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Eingeladener Vortrag
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Template Electrodeposition of Nanowire Arrays on Gold Foils Fabricated by Pulsed-Laser Deposition
(1995)
A detailed diagnostic study of the interaction of nanosecond laser pulses from the near-ultraviolet into the near-infrared
wavelength range with various types of contemporary and ancient parchments is presented. The advantages of laser
cleaning due to the absence of chemical agents, spectroscopic selectivity, micro-precision, computer-aided handling can
only be verified when physico-chemical diagnostics guarantee destructionless processing. Scanning Electron Microscopy
(SEM) data are correlated with morphological changes in dependence on the laser fluence and wavelength. The
question, to what extent the chemical degradation of collagen is affected by various laser treatment parameters, could be
resolved by Transmission Electron Microscopy (TEM) of collagen fibres collected from the outermost laser-exposed
surface layer. It is also shown how Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFT), and
Pyrolysis Capillary Gaschromatography (PY-CGC) can be employed in the chemical diagnostics of laser cleaning of
parchment. This study suggests that the ageing status of parchment artefacts plays a major role in assessing the laser
cleaning limits.
A detailed diagnostic study of the interaction of nanosecond laser pulses from the near-ultraviolet to the near-infrared wavelength range with various types of contemporary and ancient parchments is presented. The advantages of laser cleaning due to the absence of chemical agents, spectroscopic selectivity, micro-precision and computer-aided handling can only be verified when physico-chemical diagnostics guarantee destructionless processing. Scanning electron microscopy data are correlated with chemical degradation and morphological changes dependent on the laser fluence and wavelength. It is also shown how transmission electron microscopy, diffuse reflectance infrared Fourier transform spectroscopy, and pyrolysis capillary gas chromatography can be employed in the chemical diagnostics of laser cleaning of parchment. This study suggests that the ageing status of parchment artefacts plays a major role in assessing the laser cleaning limits.
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.
Optical fibers made of fused silica are a common method of transmitting high laser pulse energies. Failure of those fibers is a significant risk. The determination of laser-induced damage thresholds (LIDT) on fiber end facets according to ISO 21254 standard is needed. In the past, single pulse nanosecond laser experiments showed an improvement of LIDT with increasing fiber core diameter for 1064 nm wavelength and a constant beam diameter of 50 µm.
This paper pays particular attention to the influence of the laser beam diameter on damage resistance. All-silica fiber types (LEONI) with different core diameters (100–600 µm) were investigated using beam diameters in a range from 30 µm to 100 µm. For comparison experiments on fused silica preform material (Heraeus F300) were performed. On one hand, surface LIDT of fused silica preform material decreases significantly with increasing beam size. A model considering a random distribution of point defects explains the experimental data qualitatively. On the other hand, LIDT of fiber end facets stays constant. White light microscopy results suggest that the point defect density on fiber end facets is lower compared to the preform surface due to an excellent surface polish quality.
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.
Laser cleaning of delicate biological composite materials such as ancient parchment manuscripts from the 15th and 16th century and printed paper from the 19th century is demonstrated with an ultraviolet excimer pulsed laser at 308 nm. Laser fluence levels must stay below the ablation and destruction threshold of the parchment or paper substrate, and have to surpass the threshold of the contaminant matter. Foreign layers to be removed must exhibit a higher optical density than the artifact substrates. Synthetic carbonaceous dirt modelled by water-soluble black crayons showed a characteristically weak featureless laser-induced plasma spectroscopy spectrum near the noise limit. It turned out that laser-induced plasma spectroscopy is of limited use in monitoring halting points (or etch-stops) because it relies on the destruction not only of the laterally inhomogenously distributed contaminant but also of pigment phases on a microscopically rough parchment substrate. Laser-induced fluorescence spectroscopy, however, promises to be a valuable non-destructive testing technique for etch-stop monitoring.
Laser cleaning of soiled paper is a challenging task due to the fact that a contamination has to be removed and a fragile organic material has to be preserved. The ejection of particles forms a significant channel for the removal of unwanted surface contaminations and can be exploited for an in-situ monitoring of the cleaning procedure. 532-nm-nanosecond single and multi pulse laser cleaning of artificially soiled Whatman© paper was performed. Particles were registered with a dust monitor. These in-situ experiments were combined with ex-situ investigations of cleaning and substrate damage thresholds by means of light and scanning electron microscopic techniques. The cleaning efficiency measured by a multi-spectral imaging system was compared to the in-situ particle monitoring. Additionally, possible color changes of the paper substrate were evaluated.
Characterization of laser-generated microparticles by means of a dust monitor and SEM imaging
(2006)
Nanosecond laser (1064 nm wavelength) cleaning of artificially soiled paper as a model sample simulating a real-world artwork was performed. During the cleaning process, the ejection of particles was monitored in situ by means of a dust monitor (8 size classes, ranging from 0.3 µm to >2 µm) and ex situ using a mini-cascade impactor (MKI, 5 stages). The cleaning result was analyzed by scanning electron microscopy (SEM) considering possible laser-induced damages to the substrate. Size distributions of emitted particles were measured depending on the processing parameters: laser fluence, F, and pulse number per spot, N. High numbers of large (>2 µm) particles were collected by the mini-cascade impactor indicating a gas dynamical liftoff process. Obviously, these particles were not affected by the laser-matter interaction. The different methods (SEM, MKI, and dust monitor) are compared with respect to their usefulness for a proper interpretation of the cleaning results.
Cleaning of paper is a challenging task due to the fact that a contamination should be removed and a fragile organic original material has to be preserved. Pulsed laser cleaning of artificially soiled Whatman© filter paper samples serving as models for historical paper was performed. Different cleaning strategies employing 8-ns laser pulses at 532 nm wavelength were applied to clean paper avoiding undesired effects like discoloration (yellowing) and mechanical deterioration of the substrate. Multi shot experiments with low-energy pulses were compared with single pulse investigations utilizing high pulse energies achieving a constant energy load incident on the samples in both cases. The cleaning efficiency and possible yellowing effects were evaluated by means of a multi spectral imaging system. An extensive microscopic analysis of the cleaned parts of the samples provided insight into the remaining soiling on the surface and in the bulk of the paper material after laser treatment. As a reference, a hard and a soft eraser were used to clean the samples.
Noble metal-free nanoparticles (NPs) based on multi-principal element alloys (MPEAs) were synthesized using a one-step pulsed laser ablation in liquids (PLALs) method for the electrochemical reduction of CO2. Laser ablation was performed in pure water or poly-(diallyldimethylammonium chloride) (PDADMAC)-containing an aqueous solution of Al8Cr17Co17Cu8Fe17Ni33 MPEA targets. Transmission electron microscopy (TEM) measurements combined with energy dispersive X-ray (EDX) mapping were used to characterize the structure and composition of the laser-generated MPEA nanoparticles (MPEA-NPs). These results confirmed the presence of a characteristic elemental distribution of a core-shell phase structure as the predominant NP species. The electrocatalytic performance of the laser-generated MPEA-NPs was characterized by linear sweep voltammetry (LSV) demonstrating an enhanced electrocatalytic CO2 activity for PDADMAC-stabilized NPs. The findings of these investigations indicate that MPEAs have great potential to replace conventional, expensive noble metal electrocatalysts.
A great number of Central Asian wall paintings, archeological materials, architectural fragments, and textiles, as well as painting fragments on silk and paper, make up the so called Turfan Collection at the Asian Art Museum in Berlin. The largest part of the collection comes from the Kucha region, a very important cultural center in the third to ninth centuries. Between 1902 and 1914, four German expeditions traveled along the northern Silk Road. During these expeditions, wall paintings were detached from their original settings in Buddhist cave complexes. This paper reports a technical study of a wall painting, existing in eight fragments, from the Buddhist cave no. 40 (Ritterhöhle). Its original painted surface is soot blackened and largely illegible. Grünwedel, leader of the first and third expeditions, described the almost complete destruction of the rediscovered temple complex and evidence of fire damage. The aim of this case study is to identify the materials used for the wall paintings. Furthermore, soot deposits as well as materials from conservation interventions were of interest. Non-invasive analyses were preferred but a limited number of samples were taken to provide more precise information on the painting technique. By employing optical and scanning electron microscopy, energy dispersive X-ray spectroscopy, micro X-ray fluorescence spectroscopy, X-ray diffraction analysis, and Raman spectroscopy, a layer sequence of earthen render, a ground layer made of gypsum, and a paint layer containing a variety of inorganic pigments were identified.
This contribution compares traditional cleaning and laser methods. Partial laser cleaning with a nanosecond pulse laser (wavelength of 532 nm) has proved very promising for future application in paper conservation-restoration. Traditional cleaning methods are not always sufficient or successful in surface cleaning of objects of art. Comparative studies of traditional paper cleaning methods and laser cleaning were made on several historic picture postcards printed with the chromolithography technique.
Laser cleaning for works of art on paper might be a supplemental, noncontact method to overcome some of the limitations of traditional dry cleaning techniques. Three different types of paper (pure-cellulose filter paper, rag paper, and wood-pulp paper) were mechanically soiled with pulverized charcoal in a standardized procedure to make model samples. These samples were characterized microscopically and by means of lightness measurements using a multi-spectral imaging system. A prototype laser workstation with Laser Class I conditions for the operator was used for the cleaning experiments. For 10-ns laser pulses at a wavelength of 532 nm, a set of laser parameters was established for a successful cleaning of the samples avoiding damage to the paper substrate. Single- and multi-pulse illumination conditions were tested. An extensive microscopic analysis after laser treatment of the cleaned parts of the samples provided insight into the remaining soiling on the surface and in the bulk of the paper material.
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.
Cleaning of artificially soiled paper using nanosecond, picosecond and femtosecond laser pulses
(2010)
Cleaning of cultural assets, especially fragile
organic materials like paper, is a part of the conservation
process. Laser radiation as a non-contact tool offers
prospects for that purpose. For the studies presented here,
paper model samples were prepared using three different paper
types (pure cellulose, rag paper, and wood-pulp paper).
Pure cellulose serves as reference material. Rag and woodpulp
paper represent essential characteristics of the basic
materials of real-world artworks. The papers were mechanically
soiled employing pulverized charcoal. Pure and artificially soiled paper samples were treated with laser pulses of
28 fs (800 nm wavelength) and 8–12 ns (532 nm) duration in
a multi pulse approach. Additionally, the cellulose reference
material was processed with 30 ps (532 nm) laser pulses.
Damage and cleaning thresholds of pure and soiled paper
were determined for the different laser regimes. Laser working
ranges allowing for removal of contamination and avoiding
permanent modification to the substrate were found.
The specimens prior and after laser illumination were characterized
by light-optical microscopy (OM) and scanning
electron microscopy (SEM) as well as multi spectral imaging
analysis. The work extends previous nanosecond laser
cleaning investigations on paper into the ultra-short pulse
duration domain.
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.
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.
Until the end of the 1980s many wooden artworks underwent surface treatment by liquid preservatives, e.g. Hylotox-59. DDT (dichlorodiphenyltrichloroethane) crystal structures are formed on the wooden surfaces by the "blooming" of chlorine compounds by time. In addition to an aesthetic disturbance, it is assumed that DDT represents a health risk. Therefore, the removal of DDT crystals from the surfaces is requested. Contaminated wood with natural biocide ageing, gilded and wood carved elements and wooden samples with paint layers were provided by the Schlossmuseum Sondershausen, Germany. Laser cleaning on selected surface areas on the objects was done by means of femtosecond and nanosecond laser pulses. For the same object, cleaning results using 30-fs laser pulses at 800 nm wavelength are compared to findings utilizing 10-ns laser pulses at 1064 nm wavelength. Before and after laser treatment, chlorine measurements at the same surface position were done by X-ray fluorescence analysis (XRF) as an indicator for the presence of DDT. In this way, pointwise chlorine depletion rates can be obtained for the different pulse duration regimes and wavelengths. Additionally, the object surfaces were examined using optical microscopy and multi spectral imaging analysis.
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.
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.
Laser-induced periodic surface structures (LIPSS) were generated on two types of steel (100Cr6, X30CrMoN15-1) and two types of titanium (Ti, Ti6A14V) surfaces upon irradiation with multiple linear polarized femtosecond laser pulses in air environment (pulse duration 30 fs, central wavelength 790 nm, pulse repetition rate 1 kHz, Gaussian beam shape). Teh conditions (laser fluence, spatial spot overlap) were optimized in a sample-scanning geometry for the processing of large surface areas covered homogeneously by two different types of LIPSS - either near wavelength or sub-100 nm structures. The tribological performance of the nanostructured surfaces was characterized under reciprocating sliding at 1 Hz against a ball of hardened steel using different lubricants and normal forces. After 1000 cycles the corresponding wear tracks were characterized by optical and scanning electron microscopy. For specific conditions, the wear was strongly reduced and laser-generated nanostructures endured the tribological treatment. Simultaneously, a significant reduction of the friction coefficient was observed in the laser-irradiated LIPSS-covered areas, indicating the benefit of laser surface structuring for tribological applications. The spatially Gaussian shaped beam used for the laser processing was transformed via beam shaping into a top hat distribution at the surface of the samples for optimization. The tribological performance of the laser-induced nanostructures is discussed on the basis of different physical and chemical mechanisms.
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.
Single-pulse damage thresholds of hydrogenated amorphous carbon (a-C:H) films were measured for 8-ns laser pulses at 532-nm wavelength. Layer thicknesses from below the optical penetration depth to above the thermal diffusion length (60 nm13 µm) were examined. After correction of the damage-threshold values for the fraction of energy effectively absorbed by the material, the damage threshold was found to increase linearly with the layer thickness, also for film thicknesses below the optical penetration depth of a-C:H. The threshold fluence reached the bulk value for a layer thickness equal to the thermal diffusion length. The thermal diffusion coefficient was obtained from fitting the experimental data. Several phenomena like graphitization, blistering, exfoliation, and ablation were observed for different fluence regimes and film thicknesses.
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.
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.
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.
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.
Noble metal-free nanoparticles (NPs) based on multi-principal element alloys (MPEAs) were synthesized using a one-step pulsed laser ablation in liquids (PLALs) method for the electrochemical reduction of CO2. Laser ablation was performed in pure water or poly-(diallyldimethylammonium chloride) (PDADMAC)-containing an aqueous solution of Al8Cr17Co17Cu8Fe17Ni33 MPEA targets. Transmission electron microscopy (TEM) measurements combined with energy dispersive X-ray (EDX) mapping were used to characterize the structure and composition of the laser-generated MPEA nanoparticles (MPEA-NPs). These results confirmed the presence of a characteristic elemental distribution of a core-shell phase structure as the predominant NP species. The electrocatalytic performance of the laser-generated MPEA-NPs was characterized by linear sweep voltammetry (LSV) demonstrating an enhanced electrocatalytic CO2 activity for PDADMAC-stabilized NPs. The findings of these investigations indicate that MPEAs have great potential to replace conventional, expensive noble metal electrocatalysts.