X-ray emission (3)
- Paper (3)
Organisationseinheit der BAM
The industrial use of ultrashort laser pulses has made considerable progress in recent years. The reasons for this lie in the availability of high average powers at pulse repetition rates in the several 100 kHz range. The advantages of using ultrashort laser pulses in terms of processing precision can thus be fully exploited. However, high laser intensities on the workpiece can also lead to the generation of unwanted X-rays. Even if the emitted X-ray dose per pulse is low, the accumulated X-ray dose can become significant for high-repetition-rate laser systems so that X-ray exposure safety limits must be considered. The X-ray emission during ultrashort pulse laser processing was investigated for a pulse duration of 925 fs at 1030 nm wavelength and 400 kHz repetition rate. Industrially relevant materials such as steel,aluminum and glass were treated. Tungsten served as reference. X-ray spectra were recorded, and X-ray dose measurements were performed for laser treatment in air. For laser intensities > 2 × 10^13 W/cm2, X-ray doses exceeding the regulatory exposure limits for members of the public were found. Suitable X-ray protection strategies are proposed.
Unwanted X-ray emission in ultrashort pulse laser processing: From metallic to biological materials
(2023)
X-rays can be generated as an unwanted side effect during ultrashort pulse laser material processing of technical work pieces and even biological samples with laser intensities above 10^13 W/cm^2. First studies demonstrate the need to address this effect in industrial as well as in medical applications. This secondary hazard should be considered in work safety and risk assessment.
The removal and accelerated corrosion monitoring of metal coating systems is of general interest in materials science
and engineering technology. The femtosecond and nanosecond laser ablation and delamination at 800 nm and 532 nm,
respectively, of anodic oxide layers on aluminium alloys in electrolyte contact were investigated. Laser-induced
modifications of the oxide layer resulted in an ionic contact between electrolyte and metal, which produced a current
transient and thus allowed the in-situ electrochemical monitoring of the modification. Oxide coatings with different
optical properties, almost transparent and opaque, were examined. The transparent anodic oxides showed contrasting
ablation mechanisms in the nanosecond and femtosecond pulse duration regime: nanosecond pulses caused spallation,
whereas femtosecond treatment led to ablation. Current signals measured in the transparent film were consistent with
light absorption below the metal-oxide interface and with film spallation. Irradiation of the opaque coating yielded ionic
current transients within the so-called shock-affected-zone of the oxide layer. This investigation provided insight into the
role of the penetration depth of light and the heat-affected zone, the extent of the shock-affected zone, and the defect
formation in the coating and at the solid-solid interface between metal and oxide.
Ultra-short pulse laser seeding techniques for silicon crystallite growth on amorphous substrates
(1999)
In this paper, safety-related experiments with ultra-short laser pulses (down to 30 fs) on various components
(goggles, curtains) for laser protection are presented. The damage and failure behaviour of
protective devices has been investigated dependent on practical conditions such as pulse duration, laser
.uence, pulse number, and repetition rate.
The e.ects of laser-irradiation on materials can be roughly divided into transient ones like laserinduced
transmission (LIT) or short-lived colour centres and permanent damages like the stable colour
centres and ablation. The former e.ects are particularly important for transparent devices like laser
goggles.
To obtain a complete overview on laser safety issues and the prevention of failure there are two
important .elds of investigation:
1. the e.ects of laser radiation on human eyes and skin, and
2. on the possible protection materials.
Both .elds have been addressed during the recently .nished German project SAFEST (safety aspects
in femtosecond technology). The amount of safety data available in the ultrashort pulse region has
been increased remarkably. This allows for a re-evaluation of known laser protection materials for this
region of pulse durations and for the evaluation of new designs that promise high protection levels
while being light-weight and convenient to use.
Towards an industrial laser doping process for the selective emitter using phosphoric acid as dopant
(2011)
Different laser supported approaches have already been realized, proving the great potential of laserdoped selective emitters (LDSE). However, it is challenging to establish a low-cost process by using pulsed laser tools. So far a single-step process only leads to satisfying results utilizing cw-lasers. In this paper we have examined a two-step process to produce laser-doped selective emitters on multicrystalline textured standard silicon photovoltaic wafers (90-Ω/sq-Emitter, SiN-antireflection coating (ARC)). The precise ARC removal by near-infrared fs-laser pulses (30 fs, 800 nm), and the doping of uncoated silicon wafers by ns-laser pulses (8 ns, 532 nm) were systematically investigated. In the fs-experiment, optimum conditions for ARC removal were identified. In the nsexperiments under suitable conditions (melting regime), the phosphorous concentration underneath the wafer surface was significantly increased and the sheet resistance was reduced by nearly a factor of two. Moreover, electrical measurements on fired metallization fingers deposited on the laser processed wafers showed low contact resistances. Hence, wafer conditioning with combined fs-laser- and ns-laser-processes are expected to be a promising technology for producing selective emitters.
The influence of paper type and state of degradation on laser cleaning of artificially soiled paper
(2011)
Lasers can be a supplemental tool for restorers to overcome some of the limitations of traditional dry cleaning techniques for works of art on paper. The laser working range has to be optimized allowing for safe removal of contamination and limitation of damage to the substrate. This paper addresses the influence of paper type and state of degradation on laser working range. Three types of new paper (pure cellulose, bleached pulp paper, rag paper) were degraded and characterized with respect their degree of polymerization. Laser-induced damage thresholds of new and degraded paper were determined using SEM and viscometry. Additionally, artificially soiled model samples were made using two kinds of soiling, namely pulverized charcoal and soot-blackened standard test dust. Cleaning thresholds of soiled paper samples were evaluated. A working range for all combinations of paper and soiling between 0.05 J/cm2 and 0.5 J/cm2 was found for the application of 8-ns laser pulses at 532 nm wavelength.
In this contribution the mechanisms of formation and current applications of LIPSS are reviewed, including the colorization of technical surfaces, the control of surface wetting properties, the mimicry of the natural texture of animal integuments, the tailoring of surface colonization by bacterial biofilms, and the improvement of the tribological performance of nanostructured metal surfaces.
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 wavelength, pulse duration and repetition rate laser sources, customized micro- and nanometric spatial resolutions, and the 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.
Commercially available absorption filters (Schott BG18 and BG36) were investigated with respect to their single- and
multi-pulse ablation threshold using laser pulses from a Ti:Sapphire laser in the range between 30 and 340 fs. It could be
observed, that the threshold fluence decreases for shorter pulse durations. The similarity of the measured multi-pulse
threshold fluences with those of undoped glass material (around 1 J/cm^2 for a pulse duration of 30 fs) suggests that, for
very short pulses, the threshold is independent on the doping level and therefore, linear absorption does not significantly
contribute to laser-induced damage. For >100 pulses per spot and all pulse durations applied, the threshold fluences
saturate. This independence on the number of applied pulses leads to technically relevant damage threshold values.
Laser-induced periodic surface structures (LIPSS, ripples) are a universal phenomenon that can be observed on almost any material after the irradiation by linearly polarized laser beams, particularly when using ultrashort laser pulses with durations in the femtosecond to picosecond range. During the past years significantly increasing industrial and research activities have been reported in the field of LIPSS, since their generation in a single-step process provides a simple way of nanostructuring and surface functionalization towards the control of optical, mechanical or chemical surface properties. In this contribution the mechanisms of formation and current trends and applications of LIPSS are reviewed, including the colorization of technical surfaces, the control of surface wetting properties, the mimicry of the natural texture of animals, the tailoring of surface colonization by bacterial biofilms, the advancement of leadless medical pacemakers, and the improvement of the tribological performance of nanostructured metal surfaces.
For pulse laser materials processing often optical step index and gradient index multimode fibers with core diameters ranging from 100 to 600 μm are used. The design of a high power fiber transmission system must take into account limitations resulting from both surface and volume damage effects. Especially, breakdown at the fiber end faces and self-focusing in the fiber volume critically influence the fiber performance. At least operation charts are desirable to select the appropriate fiber type for given laser parameters.
In industry-relevant studies the influence of fiber core diameter and end face preparation on laser-induced (surface) damage thresholds (LIDT) was investigated for frequently used all-silica fiber types (manufacturer LEONI). Experiments on preform material (initial fiber material) and compact specimens (models of the cladding and coating material) accompanied the tests performed in accordance with the relevant LIDT standards ISO 21254-1 and ISO 21254 2 for 1-on-1 and S-on-1 irradiation conditions, respectively. The relation beam diameter vs. LIDT was investigated for fused silica fibers. Additionally, laser-induced (bulk) damage thresholds of fused silica preform material F300 (manufacturer Heraeus) in dependence on external mechanical stress simulating fiber bending were measured. All experiments were performed with 10-ns laser pulses at 1064 and 532 nm wavelength with a Gaussian beam profile.
Light concentration opens up the path to enhanced material efficiency of solar cells via increased conversion efficiency and decreased material requirement. For true material saving, a fabrication method allowing local growth of high quality absorber material is essential. We present two scalable fs-laser based approaches for bottom-up growth of Cu(In,Ga)Se2 micro islands utilizing either site-controlled assembly of In(,Ga) droplets on laser-patterned substrates during physical vapor deposition, or laser-induced forward transfer of (Cu,In,Ga) layers for local precursor arrangement. The Cu(In,Ga)Se2 absorbers formed after selenization can deliver working solar devices showing efficiency enhancement under light concentration.
The current state in the field of laser-induced periodic surface structures (LIPSS, ripples) is reviewed. Their formation mechanisms are analyzed in ultrafast experiments (time-resolved diffraction and polarization controlled double-pulse experiments) and technological applications are demonstrated.
The selective emitter is a well-known technology for producing highly doped areas under the metallization grid to improve the solar cell performance. In this work, the influence of laser irradiation on phosphoric acid coated multicrystalline silicon PV-wafers on the wafer surface structure, the phosphorous depth distribution and the electrical contact resistance within the laser treated area as well as the electrical series resistance of laserprocessed solar cells was evaluated. Different laser processing settings were tested including pulsed and continuous wave (cw) laser sources (515 nm, 532 nm, 1064 nm wavelength). Complementary numerical simulations using the finite element method (FEM) were conducted to explain the impact of the laser parameters on the melting behavior (melt duration and geometry). It was found that the melt duration is a key parameter for a successful laser Doping process. Our simulations at a laser wavelengths of 515 nm reveal that low-repetition rate (<500 kHz) laser pulses of 300 ns duration generate a melt duration of ~0.35 µs, whereas upon scanning cw-laser radiation at 532 nm prolongates the melt duration by at least one order of magnitude. Experimentally, the widely used ns-laser pulses did not lead to satisfying laser irradiation results. In contrast, cw-laser radiation and scan velocities of less than 2 m/s led to suitable laser doping featuring low electrical resistances in the laser treated areas.
The formation of laser-induced periodic surface structures (LIPSS) upon irradiation of semiconductors and dielectrics by linearly polarized high-intensity Ti:sapphire fs-laser pulses (τ ~100 fs, λ ~800 nm) is studied experimentally and theoretically. In the experiments, two different types of LIPSS exhibiting very different spatial periods are observed (socalled LSFL low spatial frequency LIPSS, and HSFL - high spatial frequency LIPSS), both having a different dependence on the incident laser fluence and pulse number per spot. The experimental results are analyzed by means of a new theoretical approach, which combines the generally accepted LIPSS theory of J. E. Sipe and co-workers [Phys. Rev. B 27, 1141-1154 (1983)] with a Drude model, in order to account for transient changes of the optical properties of the irradiated materials. The joint Sipe-Drude model is capable of explaining numerous aspects of fs-LIPSS formation, i.e., the orientation of the LIPSS, their fluence dependence as well as their spatial periods. The latter aspect is specifically demonstrated for silicon crystals, which show experimental LSFL periods Λ somewhat smaller than λ. This behaviour is caused by the excitation of surface plasmon polaritons, SPP, (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 fields with that of the incident laser beam, resulting in a spatially modulated energy deposition at the surface.
Upon multi-pulse irradiation, a feedback mechanism, caused by the redshift of the resonance in a grating-assisted SPP excitation, is further reducing the LSFL spatial periods. The SPP-based mechanism of LSFL successfully explains the remarkably large range of LSFL periods between ~0.6 λ and λ.
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.
Optical filters and fabrics are important parts of laser safety equipment such as goggles and curtains. A choice of these materials with varying absorption spectra is investigated with respect to their resistance to Ti:sapphire femtosecond laser radiation (800 nm wavelength, 1 kHz repetition rate). Pulse durations down to 30 fs and multiple-pulse irradiation conditions are employed to evaluate technically relevant damage thresholds. The ablation threshold fluences of the absorbing filters are comparable to those observed for transparent materials with 30-fs-pulses. These investigations together with scanning electron microscopy of the surface morphology after laser treatment provide insight into the interaction mechanism of the short pulses with the materials.
Ultrashort pulse laser materials processing can be accompanied by the production of X-rays. Small doses per laser pulse can accumulate to significant dose rates at high laser pulse repetition rates which may exceed the permitted X-ray limits for human exposure. Consequently, a proper radiation shielding must be considered in laser machining. A brief overview of the current state of the art in the field of undesired generation of X-ray radiation during ultrashort pulse laser material processing in air is presented.
Many wooden artworks are contaminated by DDT (dichlorodiphenyltrichloroethane) as a result of a surface treatment by means of the liquid preservative Hylotox-59©. It was used until the end of the 1980s. DDT crystal structures are formed on the wood surfaces by the "blooming" of chlorine compounds. In addition to an aesthetic disturbance, it is assumed that DDT represents a health risk. Even decades after applying, the toxins in the wood preservatives are still detectable because they are of low volatility in many wood samples. Contaminated waste wood with natural biocide ageing, gilded and wood carved elements of an old picture frame and wooden samples with paint layers were provided by the Schlossmuseum Sondershausen. Non-contact procedures using laser and plasma appear reasonable to remove the DDT crystals. During the experiments, health and safety issues for the operator have to be taken into account.
The removal of DDT was evaluated employing femtosecond and nanosecond laser radiation and cold atmospheric plasma techniques with different working gases (air, nitrogen, and argon). Before laser application, a chlorine measurement representing the DDT density on the wooden surface is done by X-ray fluorescence (XRF) analysis as reference. After laser processing, the XRF analysis is used again at the same surface position to determine the depletion rate. Additionally, a documentation and characterization of the sample surface is performed before and after laser and plasma treatment using optical microscopy (OM). For plasma processing with various systems a chlorine measurement is done by gas chromatographic-mass spectrometry (GCMS) analysis.
This contribution investigates laser-induced damage of thin film and bulk polymer
samples, with the focus on physical processes occurring close to the damage threshold. In-situ
real-time reflectivity (RTR) measurements with picosecond (ps) and nanosecond (ns) temporal
resolution were performed on thin polymer films on a timescale up to a few microseconds (µs).
A model for polymer thin film damage is presented, indicating that irreversible chemical
modification processes take place already below the fluence threshold for macroscopic damage.
On dye-doped bulk polymer filters (as used for laser goggles), transmission studies using fs-and
ps-laser pulses reveal the optical saturation behavior of the material and its relation to the
threshold of permanent damage. Implications of the sub-threshold processes for laser safety
applications will be discussed for thin film and bulk polymer damage.
Paper is one of the most important materials representing and witnessing human culture particularly as a carrier medium for text and image. As soiling hampers the reception of information, paper cleaning techniques are needed. Traditional mechanical and chemical cleaning methods are used by conservator-restorers. In some cases, a classical cleaning procedure of paper objects yields unsatisfactory results or a conventional treatment is even impossible. Especially, fragile paper objects cause problems due to mechanical instabilities. Laser cleaning as a non-contact method might be a way to overcome some of the limitations of classical cleaning techniques. Laser parameters have to be chosen to achieve removal of the soiling without influencing the artwork. Any immediate as well as long-term effects causing an irreversible change of the artwork have to be avoided. At present, most laser applications are found in stone and metal conservation, while laser treatment of complex organic materials like paper is still not fully developed for application in conservators' workshops. This contribution describes recent work of pulsed laser cleaning of soiled model samples. Pure cellulose, rag paper and wood-pulp paper were mechanically soiled with pulverized charcoal in a standardized procedure to make model samples representing essential characteristics of contaminated real-world artworks. Afterwards, model samples were cleaned using short and ultrashort laser pulses in the nanosecond and femtosecond time domain, respectively. An extensive analysis of the model samples after laser treatment using an optical microscope and a multi-spectral imaging system allows a comparison of the cleaning results obtained with both laser sources.
One of the most important materials presenting and witnessing human culture is paper. The cleaning of paper is often necessary because contamination must be removed so that the fragile organic substrate can be preserved. The conventional cleaning methods are mechanical or involve the application of chemicals. These methods can damage drawings or print layers to some extent or make the original paper substrate brittle. More specifically, the use of a scalpel blade can cause damage to fibers. Chemical cleaning is difficult to perform locally, can dissolve foreign matter that then migrates into the paper substrate, or involves volatile organic compounds that can be harmful to the conservator. There is, therefore, a need for new conservation technologies aimed at the safe cleaning of paper. Lasers have proved to be an appropriate tool for cleaning as the energy dose and penetration depth at the specific point of contamination can be controlled. Additionally, if used properly, laser cleaning is not destructive to the paper.
Censorship of parts of written text was and is a common practice in totalitarian regimes. It is used to destroy information not approved by the political power. Recovering the censored text is of interest for historical studies of the text. This paper raises the question, whether a censored postcard from 1942 can be made legible by applying multispectral imaging in combination with laser cleaning. In the fields of art conservation (e.g. color measurements), investigation (e.g. Analysis of underdrawings in paintings), and historical document analysis, multispectral imaging techniques have been applied successfully to give visibility to information hidden to the human eye.
The basic principle of laser cleaning is to transfer laser pulse energy to a contamination layer by an absorption process that leads to heating and evaporation of the layer. Partial laser cleaning of postcards is possible; dirt on the surface can be removed and the obscured pictures and writings made visible again. We applied both techniques to the postcard. The text could not be restored since the original ink seems to have suffered severe chemical damage.
Laser-induced periodic surface structures (LIPSS, ripples) are a universal phenomenon that can be observed on almost any material after the irradiation by linearly polarized laser beams, particularly when using ultrashort laser pulses with durations in the picosecond to femtosecond range. During the past few years significantly increasing research activities have been reported in the field of LIPSS, since their generation in a single-step process provides a simple way of nanostructuring and surface functionalization towards the control of optical, mechanical or chemical properties. In this contribution current applications of LIPSS are reviewed, including the colorization of technical surfaces, the control of surface wetting, the tailoring of surface colonization by bacterial biofilms, and the improvement of the tribological performance of nanostructured metal surfaces.