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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 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.
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.
Some nonlinear optical properties such as the nonlinear refractive index and the nonlinear effective absorption, as well as the laser-induced single-pulse ablation threshold are characterized for a series of binary and ternary silicate glasses upon irradiation with near-infrared femtosecond laser pulses (800 nm, 130 fs). The laser-induced ablation threshold varies from 2.3 J/cm² in case of potassium silicate glass up to 4.3 J/cm² in case of Fused Silica. Nonlinear refractive indices are qualitatively similar within the range 1.7-2.7×10-16 cm²/W. Complementary optical and physico-chemical properties like band gap energy and the glass transformation temperature have been measured for all the glasses.
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.
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 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.
Over the past years, many applications based on laser-induced refractive index changes in the volume of transparent materials have been demonstrated. Ultrashort pulse lasers offer the possibility to process bulky transparent materials in three dimensions, suggesting that direct laser writing will play a decisive role in the development of integrated micro-optics. At the present time, applications such as 3D long term data storage or embedded laser marking are already into the phase of industrial development. However, a quantitative estimate of the laser-induced refractive index change is still very challenging to obtain. On another hand, several microscopy techniques have been recently developed to characterize bulk refractive index changes in-situ. They have been mostly applied to biological purposes. Among those, spatial light interference microscopy (SLIM), offers a very good robustness with minimal post acquisition data processing. In this paper, we report on using SLIM to measure fs-laser induced refractive index changes in different common glassy materials, such as fused silica and borofloat glass (B33). The advantages of SLIM over classical phase-contrast microscopy are discussed.
Compositional dependent response of silica-based glasses after femtosecond laser pulse irradiation
(2013)
Femtosecond laser pulse irradiation of inorganic glasses allows a selective modification of the optical properties with very high precision. This results in the possibility for the production of three-dimensional functional optical elements in the interior of glass materials, such as optical data storage, waveguide writing, etc. The influence of the chemical glass composition to the response upon ultrashort laser irradiation has not been studied systematically. For that, simple silicabased model glasses composed of systematically varying alkaline- and earth-alkaline components were prepared, irradiated on the surface and in the volume with single fs-laser pulses (~130 fs, 800 nm), and were subsequently analyzed by means of micro-Raman spectroscopy and quantitative phase contrast microscopy in order to account for changes in the glass structure and for alterations of the optical refractive index, respectively. The Raman spectroscopic studies of the laser-irradiated spots revealed no change in the average binding configuration (the so called Q-structure), but local changes of bond-angles and bond-lengths within the glass structure structure. Those changes are explained by structural relaxation of the glass network due to densification caused by a transient laser-induced plasma generation and the following shock wave and other thermal phenomena. Glasses with a low amount of network modifiers show changes in the Si-O network while glasses with a high amount of network modifiers react primarily via variation of the nonbridging oxygen ions. The results are discussed in terms of possible structural response mechanisms and conclusions are outlined regarding glass compositions with technical suitability for fs-laser modifications.
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.
In this work, glasses with systematically varied compositions were manufactured and irradiated by single Ti:sapphire fs-laserpulses (800 nm, 120 fs), focused at the surface and into the bulk of the glass materials. The samples were tested for their ablation threshold fluence as well as for structural changes using µ-Raman-spectroscopy. Correlations between the glass composition, the material-ablation on the glass surface and the permanent changes of the refractive index inside the glass volume after the irradiation by fs-laser pulses were obtained. The results show, that the structural modifications found at the surface of the glasses and inside its volume are closely related. However, while the ablation threshold fluence of the glass surface primarily depends on the glass dissociation energy, the permanent refractive index change inside the volume is rather determined by its ability for absorbing the fs-laser pulses and the subsequent relaxation processes. The results of this work provide some guidance on how the glass composition can be varied in order to optimize the fs-laser induced modification of dielectrics.
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.
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 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.
Optical multimode fibers are applied in materials processing (e.g. automotive industry), defense, aviation technology, medicine and biotechnology. One challenging task concerning the production of multimode fibers is the enhancement of laser-induced damage thresholds. A higher damage threshold enables a higher transmitted average power at a given fiber diameter or the same power inside a thinner fiber to obtain smaller focus spots.
In principle, different material parameters affect the damage threshold. Besides the quality of the preform bulk material itself, the drawing process during the production of the fiber and the preparation of the fiber end surfaces influence the resistance. Therefore, the change of the laser-induced damage threshold of preform materials was investigated in dependence on a varying thermal treatment and preparation procedure.
Single and multi-pulse laser-induced damage thresholds of preforms (F300, Heraeus) were measured using a Q-switched Nd:YAG laser at 1064 nm wavelength emitting pulses with a duration of 15 ns, a pulse energy of 12 mJ and a repetition rate of 10 Hz. The temporal and spatial shape of the laser pulses were controlled accurately.
Laser-induced damage thresholds in a range from 150 J cm-2 to 350 J cm-2 were determined depending on the number of pulses applied to the same spot, the thermal history and the polishing quality of the samples, respectively.
High-power optical multimode fibers are essential components for materials processing and surgery and can limit the performance of expensive systems due to breakdown at the end faces. The aim of this paper is the determination of laser-induced damage thresholds (LIDT) of fibers (FiberTech) and preforms (Heraeus Suprasil F300). Preforms served as models. They were heated up to maximum temperatures of 1100, 1300 and 1500°C and cooled down to room temperature at rates of 10 K min-1 (oven) and ~105 K min-1 (quenched in air) to freeze in various structural states simulating different conditions similar to a drawing process during the production of fibers. Single- and multi-pulse LIDT measurements were done in accordance with the relevant ISO standards. Nd:YAG laser pulses with durations of 15 ns (1064 nm wavelength) and 8.5 ns (532 nm) at a repetition rate of 10 Hz were used. For the preforms, LIDT values (1-on-1) ranged from 220 to 350 J/cm² (1064 nm) and from 80 to 110 J/cm² (532 nm), respectively. A multi-pulse impact changed the thresholds to lower values. The LIDT (1064 nm wavelength) of the preforms can be regarded as a lower limit for those of the fibers.
Silver in LTCC - Interfacial reactions, transport processes and influence on properties of ceramics
(2009)
For many applications, optical multimode fibers are used for the transmission of powerful laser radiation. High light throughput and damage resistance are desirable. Laser-induced breakdown at the end faces of fibers can limit their performance. Therefore, the determination of laser-induced damage thresholds (LIDT) at the surface of fibers is essential.
Nanosecond (1064 nm and 532 nm wavelength) single-shot LIDT were measured according to the relevant standard on SiO2 glass preforms (Suprasil F300) as basic materials of the corresponding fibers. For 10 kinds of fused silica fibers (FiberTech) with core diameters between 180 µm and 600 µm, an illumination approach utilizing a stepwise increase of the laser fluence on a single spot was used. For both wavelengths, the LIDT values (0% damage probability) obtained by means of the two methods were compared. The influence of surface preparation (polishing) on damage resistance was investigated. For equal surface finishing, a correlation between drawing speed of the fibers and their surface LIDT values was found. In addition to the surface measurements, bulk LIDT were determined for the preform material.
Detailed study of laser doping processes for the selective emitter using phosphoric acid as dopant
(2011)
High-power optical multimode fibers are essential components for materials processing
and surgery and can limit the reliability of expensive systems due to breakdown at the end faces.
The breakdown threshold of fibers is determined by intrinsic materials properties and parameters of
the technology applied. The aim of this paper is the identification of technological parameters that
are crucial for the fiber quality.
Fibers were drawn from preforms of Heraeus SWU with core material F300 and a low amount of
OH-. Both, the cladding (fluorine doped SiO2) to core diameter ratio (CCDR) and the drawing speed
were varied. CCDR values between 1.05 and 1.4 were used. Afterwards, the laser-induced damage
thresholds (LIDT) of the fibers were determined. For comparison, also samples from preforms,
which underwent different thermal treatments above the transition temperature, were tested with
respect to their damage resistivity. Single and multi pulse LIDT measurements were done in
accordance with the relevant ISO standards. Nd:YAG laser pulses with durations of 15 ns (1064 nm
wavelength) and 8.5 ns (532 nm) at a repetition rate of 10 Hz were utilized. For the fibers, LIDT
values (1-on-1, 1064 nm and 532 nm) increased with growing CCDR and with decreasing drawing
velocities.
Single and multi pulse laser-induced damage thresholds (LIDT) of core, cladding, and coating materials of high-power
optical multimode fibers were determined in accordance with ISO 11254 for 532 nm and 1064 nm wavelength in the 10-ns
pulse duration regime with spatial Gaussian beam shape. For all-silica fibers, LIDT increases with rising core diameter in a range between 100-600 µm for a constant cladding-core ratio of 1.2. The damage resistance of the low refracting cladding (0.3 % fluorine doped fused silica) is comparable to the undoped SiO2 core. Coating materials show significantly lower LIDT than light-guiding parts of the fibers.
Towards an industrial laser doping process for the selective emitter using phosphoric acid as dopand
(2011)