Specific features of the bulk etching of single-crystal semiconducting silicon in aqueous KOH solutions

Bulk chemical etching of single-crystal semiconducting silicon in aqueous alkaline solutions of KOH was studied at various solution temperatures, alkaline component concentrations, and microscopic amounts of a potassium ferricyanide additive. Specific effects of these factors on the process of silicon etching are explained by comparing the corresponding activation energies. The possibility of using alkaline aqueous solutions of KOH with a potassium ferricyanide additive for fabrication of elements in microsystem technology devices is assessed.     

Hydrogen bubbles and formation of nanoporous silicon during electrochemical etching

Many nanoporous Si structures, including those formed by common electrochemical etching procedures, produce a uniformly etched nanoporous surface. If the electrochemical etch rate is slowed down, details of the etch process can be explored and process parameters may be varied to test hypotheses and obtain controlled nanoporous and defect structures. For example, after electrochemical etching of heavily n‐doped (R = 0.05–0.5 Ω·cm) silicon 〈100〉 single crystals at a current density of 10 mA cm^?2 in buffer oxide etch (BOE) electrolyte solution, defect craters containing textured nanopores were observed to occur in ring‐shaped patterns. The defect craters apparently originate at the hydrogen/BOE bubble interface, which forms during hydrogen evolution in the reaction. The slower hydrogen evolution due to low current density and high BOE viscosity allows sufficient bubble residence time so that a high defect density appears at the bubble edges where local reaction rates are highest. Current‐carrying Si? OH species are most likely responsible for the widening of the craters. Reducing the defect/doping density in silicon lowers the defect concentration and thereby the density of nanopores. Measurements of photoluminescence lifetime and intensity show a distinct feature when the few nanopores formed at the ring edges are isolated from each other. Overall features observed in the photoluminescence intensity by XPS strongly emphasize the role of surface oxide that influences these properties. Copyright © 2005 John Wiley & Sons, Ltd.     

Formation of microstructured silicon surfaces by electrochemical etching using colloidal crystal as mask

Silicon disk arrays and silicon pillar arrays with a close-packed configuration having an ordered periodicity were fabricated by the electrochemical etching of a silicon substrate through colloidal crystals used as a mask. The colloidal crystals were directly prepared by the self-assembly of polystyrene particles on a silicon substrate. The transfer of a two-dimensional hexagonal array of colloidal crystals to the silicon substrate could be achieved by the selective electrochemical etching of the exposed silicon surfaces, which were located in interspaces among adjacent particles. The diameter of the tip of the silicon pillars could be controlled easily by changing the anodization conditions, such as current density and period of electrochemical etching.     

Bulk diffusion of niobium in single-crystal titanium dioxide

The present work reports the tracer diffusion coefficient for (93)Nb in rutile TiO(2) single crystals using secondary ion mass spectrometry (SIMS). The determined tracer diffusion coefficient exhibited the following temperature dependence in air ( p(O2) = 21 kPa) over the range 1073-1573 K: D93(Nb) = (4.7 m2 s(-1))x10(-7+/-0.4) exp ((-244 +/- 9 kJ mol-1)/RT) Through comparison to the self-diffusion of (44)Ti in rutile TiO(2), (93)Nb is interpreted to diffuse via the interstitialcy mechanism. The obtained tracer diffusion data are useful for ensuring compositional control during the processing of Nb-doped TiO(2)-based semiconductors using solid-state reactions between Nb(2)O(5) and TiO(2).     

Anisotropic etching of silicon in hydrazine

This paper contains a detailed discussion of the practical issues related to the anisotropic etching of single crystal silicon using a 5050 hydrazinewater solution. Characteristics of the etchant, etching reactor design, etch procedures, safety precautions, etch rate data for typical samples and appropriate etch-masks are among the topic discussed. The etching process is carried out in a atmospheric reflux reactor, continuously purged with nitrogen. The etch rate of (100) silicon at 115°C in this hydrazine solution is nearly 3 μm/min, which is much higher than that of ethylenediaminepyrocatecholwater (EDP) solutions. Silicon dioxide, silicon nitride and most metallic thin films, except aluminium, can be used to mask the etching process. The etch rate is reduced significantly in highly-boron-doped silicon; a boron concentration of 1.5 × 10²⁰ cm⁻³ practically stops the etch. The use of the hydrazine solution for micromachining thin silicon diaphragms, cantilevers and fibers is demonstrated.     

Electrochemical etching of silicon carbide

Both n- and p-type SiC of different doping levels were electrochemically etched by HF. The etch rate (up to 1.5 μm/min) and the surface morphology of p-type 6H-SiC were sensitive to the applied voltage and the HF concentration. The electrochemical valence of 6.3 ± 0.5 elementary charge per SiC molecule was determined. At p-n junctions (p-type layer on a n-type 6H-SiC substrate) a selective etching of the p-type epilayer could be achieved. For a planar 6H-4H polytype junction (n-type, both polytypes with equal doping concentrations) the 4H region was selectively etched under UV illumination. Thus polytype junctions could be marked by electrochemical etching. With HCl instead of HF no etching of SiC occurs, but a SiO₂ layer (thickness up to 8 μm) is formed by anodic oxidation. Received: 29 October 1998 / Accepted: 27 January 1999     

Specific features of etching of the (001) surface of single-crystalline silicon in KOH-based solutions

Specific features of the micro-and nanorelief of the (001) surface of single-crystalline silicon upon etching in aqueous KOH solutions of various concentrations and at various temperatures, in the presence of new modifying additives (KMnO₄, KNO₃) and without them, were studied. The formation of the main Si(001) defects was attributed to temporary local adsorption of silicates (products of silicon etching) on the silicon surface.     

Depth profiles of arsenic in semiconductor silicon by chemical etching and non-dispersive atomic fluorescence spectrometry with hydride generation

An improved non-dispersive atomic fluorescence spectrometric determination of arsenic by sodium tetrahydroborate reduction is described. A new burner on which a small argon-hydrogen-entrained air flame can be maintained at a low hydrogen flow rate (0.15 1 min^-1) is reported. The detection limit ($\text{S}\text{N}$ = 2) is 10 pg of arsenic, and the analytical working curve is linear over four decades of concentration from the detection limit. The system is applied to depth profiling of arsenic in silicon slices. The silicon is anodized, the silica film is removed by hydrofluoric acid and the arsenic in the etching solution determined. The depth of silicon removed is measured by determining the silicon content in the etching solution by inductively-coupled plasma atomic emission spectrometry. The method permits determinations of ?10¹⁸ atoms As cm^-3 in 30-nm sections of a silicon slice with a diameter of 5.1 cm.     

Mechanisms of surface processes in silicon etching

A unified view on the mechanism allowing one to explain the experimental features governing spontaneous silicon etching by atomic fluorine is presented. Analysis of the phenomenological equation of adsorption shows a significant difference between etching mechanisms at high and low heat of adsorption on the surface being etched. As follows from the parameter estimates, one or another case can be realized under different experimental conditions. At steady-state the etching is argued to be determined only by the processes taking place on the SiF. film surface. To describe the process, it is necessary to understand the mechanism of overcoming the surface barrier for fluorine penetration into the film. At low heat of fluorine adsorption the barrier is overcome by thermal activation. In the opposite case the etching mechanism includes electron tunneling from silicon to adatoms and creation of a surface electric field. The field lowers the high energetic barrier for fluorine penetration. Based on the kinetic equations describing the electronic and atomic processes on the surface, the equation of the field strength is obtained. This equation is analyzed in different limit cases. The observed features are shown to be reproduced at some conditions on the parameters. Definite predictions on the temperature dependence of the etch rate are made.     

Determination of antimony depth profiles in semiconductor silicon by chemical etching and nondispersive atomic fluorescence spectrometry with hydride generation

After the silicon has been anodized, the silica film formed is removed by dilute hydrofluoric acid, and the antimony in the etching solution determined by nondispersive atomic fluorescence spectrometry. The amount of silicon removed is measured in the etching solution by inductively-coupled plasma atomic emission spectrometry. Down to 10¹⁸ atoms Sb cm^-3 can be determined at sectioning intervals of 50 nm.     

Photoassisted etching of silicon dioxide films

Theoretical approaches to resolving the problem of photoassisted etching of silicon dioxide as the most widely used protective layer in microelectronics are presented. A model of donor-acceptor interaction providing for the desolvation of the F^? ion involved in SiO₂ photoetching is proposed. The etchant compositions were optimized, and the effect of the most important factors on the etching process was examined. It has been shown that the maximal photoetching rate is 0.42 μm/min and the chemical contribution to etching is small, being about 0.02 μm/min.     

Determination of phosphorus death profiles in semiconductor silicon by chemical etching and filament vaporization inductively-coupled plasma atomic emission spectrometry

Silicon slices are dissolved by anodizin and removal of the silica film by hydrofluoric acid. The phosphorus in the etching solution is determined by the filament vaporization technique and the depth of silicon is measured by determining the silicon content in the etching solution by conventional inductively-coupled plasma atomic emission spectrometry. A lower limit of 10¹⁸ phosphorus atoms cm^?3 can be determined by sectioning intervals of 30–50 nm.     

Enhancement and stabilization of the photoluminescence from porous silicon prepared by Ag‐assisted electrochemical etching

In this paper, we present the results of studies on the photoluminescence (PL) of porous silicon (PSi) samples obtained by etching with the assistance of silver metal in different ways. If the Si sample, after being coated with a layer of silver nanoparticles, is electrochemically etched, its PL intensity becomes hundreds of times stronger than the PL intensity when it is chemically etched in the similar conditions. The difference in the PL intensities is explained partly by the anodic oxidation of silicon which occurs during the electrochemical etching process. The most obvious evidence that silicon had been oxidized anodically in the electrochemical etching process is the disappearance of the PSi layer and the appearance of the silicon oxide layer with mosaic structure when the anodization current density is large enough. The anodic oxidation has the effect of PSi surface passivation. Because of that, the PL of obtained PSi becomes stronger and more stable with time. Copyright © 2012 John Wiley & Sons, Ltd.     

The effect of the type of conductivity on the initiation and formation of pores in silicon during electrochemical etching

The effect of the type of Si conductivity on the initiation and formation of pores in silicon samples during electrochemical etching was studied. The difference between the pore formation processes in n- and p-conducting silicon was attributed to the properties and the nature of layers formed in the initial period of etching on the Si surface. A possible composition of the layers formed on the Si surface was proposed considering the chemistry of Si interaction with the etching agent.     

Lyotropic self-assembly of high-aspect-ratio semiconductor nanowires of single-crystal ZnO

Lyotropic nanowire dispersions are attractive precursors for semiconductor device fabrication because they permit the alignment control of active nanomaterials. The reliable production of nanowire-based mesophases, however, is very challenging in practice. We show that appropriately functionalized high-aspect-ratio nanowires of single-crystal ZnO spontaneously form nematic phases in organic and aqueous media. These systems show isotropic, biphasic, and nematic phases on increasing concentration, in reasonable agreement with Onsager's theory for rigid rods interacting via excluded volume. Suspensions were readily processed to produce films with large-area monodomains of aligned nanowires. Imprints of the director field in quiescently dried films display a propensity for bend deformation in the organic mesophase versus splay deformation in the aqueous case, suggesting that system elasticity may be tuned via surface functionalization. These results provide critical insight for the utilization of semiconductor nanowires as novel mesogens and further enable the use of solution-based routes for fabricating optoelectronic devices.     

Electron-impact-induced anisotropic etching of silicon by hydrogen

The etch rate of silicon in a hydrogen low-pressure discharge plasma can be strongly enhanced by electron bombardment, reaching presently up to 1000 Å/min. The etch rate increases linearly with increasing electron current density and hydrogen pressure (range 0.05–0.7 mbar) and decreases with increasing temperature, yielding an activation energy of –4.2 kcal/mole in a temperature range of 80 to 300°C. The etching remains anisotropic within the whole pressure range studied.     

Aluminum alloy etching in phosphoric acid solutions

The rate of dissolution of aluminum and qualitative properties (gloss and uniformity) of its surface were examined as influenced by the concentration of H₃PO₄ and fluorine-containing compounds and their nature, as well as by the temperature, pH, and various additions (acids, surfactants, inhibitors).     

Spectroscopic diagnostics of temperature-controlled trench etching of silicon

Ernission from the plasma species CCl, CN, CO, N₂, and Si was monitored during trench etching of silicon with a CHCl,₃/ N, chemistry. The temperature of the backside of the wafer was recorded simultaneously. The emission response to experimentally induced perturbations of the plasma was found to be particularly informative. One such perturbation was a sudden change of the wafer temperature through control of the He pressure under the wafer. The other perturbation involved a drastic change of the N₂, flow rate. Our results confirm the mechanism of control of the trench profile through the temperature-dependent rate of deposition of polymers on the sidewalls during etch. Further, N₂, which certainly plays a crucial role in this chemistry, may engage in a surface reaction producing CN radicals; our data are consistent with this surface reaction. Finally, an algorithm was constructed for real-time monitoring of the selectivity of .silicon to the oxide mask; selectivity is shown to be very sensitive to the presence of N₂.