Microstructuring of fused silica by laser-induced backside wet etching using picosecond laser pulses

The laser-induced backside wet etching (LIBWE) is an advanced laser processing method used for structuring transparent materials. LIBWE with nanosecond laser pulses has been successfully demonstrated for various materials, e.g. oxides (fused silica, sapphire) or fluorides (CaF₂, MgF₂), and applied for the fabrication of microstructures. In the present study, LIBWE of fused silica with mode-locked picosecond (t_p = 10 ps) lasers at UV wavelengths (λ₁ = 355 nm and λ₂ = 266 nm) using a (pyrene) toluene solution was demonstrated for the first time. The influence of the experimental parameters, such as laser fluence, pulse number, and absorbing liquid, on the etch rate and the resulting surface morphology were investigated. The etch rate grew linearly with the laser fluence in the low and in the high fluence range with different slopes. Incubation at low pulse numbers as well as a nearly constant etch rate after a specific pulse number for example were observed. Additionally, the etch rate depended on the absorbing liquid used; whereas the higher absorption of the admixture of pyrene in the used toluene enhances the etch rate and decreases the threshold fluence. With a λ₁ = 266 nm laser set-up, an exceptionally smooth surface in the etch pits was achieved. For both wavelengths (λ₁ = 266 nm and λ₂ = 355 nm), LIPSS (laser-induced periodic surface structures) formation was observed, especially at laser fluences near the thresholds of 170 and 120 mJ/cm², respectively.     

Comparing study of subpicosecond and nanosecond wet etching of fused silica

The effectiveness of the laser induced backside wet etching (LIBWE) of fused silica produced by subpicosecond (600 fs) and nanosecond (30 ns) KrF excimer laser pulses (248 nm) was studied. Fused silica plates were the transparent targets, and naphthalene-methyl-methacrylate (c = 0.85, 1.71 M) and pyrene-acetone (c = 0.4 M) solutions were used as liquid absorbents. We did not observe etching using 600 fs laser pulses, in contrast with the experiments at 30 ns, where etched holes were found. The threshold fluences of the LIBWE at nanosecond pulses were found to be in the range of 360-450 mJ cm⁻² depending on the liquid absorbers and their concentrations. On the basis of the earlier results the LIBWE procedure can be explain by the thermal heating of the quartz target and the high-pressure bubble formation in the liquid. According to the theories, these bubbles hit and damage the fused silica surface. The pressure on the irradiated quartz can be derived from the snapshots of the originating and expanding bubbles recorded by fast photographic setup. We found that the bubble pressure at 460 mJ cm⁻² fluence value was independent of the pulse duration (600 fs and 30 ns) using pyrene-acetone solution, while using naphthalene-methyl-methacrylate solutions this pressure was 4, 5 times higher at 30 ns pulses than it was at 600 fs pulses. According to the earlier studies, this result refers to that the pressure should be sufficiently high to remove a thin layer from the quartz surface using pyrene-acetone solution. These facts show that the thermal and chemical phenomena in addition to the mechanical effects also play important role in the LIBWE procedure.     

Submicrometer grating fabrication in fused silica by interferometric laser-induced backside wet etching technique

Submicrometer period fused silica gratings were produced by two-beam interferometric laser-induced backside wet etching technique (TWIN LIBWE). The fourth harmonic of a Nd:YAG laser beam was spatially filtered in two steps, and the smoothened beam was split into two parts and interfered at incident angles of 60°, 30°, 14°, and 7.7°, respectively, on the backsides of fused silica plates that were in contact with a liquid absorber. The periods of the produced fused silica gratings were, respectively, 154 nm, 266 nm, 550 nm, and 990 nm. In the next step, TWIN-LIBWE setup was completed by using a coupling rectangular prism in order to reach immersion setup, which made possible to fabricate 104 nm period fused silica grating. This is the smallest laser-generated grating constant in fused silica at present. The morphology of the etched gratings was characterized by atomic force microscope. Important parameters (modulation depth, low-pass filtered waviness, quality factor) of the produced gratings were determined. Evolution of the grating parameters was also studied in the 990 nm case: the dependence of modulation depth, waviness, and quality factor on the number of laser pulses was investigated.     

Mechanism of backside etching of transparent materials with nanosecond UV-lasers

In consequence of high interest in micro- and nanomachining of transparent materials by laser irradiation, studies on the mechanism of laser-induced backside wet etching (LIBWE) are presented. To reveal the role of the surface modification due to LIBWE the backside ablation (BSA) of LIBWE-modified fused silica (mFS) surfaces at 248 nm was investigated. The threshold fluence and the etch rate of BSA are similar to that of LIBWE and amount ∼250 mJ/cm² and 30 nm for 1 J/cm², respectively. The sample transmission after backside ablation of mFS increases and proves the decreasing thickness of the absorbing layer. Time-resolved reflection studies at LIBWE and BSA of mFS show similar patterns in the backside reflection that can be assigned an ablation process as the comparison to thin polymer films demonstrates. By fitting the BSA data to an exponential decay absorption model a modification depth and a surface absorption of about 38 nm and α ^S ∼1.3×10⁷ m⁻¹ were calculated, respectively. In conclusion of the results a new model for LIBWE is proposed.     

Influence on the laser induced backside dry etching of thickness and material of the absorber, laser spot size and multipulse irradiation

Laser induced backside dry etching method (LIBDE) was developed - analogously to the well-known laser induced backside wet etching (LIBWE) technique - for the micromachining of transparent materials. In this procedure, the absorbing liquid applied during LIBWE was replaced with solid metal layers. Fused silica plates were used as transparent targets. These were coated with 15-120 nm thick layers of different metals (silver, aluminium and copper). The absorbing films were irradiated by a nanosecond KrF excimer laser beam through the quartz plate. The applied fluence was varied in the 150-2000 mJ/cm² range, while the irradiated area was between 0.35 and 3.6 mm². At fluences above the threshold values, it was found that the metal layers were removed from the irradiated spots and the fused silica was etched at the same time. In our experiments, we investigated the dependence of the main parameters (etch rate and threshold) of LIBDE on the absorption of the different metal layers (silver, copper, aluminium), on the size of the irradiated area, on the film thickness and on the number of processing laser pulses.     

The influence of laser-induced surface modifications on the backside etching process

Spectroscopic measurements in the UV/VIS region show reduced transmission through laser-induced backside wet etching (LIBWE) of fused silica. Absorption coefficients of up to 10⁵ cm⁻¹ were calculated from the transmission measurements for a solid surface layer of about 50 nm. The temperatures near the interface caused by laser pulse absorption, which were analytically calculated using a new thermal model considering interface and liquid volume absorption, can reach 10⁴ K at typical laser fluences. The high absorption coefficients and the extreme temperatures give evidence for an ablation-like process that is involved in the LIBWE process causing the etching of the modified near-surface region. The confinement of the ablation/etching process to the modified near-surface material region can account for the low etch rates observed in comparison to front-side ablation.     

Backside etching of fused silica with Nd:YAG laser

The laser-induced backside etching of fused silica with gallium as highly absorbing backside absorber using pulsed infrared Nd:YAG laser radiation is demonstrated for the first time. The influence of the laser fluence, the pulse number, and the pulse length on the etch rate and the etched surface topography was studied. The comparable high threshold fluences of about 3 and 7 J/cm² for 18 and 73 ns pulses, respectively, are caused by the high reflectivity of the fused silica-gallium interface and the high thermal conductivity of gallium. For the 18 and 73 ns long pulses the etch rate rises almost linearly with the laser fluence and reaches a value of 350 and 300 nm/pulse at a laser fluence of about 12 and 28 J/cm², respectively. Incubation processes are almost absent because etching is already observed with the first laser pulse at all etch conditions and the etch rate is constant up to 30 pulses.The etched grooves are Gaussian-curved and show well-defined edges and a smooth bottom. The roughness measured by interference microscopy was 1.5 nm rms at an etch depth of 0.6 μm. The laser-induced backside etching with gallium is a promising approach for the industrial application of the backside etching technique with IR Nd:YAG laser.     

104 nm period grating fabrication in fused silica by immersion two-beam interferometric laser induced backside wet etching technique

A substantial extension of the method of two-beam interferometric laser induced backside wet etching (TWIN-LIBWE), the immersion TWIN-LIBWE, is used to fabricate fused silica gratings with a 104 nm period. The spatially filtered fourth harmonic of Nd:YAG laser (λ=266 nm, τ_FWHM=8 ns) pulses were split into two parts which then interfered at the backside of the fused silica target in contact with a liquid absorber (naphthalene methyl methacrylate saturated solution with a concentration of 1.85 mol/dm³). The hypotenuse of a rectangular fused silica prism is attached to the fused silica target with the use of distilled water as the immersion liquid. On steering the beams through the sides of the prisms, the angle between the two laser beams has been substantially increased. The resulting period of 104 nm is the minimal grating constant achievable under such experimental conditions and, to our knowledge, the smallest laser generated grating period in fused silica at present. PACS 42.62; 42.79; 81.65     

Laser-induced backside wet etching of fluoride and sapphire using picosecond laser pulses

Laser-induced backside wet etching (LIBWE) is a promising process for microstructuring of rigid chemical resistant and inert transparent materials. LIBWE with nanosecond laser pulses has been successfully demonstrated in a number of studies. LIBWE in a time scale of femtosecond and picosecond pulse durations has been investigated only in a few studies and just on fused silica. In the present study LIBWE of fluorides (CaF₂, MgF₂) and sapphire with a mode-locked picosecond (t _p=10 ps) laser at a UV wavelength of λ=355 nm using toluene as absorbing liquid has been demonstrated. The influence of the laser fluence and the pulse number on the etching rate and the achieved surface morphology was investigated. The etching rate grows linearly with the laser fluence in the low and high-fluence ranges with different slopes. The achieved etching rates for CaF₂ and for sapphire were in the same range. Contrary to CaF₂ and sapphire the etching rates of MgF₂ were one magnitude less. For backside etching on sapphire at high fluences smooth surfaces and at low fluences ripples pattern were found, whereas fluoride surfaces showed a trend towards crack formation.     

Micromachining of quartz crystal with excimer lasers by laser-induced backside wet etching

We fabricated a well-defined pattern of lines and spaces on the surface of a quartz crystal plate (c-SiO₂) with micron-sized features, using laser-induced backside wet etching (LIBWE). The line patterns obtained using LIBWE showed a high aspect ratio of about 3. The etch rates of fused silica (a-SiO₂) ranged from 5 to 25 nm/pulse with KrF laser irradiation from 0.4-1.3 J/cm². Threshold fluences for a-SiO₂ and c-SiO₂ were 0.23 and 0.34 J/cm², respectively. The single-pulse etch depth was not affected by the repetition rates of laser pulses from 1-50 Hz.     

Surface plasmon scattering on polymer-bimetal layer covered fused silica gratings generated by laser induced backside wet etching

Large amplitude fused silica gratings are prepared by combining the UV laser induced backside wet etching technique (LIBWE) and the two-beam interference method. The periodic patterning of fused silica surfaces is realized by s-polarized fourth harmonic beams of a Nd:YAG laser, applying saturated solution of naphthalene in methyl-methacrylate as liquid absorber. Atomic force microscopy is utilized to analyze how the modulation amplitude of the grating can be controlled by the fluence and number of laser pulses. Three types of plasmonic structures are prepared by a bottom-up method, post-evaporating the fused silica gratings by gold-silver bimetal layers, spin-coating the metal structures by thin polycarbonate films, and irradiating the multilayers by UV laser. The effect of the bimetal and polymer-coated bimetal gratings on the surface plasmon resonance is investigated in a modified Kretschmann arrangement allowing polar and azimuthal angle scans. It is demonstrated experimentally that scattering on rotated gratings results in additional minima on the resonance curves of plasmons excited by second harmonic beam of a continuous Nd:YAG laser. The azimuthal angle dependence proves that these additional minima originate from back-scattering. The analogous reflectivity minima were obtained by scattering matrix method calculations realized taking modulation depths measured on bimetal gratings into account.     

Laser processing of micro-optical components in quartz

Laser induced backside wet etching combined with the diffractive gray tone phase mask has been used for the fabrication of a micro-lens array with a single lens diameter of 1 mm and a micro-prism in quartz. The micro-lens array was tested as beam homogenizer for high power XeCl excimer laser yielding a clear improvement in the quality of the laser beam.The optimum fluence range for fabrication of micro-lenses by laser induced backside wet etching using 1.4 M pyrene in THF solution and 308 nm irradiation wavelength is 1-1.6 J/cm². The etching mechanisms of LIBWE are based on a combination of pressure and temperature jumps at quartz-liquid interface.     

Time-resolved measurements during backside dry etching of fused silica

The laser-induced backside dry etching (LIBDE) investigated in this study makes use of a thin metal film deposited at the backside of a transparent sample to achieve etching of the sample surface. For the time-resolved measurements at LIBDE fused silica samples coated with 125 nm tin were used and the reflected and the transmitted laser intensities were recorded with a temporal resolution of about 1 ns during the etching with a ∼30 ns KrF excimer laser pulse. The laser beam absorption as well as characteristic changes of the reflection of the target surface was calculated in dependence on the laser fluence in the range of 250-2500 mJ/cm² and the pulse number from the temporal variations of the reflection and the transmission. The decrease of the time of a characteristic drop in the reflectivity, which can be explained by the ablation of the metal film, correlates with the developed thermal model. However, the very high absorption after the film ablation probably results in very high temperatures near the surface and presumably in the formation of an absorbing plasma. This plasma may contribute to the etching and the surface modification of the substrate. After the first pulse a remaining absorption of the sample was measured that can be discussed by the redeposition of portions of the ablated metal film or can come from the surface modification in the fused silica sample. These near-surface modifications permit laser etching with the second laser pulse, too.     

Backside laser etching of fused silica using liquid gallium

Laser-induced backside wet etching (LIBWE) that is regularly performed with hydrocarbon solutions is demonstrated with the liquid metal gallium as a new class of absorbers for the first time. Well-contoured square etch pits in fused silica with smooth bottoms and well-defined edges were achieved already with the first pulse from a 248 nm excimer laser. The etching is characterized by a threshold fluence of 1.3 J/cm² and a straight proportional etch rate growth with the fluence up to 8.2 J/cm². In addition, the etch depth increases linearly for onward pulsed laser irradiation and gives evidence for an only marginal incubation effect. The high fluences necessary for etching originate from the high reflection losses as well as the high thermal conductivity of the metallic absorber. The suggested etch mechanism comprises the heating of the fused silica up to or beyond the fused silica melting point by the laser heated gallium and the removing of the softened or molten fraction of the material by mechanical forces from shock waves, bubbles, high pressures, or stress fields. PACS 81.65.C; 81.05.J; 79.20.D; 61.80.B; 42.55.L     

High power diode-pumped passively Q-switched and mode-locking Nd:GdVO4 laser at 912 nm

A high power diode-end-pumped passively Q-switched and mode-locking (QML) Nd:GdVO₄ laser at 912 nm was demonstrated for the first time, to the best of our knowledge. A Z-type laser cavity with Cr⁴⁺:YAG crystals as the intracavity saturable absorber were employed in the experiments. Influence of the initial transmission (T_U) of the saturable absorber on the QML laser performance was investigated. Using the T_U = 95% Cr⁴⁺:YAG, as much as an average output power of 2.0 W pulsed 912 nm laser was produced at an absorbed pump power of 25.0 W, then the repetition rates of the Q-switched envelope and the mode-locking pulse were ~ 224 kHz and ~ 160 MHz, respectively. Whereas the maximum output power was reduced to 1.3 W using the T_U = 90% Cr⁴⁺:YAG, we obtained a 100% modulation depth for the mode-locking pulses inside the Q-switched envelope.     

Indirect laser etching of fused silica: Towards high etching rate processing

The indirect laser processing approach (LIBWE) laser-induced backside wet etching allows defined microstructuring of transparent materials at low laser fluences with high quality. The optical and the thermal properties of the solid/liquid interface determine the temperatures and therefore the etching mechanism in conjunction with the dynamic processes at the interface due to the fast heating/cooling rates. The exploration of organic liquid solvents and solutions such as 0.5 M pyrene/toluene results in low etch rates (∼20 nm/pulse). By means of liquid metals as absorber here, demonstrated for gallium (Ga), etch rates up to 600 nm/pulse can be achieved. Regardless of the high etch rates a still smooth surface similar to etching with organic liquid solutions can be observed. A comparative study of the two kinds of absorbing liquids, organic and metallic, investigates the etch rates regarding the fluence and pulse quantity. Thereby, the effect of incubation processes as result of surface modification on the etching is discussed. In contrast to pyrene/toluene solution the metallic absorber cannot decompose and consequently no decomposition products can alter the solid/liquid interface to enhance the absorption for the laser radiation. Hence, incubation can be neglected in the case of the silica/gallium interface so that this system is a suitable model to investigate the primary processes of LIBWE. To prove the proposed thermal etch mechanism an analytical temperature model based on a solution of the heat equation is derived for laser absorption at the silica/gallium interface.     

Time-resolved transmission study of fused silica during laser-induced backside dry etching

Laser-induced backside dry etching (LIBDE) is a promising technique for micro- and nanomachining of transparent materials. Although several experiments have already proved the suitability and effectiveness of the technique, there are several open questions concerning the etching mechanism and the concomitant processes. In this paper time-resolved light transmission investigations of etching process of fused silica are presented. 125 nm thick silver coating was irradiated through the carrying 1 mm thick fused silica plate by single pulses of a nanosecond KrF excimer laser. The applied fluences were 0.38, 0.71 and 1 J/cm². During the etching process the irradiated spots were illuminated by an electronically delayed nitrogen laser pumped dye laser. The delay between the pump and probe pulses was varied in the range of 0 ns and 20 μs. It was found that the transmitted probe beam intensity strongly depends on the applied delays and fluences. Scanning electron microscopy and energy dispersive X-ray spectrometry of the etched surface showed the existence of silver droplets and fragments on the illuminated surfaces and silver atoms built into the treated surface layer influencing the transmission behavior of the studied samples.     

Flexible gratings fabricated in polymeric plate using femtosecond laser irradiation

Flexible gratings embedded in poly-dimethlysiloxane (PDMS) were fabricated using femtosecond laser pulses. Photo-induced gratings in a flexible PDMS plate were directly written by a high-intensity femtosecond (130 fs) Ti: Sapphire laser (λ_p=800 nm). Refractive index modifications with 4 μm diameters were photo-induced after irradiation of the femtosecond pulses with peak intensities of more than 1×10¹¹ W/cm². The graded refractive index profile was fabricated to be symmetric around the center of the focal point. The diffraction efficiency of the grating samples is measured by an He-Ne laser. The maximum value of refractive index change (Δn) in the laser-modified regions was estimated to be approximately 3.17×10⁻³.     

Effect of the ceramic grain size and concentration on the dynamical mechanical and dielectric behavior of poly(vinilidene fluoride)/Pb(Zr<Subscript>0.53</Subscript>Ti<Subscript>0.47</Subscript>)O<Subscript>3</Subscript> composites

Laser-induced backside wet and dry etching (LIBWE and LIBDE) methods were developed for micromachining of transparent materials. Comparison of these techniques is helpful in understanding the etching mechanism but was not realized due to complications in setting up comparable experimental conditions. In our comparative investigations we used a solid tin film for dry and molten tin droplets for wet etching of fused-silica plates. A tin–fused-silica interface was irradiated through the sample by a KrF excimer laser beam (λ=248 nm, FWHM=25 ns); the fluence was varied between 400 and 2100 mJ/cm². A significant difference between the etch depths of the two investigated methods was not found. The slopes of the lines fitted to the measured data (sl_LIBDE=0.111 nm/mJ cm⁻², sl_LIBDE=0.127 nm/mJ cm⁻²) were almost similar. Etching thresholds for LIBDE and LIBWE were approximately 650 and 520 mJ/cm², respectively. To compare the dependence of etch rates on the pulse number, target areas were irradiated at different laser fluences and pulse numbers. With increasing pulse number a linear rise of depth was found for wet etching while for dry etching the etch depth increase was nonlinear. Secondary ion mass spectroscopic investigations proved that this can be due to the reconstruction of a new thinner tin-containing surface layer after the first pulse.