Using IR laser radiation for backside etching of fused silica

Laser-induced backside etching of fused silica with gallium as highly absorbing liquid is demonstrated using pulsed infrared laser radiation. The influences of the laser fluence, the pulse number, and the pulse length on the etch rate and the etched surface topography were studied and the results are compared with these of excimer laser etching. The high reflectivity of the fused silica-gallium interface at IR wavelengths results in the measured high threshold fluences for etching of about 3 J/cm² and 7 J/cm² for 18 ns and 73 ns pulses, respectively. For both pulse lengths the etch rate rises almost linearly with laser fluence and reaches a value of 350 and 300 nm/pulse at a laser fluence of about 12 and 28 J/cm², respectively. The etching process is almost free from incubation processes because etching with the first laser pulse and a constant etch rate were observed. The etched surfaces are well-defined with clear edges and a Gaussian-curved, smooth bottom. A roughness of about 1.5 nm rms was measured by AFM at an etch depth of 0.95 μm. The normalization of the etch rates with respect to the reflectivity and the pulse length results in similar etch rates and threshold fluence for the different pulse widths and wavelengths. It is concluded that etching is a thermal process including the laser heating, the materials melting, and the materials etching by mechanical forces. The backside etching of fused silica with IR-Nd:YAG laser can be a promising approach for the industrial usage of the backside etching of a wide range of materials. PACS 81.65.C; 81.05.J; 79.20.D; 61.80.B; 42.55.L     

A laser dry etch process for smooth continuous relief structures in InP

A laser induced etch process is described which uses a pulsed 248 nm KrF excimer laser and Cl₂ atmosphere for the fabrication of monolithic continuously curved reliefs in InP substrate. In a bakeable processing chamber with low base pressure a wide range of laser fluences is available for damage-free etching. Especially, by photothermal heating far above the melting point, mirrorlike smooth surfaces are obtained. The etch rate characteristics are correlated to the maximum surface temperature reached during the laser pulse. The etch rate is independent of pressure and gas flux in the ranges 0.1–10 mbar and 20–300 sccm, respectively. It increases, however, with the background substrate temperature. Etch rates of up to 3.6 nm/pulse or 4.3 lm/min are possible at 20 Hz pulse repetition rate without visible surface damage. The process exhibits a smooth increase of the etch rate from 1 to 3 nm/pulse between 200 and 300 mJ/cm², which could be used for making curved reliefs by optical transmission variations on the projection mask.     

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.     

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.     

Laser etching of transparent materials at a backside surface adsorbed layer

The laser etching using a surface adsorbed layer (LESAL) is a new method for precise etching of transparent materials with pulsed UV-laser beams. The influence of the processing parameters to the etch rate and the surface roughness for etching of fused silica, quartz, sapphire, and magnesium fluoride (MgF₂) is investigated. Low etch rates of 1 nm/pulse and low roughness of about 1 nm rms were found for fused silica and quartz. This is an indication that different structural modifications of the material do not affect the etching significantly as long as the physical properties are not changed. MgF₂ and sapphire feature a principal different etch behavior with a higher etch rate and a higher roughness. Both incubation effects as well as the temperature dependence of the etch rate can be interpreted by the formation of a modified near surface region due to the laser irradiation. At repetition rates up to 100 Hz, no changes of the etch rate have been observed at moderate laser fluences.     

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     

Laser etching of fused silica using an adsorbed toluene layer

A new method for laser etching of transparent materials with a low etch rate and a very good surface quality is demonstrated. It is based on the pulsed UV-laser backside irradiation of a transparent material that is covered with an adsorbed toluene layer. This layer absorbs the laser radiation causing the etching of the solid. The threshold fluence for etching of fused silica amounts to 0.7 J/cm². The constant etch rate of about 1.3 nm/pulse that has been observed in a fluence interval from 2 to 5 J/cm² is evidence of a saturated process. The limited thickness of the adsorbed layer causes the low etch rates and the rate saturation. The etched surface structures have well defined edges and low surface roughness values of down to 0.4 nm rms. PACS 81.65.Cf; 81.05.Kf; 79.20.Ds; 61.80.Ba; 42.55.Lt     

Rapid thermal annealing of electrically-active defects in virgin and implanted silicon

Chemical etching of single-crystalline (100)Si induced by pulsed laser irradiation at 308, 423, and 583 nm has been investigated as a function of the laser fluence and C1₂ pressure. Without laser-induced surface melting, etching requires Cl radicals which are produced only at laser wavelengths below 500 nm. With low laser fluences ((308 nm)<100 mJ/cm²) etching is non-thermal and based on direct interactions between photocarriers and Cl radicals. For fluences which induce surface melting ((308 nm)>440 mJ/cm²) etching is thermally activated. In the intermediate region both thermal and non-thermal mechanisms contribute to the etch rate.     

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.     

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.     

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.     

Projection-patterned etching of silicon in chlorine atmosphere with a KrF excimer laser

The formation of relief features in silicon by a one-step process that avoids resist patterning has been achieved by laser-projection-patterned etching in a chlorine atmosphere. Etching is performed with a pulsed KrF excimer laser (λ=248 nm, τ=15 ns) and deep UV projection optics having an optical resolution of 2 μm. Etching takes place in two steps. Between laser pulses, the silicon surface is covered with a monolayer of chemisorbed chlorine atoms (one Cl per Si). During the laser pulse, surface transient heating at temperatures in excess of 1250 K results in the desorption of the reaction products (mainly SiCl₂). At laser energy densities that induce surface melting, this desorption results in a saturated etch. rate of 0.06 nm per pulse, corresponding to the removal of about 0.5 Si monolayer per pulse. At densities below the melting threshold, reduced thermal and possibly a small amount of photochemical etching result in lower etch rates. Projection of a resolution test photomask onto the silicon surface shows that the size of etched features differs from the size of the projected features and strongly depends on the laser energy density. As a result of the heat spread in silicon and of the highly nonlinear character of the etching reaction, etched features smaller than the irradiated area are obtained at all fluences in the range 350–700 mJ/cm². Etched lines having a width down to about 1.3 μm were produced. Proximity effects due to heat spread were also evidenced for small projected features (<4 μm). The characteristics of the etched patterns are compared with those obtained for GaAs etching in chlorinated gases with the same experimental set-up. Significant differences in pattern resolution for Si and GaAs etching are observed. This variation in resolution is believed to result from the fact that Si has a greater thermal diffusivity than GaAs.     

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.     

Laser projection-patterned etching of (100) GaAs by gaseous HCl and CH3Cl

Laser projection-patterned etching of GaAs in a HCl and CH₃Cl atmosphere performed using a pulsed KrF-excimer laser (=248 nm, =15 ns) and deep-UV projection optics (resolution 2 m) is reported. The etching process carried out in a vacuum system having a base pressure of 10^–6 mbar is shown to result from a purely thermochemical reaction. Etching takes place in two steps: (i) between the laser pulses, the etchant gas reacts with the GaAs surface-atomic layer to form chlorination products (mainly As and Ga monochlorides), (ii) local laser surface heating results in the desorption of these products allowing further reaction of the gas with the surface. The influence of the etching parameters (laser energy density, gas pressure and pulse repetition rate) on the etch rate and the morphology of the etched features was studied. Etch rates up to 0.15 nm per pulse, corresponding to the removal of 0.5 GaAs molecular layer, are achieved. The spatial resolution of the etching process is shown to be controlled by the heat spread in the semiconductor and by the nonlinear dependence of the etch rate on the surface temperature. As a result, etched features smaller or larger than the projected features of the photomask are achieved depending on the laser energy density. Etched lines having a width of 1.3 m were obtained at low fluences by the projection of 2 m wide lines onto the GaAs surface.     

Laser-induced etching of titanium by Br2 and CCl3Br at 248 nm

A quartz crystal microbalance (QCM) has been used to study the KrF* excimer laser-induced etching of titanium by bromine-containing compounds. The experiment consists of focusing the pulsed UV laser beam at normal incidence onto the surface of a quartz crystal coated with 1 m of polycrystalline titanium. The removal of titanium from the surface is monitored in real time by measuring the change in the frequency of the quartz crystal. The dependence of the etch rate on etchant pressure and laser fluence was measured and found to be consistent with a two-step etching mechanism. The initial step in the etching of titanium is reaction between the etchant and the surface to form the etch product between laser pulses. The etch product is subsequently removed from the surface during the laser pulse via a laser-induced thermal desorption process. The maximum etch rate obtained in this work was 6.2 Å-pulse^–1, indicating that between two and three atomic layers of Ti can be removed per laser pulse. The energy required for desorption of the etch product is calculated to be 172 kJ-mole^–1, which is consistent with the sublimation enthalpy of TiBr₂ (168 kJ-mole^–1). The proposed product in the etching of titanium by Br₂ and CCl₃Br is thus TiBr₂. In the etching of Ti by Br₂, formation of TiBr₂ proceeds predominantly through the dissociative chemisorption of Br₂. In the case of etching with CCl₃Br, TiBr₂ is formed via chemisorption of Br atoms produced in the gas-phase photodissociation of CCl₃Br.     

CO2 laser ablative etching of polyethylene terephthalate

Films of polyethylene terephthalate (PET) can be successfully etched with 9 m radiation from a pulsed TEA CO₂ laser. The relationship between etch depth and fluence is broadly similar to that observed for excimer laser etching but with a less well-defined threshold. Time-resolved photoacoustic measurements of stress waves generated in the interaction show that at a fluence of 1.8 J cm^–2 ablation occurs 100–200 ns after the start of the laser pulse, a time which is consistent with the rate of thermal decomposition of PET. The volatile products of ablation are carbon monoxide, carbon dioxide, methane, ethyne, ethene, benzene, ethanal, and small quantities of other products. For fluences close to and appreciably above the threshold the ablated material consists predominantly of involatile species of relatively high molecular weight, whereas at higher fluences substantial fragmentation of the polymer to small molecules occurs.School of Chemistry     

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.     

High-speed etching of hexagonal GaN by laser ablation and successive chemical treatment

Photostimulated direct etching of GaN has been demonstrated with extremely high etching rate up to 135 nm/pulse. The process consists of laser irradiation and ex-situhydrochloric acid treatment. Not only deep etching but also a highly planarized surface are obtained by an increase in laser fluence and the number of pulses. Seven-pulse irradiation at 1 J/cm² decreases surface average roughness (R_a) to ~2 nm from ~10 nm of the untreated sample. No deep-level emission (450-600 nm) is detected in photoluminescence measurement on the samples irradiated with laser fluences as high as 3 J/cm².     

Laser-assisted etching of gallium arsenide in chlorine at 308 nm

Xenon chloride (308 nm) excimer laser-assisted etching of GaAs (100) in Cl₂ was demonstrated and characterized with respect to laser and gas parameters. The etch rate increased linearly with laser fluence from thresholds in the range of 50 to 75 mJ/cm² to the highest fluence studied, 650 mJ/cm². For a laser fluence of 370 mJ/cm², the etch rate varied with Cl₂ pressure reaching a maximum at a Cl₂ pressure of about 2 Torr. The etch rate decreased monotonically with Ar buffer gas pressure because of redeposition of GaCl₃ products into the etched channel. The redeposited GaCl₃ affected the etch rate and the etch morphology. The etch rate and morphology also varied with laser repetition rate. The mobility of chlorine on the surface also plays an important role in the etching mechanism.