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.     

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.     

Wet-chemical etching of Mn-Zn ferrite by focused Ar+-laser irradiation in H3PO4

Maskless etching of Mn-Zn ferrite in H₃PO₄ aqueous solution by Ar⁺-ion laser irradiation has been investigated to obtain high etching rates and aspect-ratios of etched grooves. The etching processes have been found to be photochemical in the low laser power region and thermochemical in the high laser power region. High etching rates of up to 340 μm/s and an aspect-ratio of 30 for slab structures have been achieved. In the case of high aspect-ratio structure, the etching rate was limited by the low diffusion efficiency of etched products in the etchant. Periodic ripple structures have been observed under specific etching conditions.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

High-rate laser-direct-write dry etching of titanium

Titanium surfaces can be etched spatially selective in a chlorine atmosphere under 488 nm cw Ar⁺-laser irradiation focused to 3 m with well-controlled etch depth and high etch rate. By scanning the substrate, patterns can be generated by laser direct writing with high scan speed. The dependence of the etch rate on various parameters, such as laser power, scan speed and chlorine pressure, is described, and the impact on three-dimensional structuring of titanium is discussed.     

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.     

Maskless photoassisted etching of N-type Ga0.47In0.53As in basic solutions

The maskless photoassisted etching of n-type Ga_0.47In_0.53As is examined for basic KOH solutions in comparison with GaAs and InP material. The etch rate increases with laser intensity and with carrier concentration up to a saturation value. The best etch rate is obtained with molar KOH in ethyl alcohol (7 ms^–1 for laser intensity 10⁴ W cm^–2). Selective etching have been realized on heterojunction in order to isolate p-n junctions without the help of masks.     

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     

Sputtering of solid argon by keV electrons

Thermochemical maskless etching of compound semiconductors (GaAs, InP, InSb, and GaP) has been performed by focused Ar-laser irradiation in chloride gas atmospheres. A controlled minimum linewidth of down to 0.6 m with a maximum etching rate of up to 13 m/s has been obtained. Minimum laser powers necessary for thermochemical etching in each of compound semiconductors were found to be 0.24, 0.56, and 0.06 W, corresponding to minimum local temperature rises of 190, 515, and 110°C for GaAs, InP, and InSb, respectively. Etching rates exhibited Arrhenius behavior with activation energies of 3.6–3.9 kcal/mole. Etching at excessively higher laser powers than those minimum powers was found, by microprobe photoluminescence measurements, to degrade the optical quality of the etched substrate.     

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-induced chemical etching of ceramic PbTi1−xZrxO3

The laser-induced etching of ceramic PbTi_1–xZr_xO₃ in a hydrogen atmosphere and in air has been investigated. Visible Ar⁺ and Kr⁺ laser radiation was employed in most of the experiments. In H₂ atmosphere, regular patterning of the ceramic is possible. Average etch rates reach up to about 250 m/s.     

Laser-induced deposition of Ni lines on ferrite in NiSO4 aqueous solution

Maskless deposition of nickel lines on single crystalline Mn-Zn ferrite (MnO:ZnO:Fe₂O₃=31:17:52) has been investigated in a NiSO₄ aqueous solution by Ar⁺ laser irradiation. A high deposition rate of up to 36.4m/s was achieved by a single scan of laser beam. The purity of deposited nickel layers is up to 86%. In particular, well-defined values of laser power and laser irradiation time were necessary for effective deposition. The deposition process was found to be a thermochemical process.On leave from D. S. Scanner Co., Ltd., 5-3-7. Fukushima, Osaka 553, Japan     

Shallow surface etching of organic and inorganic compounds by electrospray droplet impact

The electrospray droplet impact (EDI) was applied to bradykinin, polyethylene terephthalate (PET), SiO₂/Si, and indium phosphide (InP). It was found that bradykinin deposited on the stainless steel substrate was ionized/desorbed without the accumulation of radiation products. The film thickness desorbed by a single collisional event was found to be less than 10 monolayers. In the EDI mass spectra for PET, several fragment ions were observed but the XPS spectra did not change with prolonged cluster irradiation. The etching rate for SiO₂ by EDI was measured to be ∼0.2 nm/min. The surface roughness of InP etched by EDI was found to be one order of magnitude smaller than that etched by 3 keV Ar⁺ for about the same etching depths. EDI is capable of shallow surface etching with little damage left on the etched surface.     

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