Direct writing of Ag-lines on Mn-Zn ferrite by laser-induced thermal decomposition by CH3COOAg

Laser-induced direct writing of silver lines on a ferrite surface from a silver acetate (CH₃COOAg) thin layer has been investigated. The deposition is a thermochemical process and the threshold temperature for thermal decomposition of CH₃COOAg is about 380° C. About 100% of Ag in the deposited lines has been achieved. The width of the deposited Ag-lines increased with the increase in laser power, and it can be accurately estimated by the temperature profile induced by laser irradiation within the power region below the melting point of ferrite. A line thickness of micron order can be formed both on a ferrite surface and on a deposited SiO₂ surface, whereas the line width decreased with the increase in beam dwell time due to the vaporization of both CH₃COOAg precursor and deposited Ag material.On leave from D. S. Scanner Co., Ltd., 5-3-7, Fukushima, Osaka 553, JapanOn leave from Sensor Device Laboratory, Central Research Institute, Glory Co. Ltd., Hyogo 670, Japan     

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.     

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.     

Basic mechanisms in laser etching and deposition

Laser-induced chemical processing of solid surfaces has the potential for being an important and powerful technique for fabrication of a variety of devices. Successful applications rest on a detailed understanding of the nature of laser-induced reactions and their effects on the properties of materials. In this paper fundamental studies illustrating key features of laser etching and deposition are reviewed. Topics covered include the effect of the choice of precursor and deposition conditions on film composition and morphology, self-propagation of exothermic reactions, thermal and electronic effects in laser-assisted etching of semiconductors, metals and polymers, and special aspects of laser-surface photophysics as they may affect chemical reactions.     

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.     

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 generated microstructures

Deposition and etching processes based on the interaction of laser light with a substrate surface and molecules of the surrounding ambient are discussed in this tutorial review. This laser writing approach is based on photolytic, pyrolytic, or photoelectrochemical microreactions. The fundamental properties of such reactions and corresponding processing parameters (e.g. deposition or etch rate, resolution) are discussed. Important published results for deposition by photolysis, pyrolysis, and etching are summarized in the form of tables. A special list of potential applications for such techniques and a list of all materials used thus far for laser deposition and etching are included.     

Femtosecond excimer-laser-induced structure formation on polymers

Structure formation upon 500 fs 248 nm KrF-laser irradiation of PolyEthylene Terephthalate (PET) and PolyImide (PI) has been investigated. The results obtained with fs pulses have been compared to those with ns pulses.     

Formation of monoclinic zirconia at the anodic face of tetragonal zirconia polycrystalline solid electrolytes

The stability of yttria tetragonal zirconia polycrystalline (Y-TZP) materials with and without the addition of alumina has been investigated during charge flow in solid electrolyte cells. A considerable amount of monoclinic zirconia is formed (up to 50–60%) on the anodic side of the solid electrolyte discs during current flow. The thickness of the surface layer in which maximum transformation takes place was determined to be 3–4.5 m. On the cathodic side, the amount of monoclinic zirconia detected was relatively small (< 5%). The amount of monoclinic formed on the anodic side varied with the microstructure of the ceramic and was considerably less in materials free of pores and with uniform grain size distribution. Relaxation experiments indicate that the tetragonal to monoclinic zirconia phase transformation is related to the oxygen evolution reaction and is not due to oxygenion transport within the solid electrolyte. The observed behaviour has been explained in terms of the creation of space charge layers at the electrode/electrolyte interface leading to the saturation of vacancies by oxygen ions and instability of the tetragonal phase in the surface region on the anodic side of the solid electrolyte.     

Melting and solidification in laser-irradiated HgCdTe

The results of the numerical analysis of the effects induced by pulsed Nd:YAG and ruby laser on Hg_0.8Cd_0.2Te are presented. The proposed model facilitates the planning of HgCdTe laser processing and the choice of the processing parameters such as: melt depth, melt duration of the surface layer and melt front velocity, as well as the irradiation parameters. The influence of the optical parameters and the temperature dependence of the HgCdTe thermal parameters on the results of laser irradiation are specially analyzed.     

Excimer-laser ablation and micro-patterning of ceramic Si3N4

3 N₄ has been investigated. The ablation threshold in air, Φ_th, is around 0.3±0.1 J/cm² with ArF- and 0.9±0.2 J/cm² with KrF-laser radiation. With fluences Φ_th<Φ<4 J/cm² the irradiated surface is either very flat or it exhibits a cone-type structure, depending on the number of laser pulses employed. With fluences of 5 to 10 J/cm², the sample surface becomes very smooth, much smoother than the original mechanically polished surface. Pores, scratches, and cracks observed on the non-irradiated surface are absent within the illuminated area. In this regime, the ablation rates are typically 0.1 to 0.2 μm/pulse. Received: 10 April 1997/Accepted: 11 April 1997     

Photocatalytic activity of dc magnetron sputter deposited amorphous TiO2 thin films

For photocatalytic thin film applications TiO₂ is one of the most important materials. The most studied TiO₂ crystal phase is anatase, though also rutile and brookite show good photoactivity. Usually anatase or a mixture of rutile and anatase is applied for powder or thin film catalysts. It has been claimed that amorphous films do not exhibit any or only a very low photocatalytic activity.We have deposited amorphous thin films by dc magnetron sputtering from sub-stoichiometric TiO_2−x targets. The coatings are transparent and show a photocatalytic activity half of that of a thin layer of spin-coated reference photocatalyst powder. Annealing the thin films to yield anatase crystallization more than doubles their photocatalytic activity. At the same film thickness these thin films show the same activity as a commercially available photocatalytic coating.The dependence of the photocatalytic activity on deposition parameters like gas pressure and sputter power is discussed. A decrease in film density, as deduced from the refractive index and the microstructure, resulted in an increase in photocatalytic activity. Film thickness has a marked influence on the photocatalytic activity, showing a strong increase up to 300-400 nm, followed by a much shallower slope.     

Dissociative adsorption of alkanes on clean and sulfur-modified nickel surfaces

Recent studies of the dissociative adsorption of methane on clean Ni(111), Ni(100), Ni(110), and sulfur-modified Ni(100), as well as ethane, propane, and n-butane on Ni(100) have been carried out under the high incident flux conditions of 1.00 Torr methane, 0.10 Torr ethane, 0.01 Torr propane, and 0.001 Torr n-butane, respectively. It has been found that the activation energies for these processes range from 3.1±1.0 to 13.3±1.5 kcal mol^–1. A comparison with the results of corresponding molecular beam studies suggests that the effects of vibrational energy on sticking probabilities must be accounted for and the sticking probabilities of molecules with very low normal kinetic energies must be accurately known when attempting to model high pressure processes using molecular beam techniques. While dissociation of ethane, propane, and n-butane on Ni(100) is believed to proceed primarily via a trapped molecular precursor, the results on sulfur-modified Ni(100) surface indicate that the direct channel to methane dissociation likely dominates and the contribution from the trapped molecular precursor mechanism is likely relatively small, with the sulfur atoms poisoning this reaction by a simple site blocking mechanism.     

Photoredox laser chemistry of transition metal oxides

Received: 26 May 1997/Accepted: 17 July 1997     

Lase action on resonant molecular flows through capillaries

New experimental results are reported pointing to the possibility of a laser control of the resonant gases transit through capillaries in the Knudsen and intermediate regimes.     

Work function of sol-gel indium tin oxide (ITO) films on glass

Indium tin oxide (ITO) films (physical thickness, 250-560 ± 25 nm) were deposited on soda lime silica (SLS) glass and silica layer coated (∼200 nm physical thickness) SLS glass substrates by sol-gel technique using alcohol based precursors containing different In:Sn atomic percentages, namely, 90:10, 70:30, 50:50, 30:70. Cubic phase of In₂O₃ was observed up to 50 at.% Sn while cassiterite SnO₂ phase was observed for 70 at.% Sn. Work function of the films was evaluated from inelastic secondary electron cutoff of ultraviolet photoelectron spectroscopy (UPS) energy distribution curve (EDC) obtained under two experimental conditions (i) as-introduced (ii) after the cleaning of the surface by sputtering. Elemental distribution and the presence of oxygen containing contaminant and carbon contaminant of the samples were done by XPS analysis under same conditions. The work function changed little due to the presence of surface contaminants. It was in the range, 3.9-4.2 eV (±0.1 eV).     

Energy accommodation and reactivity of O2 on tungsten

We have determined by direct molecular beam velocity measurements that translational energy accommodation of O₂ molecules scattered from a hot polycrystalline tungsten target is inefficient at high surface temperatures. Translational energy accommodation is inefficient whether the surface is clean or covered with oxygen to a varying extent, even though in the latter case the scattering is diffuse. On a clean tungsten surface the scattering of the O₂ was approximately specular and the reaction probability of O₂ was constant and greater than 90% over the temperature range 1000K to 2800 K. It was shown by simultaneous helium scattering that atomic surface roughness of an oxygen chemilayer, rather than trapping, is a major cause of the observed diffuse scattering of oxygen. At the lowest surface temperature of 1000 K, with an oxygen chemilayer present, the velocity of the most probable number density of the scattered O₂ was lower than in the incoming beam or than that expected for complete equilibration with the 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.     

Mechanism and speed of initial step of oxygen chemisorption-O2 on W

A direct first step in the mechanism for the initial oxidation of a polycrystalline tungsten surface, the catalyzed dissociation of O₂ on it, or the formation of WO _X by O₂ at intermediate temperatures is shown to occur in ∼10⁻¹³ s. Molecular beam experiments demonstrated that the reactivity was greater than 90%, the unreacted O₂ was substantially unaccommodated in translational energy to the surface temperature, and the reaction probability was nearly independent of surface temperature from 2800 to 415 K although there was a small increase at 415 K. The general conditions when no molecular surface precursor state contributes to the surface reactivity are discussed.     

Isotope effects in electron impact desorption of CO and O2 adsorbed on the (110) plane of tungsten

Results on the isotope effect for total and ionic desorption cross sections in the electron impact desorption of various binding states of CO on the (110) plane of tungsten, and of oxygen on this plane are presented and discussed. It is shown that the observations allow a dissection of cross sections into excitation cross sections and escape probabilities, and that the latter can be used to estimate lifetimes of excited or ionic states. It is found that excitation cross sections for total desorption are of the order of 10⁻¹⁶–10⁻¹⁷ cm², but seem to be significantly smaller in some cases for excitation to ionic states, suggesting that different excitations are involved. In all cases examined here the isotope effect for total desorption is much smaller than for ion production. This can be explained by the fact that ion lifetimes are somewhat shorter than those of excited neutrals. Lifetimes are estimated, in the cases examined, to be of the order of 10⁻¹⁴s.