Laser-induced dry chemical etching of Mn-Zn ferrite in CCl2F2 atmosphere

Maskless etching of Mn-Zn ferrite in dichlorodifluoromethane (CCl₂F₂) by Ar⁺-ion laser (514.5 nm line) irradiation has been investigated to obtain high etching rates and aspect-ratio of etched grooves. The etching reaction was found to be thermochemical. High etching rates of up to 360 m/s, which is about one order of magnitude higher than that in a CCl₄ gas atmosphere and even higher than that in a H₃PO₄ solution, have been achieved. A maximum aspect-ratio of 6.9 was obtained.     

Comparison of laser-induced etching behavior of III–V compound semiconductors

Laser-induced maskless etching of III–V compound semiconductors (InSb, GaAs, and InP) in a KOH aqueous solution by irradiation with a focused argon-ion laser has been investigated to obtain high etching rates and aspect ratios of etched grooves. The etching rate at low laser power was found to depend on the carrier density of the sample and its type. With the increase of the laser power, the etching reaction becomes primarily a thermochemical reaction. High etching rates and aspect ratios have been achieved with a single scan of the laser beam. The damage induced by laser wet etching is less than that by laser dry etching, and the damage at the etched side wall is less than that at the etched bottom. Grooves with locally controlled depth and slab structures have been fabricated for application.     

Thermochemical dry etching of single crystal ferrite by laser irradiation in CCl4 gas atmosphere

Single crystal ferrite has been etched by focused Ar⁺ laser irradiation in a CCl₄ gas atmosphere. The etched groove showed cracks due to thermal stresses when samples were etched by a laser vaporization process in a vacuum, while in a CCl₄ atmosphere, such cracks were not observed. An etching rate of 68 /s obtained for a thermochemical process by laser irradiation was four orders of magnitude higher than that for a wet chemical etching process. A high aspect (depth-to-width) ratio of up to 10 was obtained for etched grooves. Under specific conditions, bending of the groove and orientation dependence in etching rate were observed.     

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     

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.     

InGaAsP/InP 1.55-μm lasers with chemically assisted ion beam-etched facets

Chemically assisted ion beam etching (CAIBE) involving an Ar ion beam and a halogen ambient gas (Cl₂, IBr₃) has been used to etch high-quality laser facets for InGaAsP/InP bulk lasers (1.55 m). We achieved eich rates of 40.0–75.0 nm min^–1 at substrate temperatures between-5 and +10°C. These low temperatures have allowed us to utilize UV-baked photoresists as well as PMMA as etch masks, facilitating very simple process development. Higher substrate temperatures (50 to 120°C) yield still higher etch rates, but at the expense of severely degraded surface morphologies. Angle resolved x-ray photoelectron spectroscopy (XPS) was investigated for observing etched InP surfaces. A disproportioned surface has been detected after etching in the higher temperature range; low temperatures yield stoichiometric surfaces.     

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.     

Laser-induced trench etching of GaAs in aqueous KOH solution

Maskless etching of n-type GaAs in a KOH aqueous solution by irradiation of an argonion laser has been investigated to obtain high etching rates and aspect-ratios of etched grooves. High etching rates of up to 805 m/s and an aspect ratio of 8 have been achieved by a single scan of a laser beam. Microprobe photoluminescence (PL), Raman scattering, and Auger electron spectroscopy (AES) measurements were carried out on the trench surface to characterize damage induced by laser wet etching.     

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     

Laser-assisted etching of diamonds in air and in liquid media

2 O, (CH₃)₂SO). Diamond samples are virtually transparent at this wavelength, and the coupling of laser radiation to diamond is via the formation of a thin graphitized layer at the diamond surface. The etching rate in liquid media is slightly higher than in air at otherwise equal conditions and is as high as 50 μm/s for etching with a scanning laser beam. Raman spectra measurements carried out on diamond samples etched in air show the presence of glassy carbon on the surface, whereas for samples etched in a liquid the diamond peak at 1332 cm^-1 dominates with significantly lower intensity of the glassy carbon peak. Electroless copper deposition on the laser-etched features is studied to compare the catalytic activity of the diamond surface etched in air with that etched in liquids. Possible mechanisms responsible for the observed difference both in the structure of the etched area and in the electroless Cu deposition onto the surface etched in various media (air or liquids) are discussed. Received: 2 August 1996/Accepted: 7 January 1997     

Chemical etching of crystal and thin film cadmium telluride

Single crystal p-CdTe and thin film p-CdTe, made by an air annealing of electrodeposited n-CdTe, were subjected to chemical etching by bromine in methanol (BM) and by potassium dichromate-sulphuric acid (KD). XPS and SIMS gave both qualitative and quantitative information on the effects. Etch rates were determined. For the concentrations examined, KD etched more rapidly than BM etched, and gave much deeper Cd depletion regions. In films which had been BM etched and washed, Br was present throughout the film. After KD etching, a very small amount of Cr was still present in films. The results indicate that the etchants travel along grain boundaries. Both etches left surfaces rich in Te⁰. In addition, BM produced CdBr₂ and TeBr₄, both removable by washing. Varying the concentration of BM did not increase the maximum depletion depth of 2 nm. Diluting KD reduced the Cd depletion region. Conditions to give a desired Cd depletion depth were established.     

Fabrication of Step-and-Flash Imprint Lithography (S-FIL) templates using XeF<Subscript>2</Subscript> enhanced focused ion-beam etching

The fabrication of Step-and-Flash Imprint Lithography (S-FIL) templates with line widths of 50 nm is described in this work. The structures have been patterned using a Ga⁺ focused ion beam (FIB) in a quartz template. FIB milling is generally accompanied with re-deposition effects, which represent a hindrance to densely patterned nanostructures required in most NIL applications. To reduce these re-deposition effects, in this research, xenon difluoride (XeF₂) enhanced FIB etching was applied that also increases the material removal rates in comparison to pure kinetic ion sputtering. To optimise the process when using XeF₂ gas the following ion scanning parameters have been examined: ion dose, beam current, dwell time and beam overlap (step size). It has been found that the assisting gases at very low doses do not bring significant etching enhancements whilst the sputtering rates have increased at high doses. Using the XeF₂ gas-assisted etching, FIB structuring has been used to fabricate <100 nm structures onto quartz S-FIL templates. The presence of XeF₂ considerably enhances the etching rate of quartz without any significant negative effects on the spatial resolution of the FIB lithographic process and reduces the template processing time.     

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.     

Optimized ICP etching process for fabrication of oblique GaN sidewall and its application in LED

Inductively coupled plasma (ICP) etching of GaN is systemically investigated by changing ICP power/RF bias power, operating pressure, and Cl₂/BCl₃ gas mixing ratio. The hexagonal etch pits related to screw dislocation existing along GaN epitaxial layer were observed on the etched GaN surface after ICP etching. The intensity of band-edge emission is significantly reduced from the etched n-GaN surface, which reveals that plasma-induced damage are generated after ICP etching. The oblique sidewall is transferred into GaN using a combination of Cl₂/BCl₃ plasma chemistry and hard mask SiO₂. By adjusting ICP etching process parameters, oblique sidewalls with various oblique angles can be formed, allowing for conformal metal lines coverage across the mesa structures, which can play an important role in the interconnection of multiple microchips for light emitting diodes (LEDs) fabrication.     

XeCl laser controlled chemical etching of aluminum in chlorine gas

The 308 nm XeCl laser assisted etching process of thin Al metal films on Si substrate in Cl₂ gas was investigated. Etch rates were measured versus the laser fluence on the sample, the laser repetition rate, the Cl₂ pressure and the sample temperature. Irradiation experiments under vacuum of films which were previously exposed to Cl₂, and laser assisted etching in rare gases, nitrogen and air mixtures with Cl₂ were also performed to elucidate the mechanism of the etching process. The surface morphology was investigated by scanning electron microscopy. The results show that a) Etch rates of up to about 1.5 m per pulse are obtained which are strongly dependent on the Cl₂ pressure and sample temperature. b) The etching mechanism is essentially a chemical chlorination of the Al in between the laser pulses which is followed by photo-ablation of the reaction products, c) AlCl₃ evaporation and redeposition processes can explain the observed results. d) The Al films can be etched fully and cleanly without damage to the smooth Si substrate. e) Etching through adjacent or imaged mask on the Al film yielded relatively smooth and well defined Al walls with structures of the order of 1 m.     

Fast etching and metallization of SiC ceramics with copper-vapor-laser radiation

The etching of polycrystalline SiC is studied with the help of radiation of a copper-vapor laser either in air or under the layer of a liquid (H₂O, DMSO). The etching rate in air is as high as 0.24 m/pulse, in DMSO 0.07 gm/pulse at an energy density of 16 J/cm². The etched surface is characterized with Scanning Electron Microscopy (SEM) and X-ray diffractometry. Etching of SiC ceramics in air revealed the partial amorphization of SiC and the formation of microcrystals of elementary Si with an average size of 300 Å. The etched surface of SiC ceramics takes on the ability to reduce Cu from a corresponding electroless plating solution. The adherence of the deposit is as high as 30 N/mm² and is a function of the scanning velocity of the laser beam.     

Effect of radio frequency power on the inductively coupled plasma etched Al0.65Ga0.35N surface

The etching effects on the surface and electrical characteristics of high Al mole fraction Al_xGa_1−xN (x = 0.65) have been characterized by X-ray photoelectron spectroscopy (XPS) and transfer length method (TLM) as a function of radio frequency power. XPS results show that the Ga-N and Al-N peaks move to the lower energy after ICP etchings. An increase in the amount of oxygen and a decrease in the amount of nitrogen are observed for the etched samples along with the RF power. The annealing at 450 °C is partly effective on removing the oxygen amount which would come from the C-O component and recovering the N deficiencies on the surface of etched sample. The extracted sheet resistance of the AlGaN layer from TLM increases gradually after ICP etching with an increase of RF power. The correlation between the XPS peaks and the electrical properties of the etched samples has been discussed and the annealing effect on the inverse leakage current of the p-i-n AlGaN solar blind UV detector is examined.     

Excimer-laser etching on silicon

Studies have been made of poly- and single Si etching induced by excimer-laser irradiation of the silicon surfaces in halogenated gases. Etching was investigated for different conduction types, impurity concentrations and crystallographic planes. Chlorine atoms accept electrons generated in photoexcited, undoped p-type Si, thus becoming negative ions which are pulled into the Si. However, the n⁺-type Si is etched spontaneously by Cl^– as a result of the availability of conduction electrons. Fluorine atoms, with the highest electronegativity, take in electrons independent of whether the material is n- or p-type. And thus, the easy F^– ion penetration into Si causes spontaneous etching in both types. New anisotropic etching for n⁺ poly-Si is investigated because of its importance to microfabrication technology. Methyl methacrylate (MMA) gas, which reacts with Cl atoms, produces a deposition film on the n⁺ poly-Si surface. The surface, from which the film is removed by KrF (5 eV) laser irradiation, is etched by Cl atoms, while the film remains on the side wall to protect undercutting. However, with the higher photon energy for the ArF (6.4 eV) laser, the Si-OH bonds are broken and electron traps are formed. These electrontrapping centers are easily annealed out in comparison to the plasma-induced centers. Pattern transfer etching for n⁺ poly-Si has been realized using reflective optics. The problems involved in obtaining finer resolution etching are discussed.     

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     

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.