Etching of SiC by energetic F2: Molecular dynamics simulation

Molecular dynamics (MD) simulations were performed to investigate F₂ continuously bombarding silicon carbide (SiC) surfaces with energies in the range of 50-200 eV at normal incidence and room temperature. The Tersoff-Brenner form potential was used. The simulation results show that the uptake of F atoms, the etch yields of C and Si from the initial substrate, and the surface structure profile are sensitive to the incident energy. Like occurrence in Si etching, steady-state etching is observed and an F-containing reaction layer is formed through which Si and C atoms are removed. A carbon-rich surface layer after bombarding by F₂ is observed which is in good agreement with experiments. In the reaction layer, SiF in SiF₂ species are dominant; with increasing incident energy, the total fraction of SiF and SiF₂ increases, while the amount of SiF₃ and SiF₄ decreases. Finally, etching mechanisms are discussed.     

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.     

Measurement of optical and electrical properties of silicon microstructuring induced by ArF excimer laser at SF6 atmosphere

The irradiation of ArF excimer laser (193 nm) on Si wafer (〈1 1 1〉, n-type, arsenic-doped, 0.01 Ω cm) in SF₆ atmosphere, from vacuum to 1000 mbar, creates a regular self-assembled microstructure owning to a great number of microconical spikes covered with SiF₂ (fluorosilyl) layer containing sulfur impurities. The geometry of microstructure as well as the layer thickness varies with the gas pressure and the laser parameters, particularly duration, pulse energy and the dose. In this work, the electrical properties of the layer on the microstructured silicon have been investigated based on electrical impedance spectroscopy (EIS). The measured impedance significantly changes regarding to the unirradiated samples. It was shown that the corresponding electrical conductance and the dielectric constants of the layer are strongly dependent on the gas pressure and UV dose. The layer thickness was also determined in terms of SF₆ pressures.     

Molecular dynamics simulation of deposition and etching of Si bombarding by energetic SiF

In this study, SiF interaction with amorphous Si surface at normal incidence was investigated using molecular dynamics simulation at 300 and 600 K. The incident energies of 50, 100 and 200 eV were used. The results show that the deposition rate is not sensitive to the incident energy, while with increasing the surface temperature, the deposition rate decreases. The etch yield is sensitive to the incident energy and the surface temperature. The etch yield increases with increasing incident energy and temperature. After bombarding, a Si_xF_y interfacial layer is formed. The interfacial layer thickness increases with increasing incident energy mainly through enhanced penetration of the silicon lattice. In the interfacial layer, for SiF_x (x = 1-3) species, SiF is dominant and only little SiF₃ is present. At the outmost and innermost of the interfacial layer, SiF species is dominant. Most of SiF₃ species is concentrated above the initial surface.     

Laser-induced chemical etching of silicon in NF3 atmosphere

Chemical etching of single-crystal Si in an NF₃ atmosphere is performed by continuous irradiation with an Ar⁺ laser at 514.5 nm. The etching process proves to be a thermally stimulated chemical reaction between solid Si and NF₃ gas. The experimental results show how the depth and width of the etched grooves depend on laser power, scan speed, and gas pressure. The etch rates observed may exceed 25 m/s.     

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.     

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.     

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-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.     

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.     

Laser-induced high-quality etching of fused silica using a novel aqueous medium

Laser-induced backside wet etching of fused-silica plates using an aqueous solution of naphthalene-1,3,6-trisulfonic acid trisodium salt (Np(SO₃Na)₃) is reported. A KrF excimer laser was employed as a light source. The etch rate varied greatly with the concentration of the solution and the laser fluence. For lower concentration solutions, the etch rate increased linearly with laser fluence. For highly concentrated solutions, however, the etch rate increased abruptly at higher fluence. Well-defined line-and-space and grid micropatterns were fabricated using a low etch rate. The etched surface was as flat as the surface of the virgin plates and the etched pattern was free of debris and microcracks. The formation and propagation of shockwaves and bubbles in the solution during the etch process were monitored. High pressure, as well as the high temperature generated by the photothermal process, plays a key role in the etching process. Received: 8 April 2002 / Accepted: 12 April 2002 / Published online: 19 July 2002     

Effect of gas residence time on the morphology of silicon surface etched in SF6 plasmas

This paper describes the effect of the SF₆ gas residence time on the morphology of silicon (1 0 0) samples etched in a reactive ion etching system. Profilometry and atomic force microscopy techniques were used to characterize the etching process focusing attention on the evolution of the surface morphology. Under the condition of variable pressure and gas flow rate, the decrease of the residence time leads to an increase of the silicon etch rate concomitantly with an increase of the surface roughness. Contrary fact is observed when the gas flow is fixed and the pressure is varied. Here, the increasing of residence time leads to a constant increase of silicon etch rate with small variations in final surface roughness. To better understanding this resident time effect, mass spectrometry analyses were realized during the discharge for both gas flow conditions.     

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.     

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.     

Positive and Negative Pulse Etching Method of Porous Silicon Fabrication

We present a new method in which both positive and negative pulses are used to etch silicon for fabrication of porous silicon （PS） monolayer. The optical thickness and morphology of PS monolayer fabricated with different negative pulse voltages are investigated by means of reflectance spectra, scanning electron microscopy and photoluminescence spectra. It is found that with this method the PS monolayer is thicker and more uniform. The micropores also appear to be more regular than those made by common positive pulse etching. This phenomenon is attributed to the vertical etching effect of the PS monolayer being strengthened while lateral etching process is restrained. The explanation we propose is that negative pulse can help the hydrogen cations （H^＋） in the electrolyte move into the micropores of PS monolayer. These H^＋ ions combine with the Si atoms on the wall of new-formed micropores, leading to formation of Si-H bonds. The formation of Silt bonds results in a hole depletion layer near the micropore wall surface, which decreases hole density on the surface, preventing the micropore wall from being eroded laterally by F^- anions. Therefore during the positive pulse period the etching reaction occurs exclusively only at the bottom of the micropores where lots of holes are provided by the anode.     

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     

Fluorine etching on the Si(111)-7×7 surfaces using fluorinated fullerene

Fluorine etching on the Si(1 1 1)-7×7 surfaces using fluorinated fullerene molecules as a fluorine source has been investigated. At room temperature, adsorbed fluorinated fullerene molecules reacted with the Si(1 1 1)-7×7 surface to create a localized distribution of fluorine on the surface. Nanoscale etch pits were created by annealing at 300 °C, due to the adsorption of the fluorine localized around the C₆₀F_x molecules. Annealing at 400 °C resulted in the delocalized fluorine distribution on the surface and healing of the etch pits, due to the enhancement of the diffusion of both the fluorine and silicon atoms. Subsequent annealing at 500 °C led to desorption of SiF₂ reactants formed on the surface. The fluorine diffusion process was found to be an elemental process in the etching because the diffusion of adsorbed fluorines is a key for the formation of the SiF₂ species and their subsequent desorption.     

248 nm laser etching of GaAs in chlorine and ozone gas environments

KrF laser etching of GaAs in Cl₂ and O₃ gas ambients by direct laser illumination is reported. The etch depth per pulse in Cl₂ was found to be linear versus the laser fluence on the sample in the 0.2–1.1 J/cm² range. It increased as a function of the Cl₂ pressure up to 6 Torr and slightly decreased for pressures above this value. It also decreased as a function of the laser repetition rate. Very smoothly etched surfaces were obtained after irradiation using the Cl₂ and O₃ etching gases. Auger analysis of the etched GaAs surfaces shows almost no traces of chlorine after etching in Cl₂, whereas a thick oxide layer of about 1500 Å thickness was found after etching in ozone.     

Further investigation on the formation mechanisms of (NH4)2SiF6 synthesized by dry etching technique

The validity of two formation mechanisms of ammonium silicofluoride (ASF), which are proposed to take place when a silicon surface is exposed to the vapor of HNO₃/HF acid mixture is investigated. Of the two proposed mechanisms regarding the synthesis of ASF on silicon surface, validity of the first predicting the release of hydrofluosilicic acid (H₂SiF₆) at the intermediate stage is examined by FTIR spectroscopy and the second mechanism suggesting O₂ release is investigated using the Winkler technique. IR absorbance bands of SiF₆²⁺ are observed on the fresh samples prepared at low (1/100) HNO₃/HF volume fractions. No significant amount of oxygen is detected during the synthesis of ASF films on silicon surface by dry etching technique. These two observations together provide firmer support for the validity of the second mechanism.     

样品温度对CF3+ 与Si表面相互作用影响的分子动力学模拟

利用分子动力学模拟方法研究了不同温度下CF_x层对CF⁺₃刻蚀Si表面过程的影响.由模拟数据可知,温度对C和F的沉积有显著的影响,通过提高样品的温度,物理刻蚀得到了加强,而化学刻蚀被减弱.同时,随着温度的升高,Si的刻蚀率相应增加.刻蚀产物中的SiF,SiF₂的量随温度的增加而增加,SiF₃的量与基体温度没有直接的关系.Si刻蚀率的增加主要是通过提高SiF,SiF_{2相似文献}