Au-assisted electroless etching of silicon in aqueous HF/H2O2 solution

The Au-assisted electroless etching of p-type silicon substrate in HF/H₂O₂ solution at 50 °C was investigated. The dependence of the crystallographic orientation, the concentration of etching solution and the silicon resistivity on morphology of etched layer was studied. The layers formed on silicon were investigated by scanning electron microscopy (SEM). It was demonstrated that although the deposited Au on silicon is a continuous film, it can produce a layer of silicon nanowires or macropores depending on the used solution concentration.     

Formation of aligned silicon-nanowire on silicon in aqueous HF/(AgNO3 + Na2S2O8) solution

Highly oriented silicon nanowire (SiNW) layer was fabricated by etching Si substrate in HF/(AgNO₃ + Na₂S₂O₈) solution at 50 °C. The morphology and the photoluminescence (PL) of the etched layer as a function of Na₂S₂O₈ concentration were studied. The SiNW layers formed on silicon were investigated by scanning electron microscopy (SEM) and energy-dispersive X-ray (EDX). It was demonstrated that the morphology of the etched layers depends on the Na₂S₂O₈ concentration. Room-temperature photoluminescence (PL) from etched layer was observed. It was found that the utilisation of Na₂S₂O₈ decreases PL peak intensity. Finally, a discussion on the formation process of the silicon nanowires is presented.     

Fabrication of silver-coated silicon nanowire arrays for surface-enhanced Raman scattering by galvanic displacement processes

Silver-coated silicon nanowire (SiNW) arrays were prepared utilizing galvanic displacement processes consisting of three steps: galvanic displacement deposition of silver particles using a HF-AgNO₃ or NH₄F-AgNO₃ aqueous solution; formation of SiNW arrays by a silver-assisted chemical etching process conducted in the HF-H₂O₂ aqueous solution; deposition of silver particles on the SiNW arrays from the NH₄F-AgNO₃ aqueous solution. The effects of the morphology of pre-deposited silver particles and deposition solution on the formation of silver-coated SiNW arrays were discussed. Surface-enhanced Raman scattering (SERS) performances have been studied using Rhodamine 6G (R6G) probe molecules on the silver-coated SiNW substrates.     

Oxidizing agent concentration effect on metal-assisted electroless etching mechanism in HF-oxidizing agent-H2O solutions

The mechanism of metal-assisted electroless etching of silicon in HF-oxidizing agent-H₂O etching system as a function of oxidizing agent concentration was studied. Three types of oxidizing agent were experimented namely Na₂S₂O₈, K₂Cr₂O₇ and KMnO₄. Their concentrations were varied from 0.05 M to 0.3 M. The layers formed on silicon were investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD) and energy-dispersive X-ray (EDX). It is shown that an insoluble solid-phase film (K₂SiF₆) form on silicon surface when concentration of K₂Cr₂O₇ or KMnO₄ increases in chemical solutions. On other hand, when Na₂S₂O₈ concentration increases, the surface roughness decreases without any chemical complex formation.     

Metal nanorod production in silicon matrix by electroless process

Metal filled Si nanopores, that is, metal nanorods in an Si matrix, are produced by an electroless process that consists of three steps: (1) electroless displacement deposition of metal nanoparticles from a metal salt solution containing HF; (2) Si nanopore formation by metal-particle-enhanced HF etching; and (3) metal filling in nanopores by autocatalytic electroless deposition. Ag nanoparticles produce Si nanopores whose sizes are a few tens of nm in diameter and ca. 50 nm deep. Au nanoparticles produce finer and straighter nanopores on Si than the Ag case. These nanopores are filled with a Co or a Co-Ni alloy by autocatalytic deposition using dimethylamine-borane as a reducing agent. Phosphinate can be used as a reducing agent for the Au-deposited-and-pore-formed Si. The important feature of this process is that the metal nanoparticles, that is, the initiation points of the autocatalytic metal deposition, are present on the bottoms of the Si nanopores.     

Structural, optical and photoelectrochemical characterization of CdS nanowire synthesized by chemical bath deposition and wet chemical etching

Nanocrystalline thin films of CdS have been grown onto flexible plastic and titanium substrates by a simple and environmentally benign chemical bath deposition (CBD) method at room temperature. The films consist of clusters of CdS nanoparticles. The clusters of CdS nanoparticles in the films were successfully converted into nanowire (NW) networks using chemical etching process. The possible mechanism of the etching phenomenon is discussed. These films were examined for their structural, surface morphological and optical properties by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM) and UV-vis spectrophotometry techniques, respectively. Photoelectrochemical (PEC) investigations were carried out using cell configuration as n-CdS/(1 M NaOH + 1 M Na₂S + 1 M S)/C. The film of nanowires was found to be hexagonal in structure with the preferential orientation along the (0 0 2) plane. The nanowires have widths in the range of 50-150 nm and have lengths of the order of a few micrometers. Optical studies reveal that the CdS nanowires have value of band gap 2.48 eV, whereas it is 2.58 eV for nanoparticles of CdS. Finally, we report on the ideality of junction improvement of PEC cells when CdS nanoparticles photoelectrode converted into nanowires photoelectrode.     

Enhancement of electron field emission by carbon coating on vertically aligned Si nanowires

Electron field emission properties of vertically aligned Si nanowires, synthesized by chemically etching p-type Si wafers with different etching times were investigated in detail. Fabrication of Si nanowires was confirmed by field emission scanning electron microscopic investigation. It was observed that a thin layer of amorphous carbon coating over the grown Si nanowires enhanced the field emission properties significantly.     

Microfabrication of freestanding porous silicon particles containing spectral barcodes

A method to microfabricate micron‐scale freestanding porous silicon photonic crystal particles is described. An electrochemically prepared film of porous silicon on a crystalline silicon substrate is patterned with an SU8‐25 photoresist, and the unmasked porous silicon is removed with a chlorine plasma reactive ion etch. Porous microparticles are then removed from the substrate by electropolishing. Scanning electron microscopy and microscopic reflection spectroscopy are used to characterize the geometry and optical properties of the freestanding particles. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Catalysis of dispersed silver particles on directional etching of silicon

Silver particles are dispersed on silicon by magnetron sputtering and post-annealing to investigate the catalytic effects of individual silver particles on wet etching of silicon surface. According to scanning electron microscopy, dispersed deep holes are present and the major etching direction is vertical to the surface of a Si(1 0 0) wafer or inclined to that on a Si(1 1 1) wafer. Our experiments indicate that the effect of the anisotropy of Si on directional etching is fundamental and the wafer resistivity and experimental process have important influence on the etching results. In addition, aggregation of silver particles and random horizontal etching on the surface of the wafer are caused by the local imbalance between the oxidant and HF. Our results enable better understanding of the catalytic effects of metal particles on silicon and are helpful to the preparation new silicon nanostructures.     

Critical diameters and temperature domains for MBE growth of III–V nanowires on lattice mismatched substrates

We report on the growth properties of InAs, InP and GaAs nanowires (NWs) on different lattice mismatched substrates, in particular, on Si(111), during Au‐assisted molecular beam epitaxy (MBE). We show that the critical diameter for the epitaxial growth of dislocation‐free III–V NWs decreases as the lattice mismatch increases and equals 24 nm for InAs NWs on Si(111), 39 nm for InP NWs on Si(111), 44 nm for InAs NWs on GaAs(111)B, and 110 nm for GaAs NWs on Si(111). When the diameters exceed these critical values, the NWs are dislocated or do not grow at all. The corresponding temperature domains for NW growth extend from 320 °C to 340 °C for InAs NWs on Si(111), 330 °C to 360 °C for InP NWs on Si(111), 370 °C to 420 °C for InAs NWs on GaAs(111)B and 380 °C to 540 °C for GaAs NWs on Si(111). Experimental values for critical diameters are compared to the previous findings and are discussed within the frame of a theoretical model. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Time-resolved transmission study of fused silica during laser-induced backside dry etching

Laser-induced backside dry etching (LIBDE) is a promising technique for micro- and nanomachining of transparent materials. Although several experiments have already proved the suitability and effectiveness of the technique, there are several open questions concerning the etching mechanism and the concomitant processes. In this paper time-resolved light transmission investigations of etching process of fused silica are presented. 125 nm thick silver coating was irradiated through the carrying 1 mm thick fused silica plate by single pulses of a nanosecond KrF excimer laser. The applied fluences were 0.38, 0.71 and 1 J/cm². During the etching process the irradiated spots were illuminated by an electronically delayed nitrogen laser pumped dye laser. The delay between the pump and probe pulses was varied in the range of 0 ns and 20 μs. It was found that the transmitted probe beam intensity strongly depends on the applied delays and fluences. Scanning electron microscopy and energy dispersive X-ray spectrometry of the etched surface showed the existence of silver droplets and fragments on the illuminated surfaces and silver atoms built into the treated surface layer influencing the transmission behavior of the studied samples.     

Growth process and wear resistance for ceramic coatings formed on Al-Cu-Mg alloy by micro-arc oxidation

The growth process, distribution of chemical elements, phase constitutions and relative wear resistance of the ceramic coatings formed on Al-Cu-Mg alloy by ac micro-arc oxidation are investigated by scanning electron microscopy (SEM), energy dispersive X-ray spectroscope (EDX), X-ray diffraction (XRD) and reciprocating friction and wear tests. The results indicate that there are three stages with the formation of the ceramic coatings: (1) the formation of ceramic particles, (2) sintering growth in sawtooth structure, (3) the increase of thickness by remolting and sintering. The ceramic coatings are made up of a mixture of α-alumina, γ-alumina and amorphous alumina, whose relative contents varied with the position in the ceramic coatings, respectively. The chemical elements altered in ceramic coatings produced in different electrolytes and varied along the depth in ceramic coatings obtained in phosphate electrolyte. Meanwhile, the results of friction and wear tests against Gr15 after 16 h indicate that the weight loss of ceramic coatings became almost unchanged.     

Electrical and photocatalytic properties of Na2Ti6O13 nanobelts prepared by molten salt synthesis

Single-crystalline Na₂Ti₆O₁₃ nanobelts were prepared on large-scale by molten salt synthesis at 825 °C for 3 h. The obtained nanobelts have typical width of less than 200 nm and thickness of 10-30 nm, and length up to 10 μm. The growth direction of the nanobelts was determined to be along [0 1 0]. Electrical transport property of an individual nanobelt was measured at room temperature and ambient atmosphere, and results showed that the nanobelts are semiconductor. Na₂Ti₆O₁₃ nanobelts exhibited good photocatalytic efficiency for the degradation of RhB under UV irradiation.     

Synthesis of ZnO hollow spherical structures with different surface-to-volume ratios

ZnO hollow spherical structures with different surface-to-volume ratios were prepared using solid Zn microspheres as template via a simple oxygen-controlled thermal evaporation approach. The results of scanning electron microscopy testify that ZnO hollow spherical structures with different morphologies can be realized by changing oxygen supply. The corresponding transmission electron microscopy images further reveal that the prepared spherical structures are hollow, and nanorods epitaxially grow from the surface of the sphere shell along the [0001] direction. A series of experiments indicates that the formation of hollow spherical structures involves the oxidization on the surface of Zn microspheres, sublimation of Zn, and growth of ZnO nanorods.     

Examination of the oxidation resistance of high-alloyed tool steels at elevated temperatures

In the present work the structure of two different tool steels is examined before and after oxidation up to 1000 °C in air. The materials under examination have different chromium contents. Also, the first contains vanadium (S1 tool steel) and the second tungsten (S2 tool steel) as alloying element, while the rest are common. The examination took place by thermogravimetric analysis, scanning electron microscopy, transmission electron microscopy and X-ray diffraction. From this study it is deduced that the structure of the two steels, before oxidation, has several distinguishing differences mostly in the chromium distribution in the iron matrix. The oxidation tests revealed that S2 oxidizes at higher temperatures than S1, but finally, at 1000 °C, S2 tool steel has greater mass gain, because it oxidizes at a higher rate.     

A combined study of the oxidation mechanism and resistance of AISI D6 steel exposed at high temperature environments

In this work it is thoroughly examined the oxidation performance of D6 tool steel under isochronal and isothermal oxidations. Isochronal oxidation tests, from ambient temperature to 1000 °C, revealed the oxidation rate of the coupons at different temperatures. Four different temperatures were selected for the isothermal oxidation test, which correspond to different oxidation rates. The oxidation and the examination of the samples were accomplished by thermogravimetric analysis (TG) in air with which the mass gain of the samples due to oxidation was simultaneously acquired. The samples were, also, examined by scanning electron microscopy (SEM), in order to observe their surface before and after the oxidation tests. X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) were used for the accurate identification of the as formed oxides. The results revealed that in every case two distinct layers of oxides were formed while their composition was different, depending on the temperature of oxidation. Furthermore, the thickness of the as formed oxides is increased when the oxidation is performed at higher temperatures.     

Selective vapor phase etching of SiGe by HCl in a RPCVD reactor

Chemical vapor phase etching of epitaxial SiGe by HCl was investigated using a single wafer reduced pressure CVD (RPCVD) system. For the sample preparation, patterning and dry etching were performed on the Si substrate with SiGe buried layers to open the sidewalls of the buried SiGe layers. The etchrate of the lateral direction was measured. The etchrate of SiGe is increasing with increasing SiGe thickness saturating at SiGe thicknesses higher than ∼25 nm. This result could be caused by diffusion effects of molecules in the narrow trenches during the etching. At the same SiGe thickness, the etchrate of SiGe is increasing with increasing etching temperature. B doping does not affect the etchrate of SiGe. P doping is increasing and C doping is decreasing the etchrate. Facet formation of the etchfront of Si and SiGe depends on initial surface orientation. These results enable improved process controllability of the etching process using doped layers for different applications.     

The effects of hydrogen plasma pretreatment on the formation of vertically aligned carbon nanotubes

The effects of H₂ plasma pretreatment on the growth of vertically aligned carbon nanotubes (CNTs) by varying the flow rate of the precursor gas mixture during microwave plasma chemical vapor deposition (MPCVD) have been investigated in this study. Gas mixture of H₂ and CH₄ with a ratio of 9:1 was used as the precursor for synthesizing CNTs on Ni-coated TiN/Si(1 0 0) substrates. The structure and composition of Ni catalyst nanoparticles were investigated by using scanning electron microscopy (SEM) and cross-sectional transmission electron microscopy (XTEM). Results indicated that, by manipulating the morphology and density of the Ni catalyst nanoparticles via changing the flow rate of the precursor gas mixture, the vertically aligned CNTs could be effectively controlled. The Raman results also indicated that the intensity ratio of the G and D bands (I_D/I_G) is decreased with increasing gas flow rate. TEM results suggest H₂ plasma pretreatment can effectively reduce the amorphous carbon and carbonaceous particles and, thus, is playing a crucial role in modifying the obtained CNTs structures.     

Enhanced etching of silicon didioxide guided by carbon nanotubes in HF solution

This paper describes a new method to create nanoscale SiO₂ pits or channels using single-walled carbon nanotubes (SWNTs) in an HF solution at room temperature within a few seconds. Using aligned SWNT arrays, a pattern of nanoscale SiO₂ channels can be prepared. The nanoscale SiO₂ patterns can also be created on the surface of three-dimensional (3D) SiO₂ substrate and even the nanoscale trenches can be constructed with arbitrary shapes. A possible mechanism for this enhanced etching of SiO₂ has been qualitatively analysed using defects in SWNTs, combined with H₃O⁺ electric double layers around SWNTs in an HF solution.     

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.