A periodic array of silicon pillars fabricated by photoelectrochemical etching

A periodic array of silicon pillars was photoelectrochemically fabricated using the two-step etching process with a n-type Si (1 0 0) substrate. Two key factors, backside illumination and anodic bias, were required to obtain a high-aspect ratio macropore array of silicon. It was found that the initial pore could be separated into two different pores when the applied anodic bias was greater than a certain critical value. The pore size of the macroporous silicon with a high porosity was increased by anisotropic etching in an alkaline solution. Due to destruction of the pore sidewalls, KOH etching allowed for the fabrication of silicon pillars on a large-scale wafer with an improved uniformity. The anisotropic etching behavior of KOH solution led to necking of the silicon pillars when the etching time exceeded 60 s.     

Carbide-derived-carbons with hierarchical porosity from a preceramic polymer

Synthesis of carbon by extraction of metals from carbides has been successfully used to produce a variety of micro-porous carbide-derived carbons (CDCs) with narrow pore size distributions and tunable sorption properties. This approach is of limited use when larger mesopores are targeted, however, because the relevant synthesis conditions yield broad pore size distributions. Here we demonstrate the porosity control in the 3-10 nm range by employing preceramic polymer-derived silicon carbonitride (SiCN) precursors. Polymer pyrolysis in the temperature range 600-1400 °C prior to chlorine etching yields disordered or graphitic CDC materials with surface area in the range 800-2400 m² g⁻¹. In the hierarchical pore structure formed by etching SiCN ceramics, the mesopores originate from etching silicon nitride (Si₃N₄) nano-sized crystals or amorphous Si-N domains, while the micropores come from SiC domains. The etching of polymer-derived ceramics allows synthesis of porous materials with a very high specific surface area and a large volume of mesopores with well controlled size, which are suitable for applications as sorbents for proteins or large drug molecules, and supports for metal catalyst nanoparticles.     

Negative potential dissolution (NPD)-advanced and rapid texturing method of as-cut silicon

Texturing of as-cut p-type boron doped (1 1 1) oriented silicon has been carried out by negative potential dissolution (NPD) in KOH solutions in the dark. The use of KOH in concentrations of 16-32 wt.% results in massive silicon texturing with a formation of coined triangles pits morphology. This morphology can be formed within a short etching time of less than a minute. At higher KOH concentrations (50 wt.% KOH) and under similar conditions as-cut silicon surface is being polished. NPD current-time profile has a distinguished “U” shape. Detailed mechanism accounting for NPD texturing is provided explaining this characteristic. NPD process allows a rapid etching of as-cut (1 1 1) p-type silicon by a factor of 100, compared with etching rate at OCP. NPD allows the texturing of silicon within a very short period of time once the potentials are more negative than −10 V. As the potential is further negatively shifted, silicon etch-rate increases, as well. NPD also provides a marked distinguish between two processes: texturing and polishing; a transformation between texturing and polishing is feasible once.     

Experimental study of macropore formation in p-type silicon in a fluoride solution and the transition between macropore formation and electropolishing

Anodic dissolution of p-Si is studied in diluted fluoride solution (HF 0.05 M + NH₄F 0.05 M, pH 3), with special focus on the physico-chemical parameters which govern the morphology of pore formation (crystallographic orientation, applied potential, and etching time). The effect of potential has been investigated in the transition region between macropore formation and electropolishing. Upon increasing the anodization potential, the pore cross-section changes from circular to square shape, and the bottom of the pores changes from a rounded to a V-shaped profile. Prolonged etching of the contour of (1 1 0) p-Si disks in the regime of porous silicon formation allows for a comparison of the etching characteristics of the orientations. SEM observation indicates indeed different morphologies as a function of the crystal orientation, and the formation of fractal-like structures is obtained for some orientations. In the same geometry and at a potential just above the onset of the electropolishing regime, prolonged anodization allows for a direct measurement of the Si thickness removed as a function of the crystallographic orientation. We clearly observe the etching anisotropy, with etch depth τ(1 1 1) < τ(1 1 0) < τ(1 0 0). This sequence, similar to that observed for current density in more concentrated HF, differs from that observed for the chemical etching of Si in an alkaline solution.     

Fabrication of flat silicon surfaces using ion-exchange particles in ultrapure water

A silicon etching process using an ultrafine particle dispersion is proposed. The ultrafine particles contain quaternary ammonium hydroxide groups as ion-exchange groups, giving an alkaline dispersion. In the etching process, the fine particles and impurity ions can be easily separated by filtration or dialysis. Dialysis led to a decrease in the concentration of impurities in the dispersion, which included heavy metal ions and alkali metal ions known to result in a rough etched surface and affect the electronic properties of the semiconductor. Our proposed method is applicable to the surface planarization of silicon single crystals, manufacture of semiconductor devices, and fabrication of MEMS (micro-electro and mechanical systems). In addition, the etching waste can be reused after removal of the impurity ions by dialysis. Thus, the method has low environmental burden. Using the proposed alkaline etching dispersion, cathodic electrochemical etching of a silicon single crystal was demonstrated. The etching characteristics, properties of the etched surface, and effects of particle size were evaluated. The roughness of a 2 μm × 2 μm etched p-Si(0 0 1) surface was measured to be 0.1228 nm Ra (center line average roughness) by AFM.     

Catalytic etching of {100}-oriented diamond coating with Fe, Co, Ni, and Pt nanoparticles under hydrogen

Etching of a highly {100}-oriented diamond coating, {100}HODC, with hydrogen gas using Fe, Co, Ni, and Pt nanoparticles as a catalyst was examined at high temperatures over 700 °C by high-resolution scanning electron microscopy and Raman spectroscopy. The metal atoms vacuum-evaporated onto the {100}HODC formed nanoparticles themselves when heated at high temperatures; e.g. 700 °C, in a flowing gas mixture of H₂ (10%) + N₂ (90%). At 800 °C, short nano-channels and etch pits holding metal nanoparticles were formed by Fe, Co, and Ni. The shapes of the Co and Ni nanoparticles in the etch pits were affected by the shape of the etch pits; reversed pyramidal shape. On the other hand, the top view of the Fe nanoparticles embedded in the etch pits showed a distorted round shape, probably due to the formation of something such as iron carbide, while the carbon content was unknown. Apparently, etching of the {100}HODC by Pt nanoparticles was observed after the treatment at 1000 °C. The difference in the catalytic etching behavior among these metal particles, the potential etching mechanism of diamonds with hydrogen by metal nanoparticles, probably as melted metal nanoparticles, and the formation mechanism of vacant etch pits were discussed.     

Triangle pore arrays fabricated on Si (111) substrate by sphere lithography combined with metal-assisted chemical etching and anisotropic chemical etching

ABSTRACT: The morphological change of silicon macropore arrays formed by metal-assisted chemical etching using shape-controlled Au thin film arrays was investigated during anisotropic chemical etching in tetramethylammonium hydroxide (TMAH) aqueous solution. After the deposition of Au as the etching catalyst on (111) silicon through a honeycomb mask prepared by sphere lithography, the specimens were etched in a mixed solution of HF and H2O2 at room temperature, resulting in the formation of ordered macropores in silicon along the [111] direction, which is not achievable by conventional chemical etching without a catalyst. In the anisotropic etching in TMAH, the macropores changed from being circular to being hexagonal and finally to being triangular owing to the difference in etching rate between the crystal planes.     

Dry etching of diamond nanowires using self-organized metal droplet masks

In a top-down approach diamond nanowires (DNW) were fabricated by anisotropic oxygen plasma etching of undoped or boron doped polycrystalline diamond layers. Dewetting an evaporated metal film, resulting in randomly distributed metal droplets of 5-50 nm in diameter, created the etching mask. This study focused on the investigation of the effect of the metal layer type, i.e., Al, Ti, Co, Ni, Cu, Pd, Pt and Au, and thickness on surface density, shape and size of the resulting droplets. Two dry etching techniques were studied: (1) Capacitively Coupled Plasma Reactive Ion Etching (CCP-RIE) and (2) Inductively Coupled Plasma Reactive Ion Etching (ICP-RIE). Using CCP-RIE diamond etch rates were between 10 nm/min and 50 nm/min; however, diamond/Ni selectivity was not high enough to fabricate nanowires > longer than 250 nm. ICP-RIE etching created tapered, high aspect diamond nanostructures at 1000 W plasma power, 10 W platen power for ion acceleration and long etching times (> 40 min) while preserving the mask. Anisotropy can be improved by the addition of Ar in the plasma and the reduction of the pressure. So far, vertically aligned diamond nanowires of 800 nm in length were obtained by ICP-RIE etching in appropriate conditions.     

Controlled morphology and optical properties of n-type porous silicon: effect of magnetic field and electrode-assisted LEF

Fabrication of photoluminescent n-type porous silicon (nPS), using electrode-assisted lateral electric field accompanied with a perpendicular magnetic field, is reported. The results have been compared with the porous structures fabricated by means of conventional anodization and electrode-assisted lateral electric field without magnetic field. The lateral electric field (LEF) applied across the silicon substrate leads to the formation of structural gradient in terms of density, dimension, and depth of the etched pores. Apart from the pore shape tunability, the simultaneous application of LEF and magnetic field (MF) contributes to a reduction of the dimension of the pores and promotes relatively more defined pore tips as well as a decreased side-branching in the pore walls of the macroporous structure. Additionally, when using magnetic field-assisted etching, within a certain range of LEF, an enhancement of the photoluminescence (PL) response was obtained.     

Electroplating synthesis and electrochemical properties of macroporous Sn-Cu alloy electrode for lithium-ion batteries

Macroporous material of Sn-Cu alloy of different pore sizes designated as anode in lithium-ion batteries were fabricated through colloidal crystal template method. The structure and electrochemical properties of the macroporous Sn-Cu alloy electrodes were examined by using scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and galvanostatic cycling. The results demonstrated that the electrodes of macroporous Sn-Cu alloy with pore size respectively of 180 and 500 nm can deliver reversible capacity of 350 and 270 mAh g⁻¹ up to 70th cycles of charge/discharge. The cycle performance of the macroporous Sn-Cu alloy of 180 nm in pore size is better than that of the macroporous Sn-Cu alloy with 500-nm-diameter pores. It has revealed that the porous structure of the macroporous Sn-Cu alloy material is of importance to strengthen mechanically the electrode and to reduce significantly the effect of volume expansion during cycling.     

Formation of nanostructured silicon surfaces by stain etching

In this work, we report the fabrication of ordered silicon structures by chemical etching of silicon in vanadium oxide (V₂O₅)/hydrofluoric acid (HF) solution. The effects of the different etching parameters including the solution concentration, temperature, and the presence of metal catalyst film deposition (Pd) on the morphologies and reflective properties of the etched Si surfaces were studied. Scanning electron microscopy (SEM) was carried out to explore the morphologies of the etched surfaces with and without the presence of catalyst. In this case, the attack on the surfaces with a palladium deposit begins by creating uniform circular pores on silicon in which we distinguish the formation of pyramidal structures of silicon. Fourier transform infrared spectroscopy (FTIR) demonstrates that the surfaces are H-terminated. A UV-Vis-NIR spectrophotometer was used to study the reflectance of the structures obtained. A reflectance of 2.21% from the etched Si surfaces in the wavelength range of 400 to 1,000 nm was obtained after 120 min of etching while it is of 4.33% from the Pd/Si surfaces etched for 15 min.     

Gaseous infiltration method for preparation of three-dimensionally ordered macroporous polyethylene

Three-dimensionally ordered macroporous polyethylenes (3DOM PE) with pore size ranging from 135 nm to 410 nm were prepared using supported catalysts on the surface of silica microsphere as template, followed infiltration of gaseous ethylene and polymerization. The morphology of 3DOM PE was characterized by SEM and the reflectance spectrum was recorded by UV-vis. It is shown that the pores are uniform, flexible and arranged in a highly ordered fashion. Reflectance spectrum of 3DOM PE also provided verification of the uniform nature of the sample. Moreover, the effect of confined space on polymerization was investigated by GPC and DSC. The results indicate that the porous PE possesses higher M_w compared with bulk PE, and exhibits lower melting temperature and crystallinity than those of bulk PE.     

Bottom-up self-assembly of macroporous ZnO nanostructures for photovoltaic applications

The present study utilized a template-assisted electrodeposition route for the bottom-up epitaxial growth of macroporous zinc oxide nanostructures. To this end, the ZnO seed layer was coated on the p-type silicon substrates using a radio frequency magnetron sputtering technique to form a p-n heterojunction. Then, polymer microspheres were implanted on ZnO/Si substrates to act as a template. Subsequently, ZnO nanostructures were electrodeposited through the interstitial spaces between the microspheres. After the deposition, the microspheres were removed by dissolving in chloroform solvent, forming a porous structure. The planar and cross-sectional electron microscopy analyses exhibited a uniform macroporous morphology with an average pore diameter of ∼1 μm. The pores were homogeneously distributed on the surface of the electrodeposited ZnO layer. The advantage of this technique over the top-down approaches, such as electrochemical etching, is that the porosity and size of pores can be easily adjusted by varying the concentration and diameter of microsphere templates. The optical investigations revealed enhancement in photon absorption and photoluminescence (PL) intensity due to multiple light scattering in the pore walls of the deposited ZnO nanostructures. For the templated sample, a PL blue shift was observed due to the reduction in crystallite size of ZnO nanostructures. A heterojunction thin film solar cell was designed by the metallization of ZnO/p-Si samples to study the power conversion capability of macroporous ZnO nanostructures. The photovoltaic performance of the developed devices was evaluated under a solar light simulator. The device based on the templated sample showed increased shunt resistance and reduced series resistance compared to the flat sample. The optoelectrical results indicated an efficiency improvement for the fabricated solar cells based on the macroporous ZnO sample due to its higher exposed area and increased rate of electron-hole generation.     

The influence of formation conditions on the growth and morphology of carbon trees

Carbon trees, quite different from those previously reported, have been produced by the catalytic chemical vapor deposition of toluene using ferrocene as the catalyst precursor. The influences of formation conditions such as catalyst mass, toluene flow rate, and reaction time on the tree growth and morphology have been investigated. The yield of carbon trees is greatly affected by catalyst quantity. A lower toluene flow rate (50-100 ml/min) or shorter reaction time (10-30 min) leads to trees with thinner (several microns) and filamentous branches, while a higher toluene flow rate (greater than 200 ml/min) or longer reaction time (60-120 min) produces thicker (tens of microns) and spherical branches. Results suggest that the morphology of the carbon trees can be adjusted by varying the reaction conditions.     

Porous Si layers—Preparation, characterization and morphology

Porous silicon layers (PSL) of nano- and micro-structures were prepared by metal-assisted electroless etching of silicon in HF-oxidizing agent aqueous solutions. The effect of oxidizing agent and HF content on the characteristics of the formed porous layers was investigated. A thin Pt film was electroless deposited on p-Si〈1 0 0〉 prior to immersion in the etching solution. The properties and morphology of the PSL formed by this method were investigated by electrochemical impedance spectroscopy (EIS) scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) technique. The characteristics of the PSL were found to be affected by the constituents of the etching medium and also, the etching time. Potassium bromate (KBrO₃), potassium iodate (KIO₃), and potassium dichromate (K₂Cr₂O₇) have been used as oxidizing agents. Pt-assisted etching of p-Si for 1 h in an etching solution consisting of 22.0 M HF and 0.05 M of KBrO₃, results in the formation of nano- and micro-pores on the Si surface. The use of 0.05 M KIO₃ or K₂Cr₂O₇ as oxidizing agent has led to the formation of a deposit on the silicon surface. At relatively higher concentration [>0.05 M] of K₂Cr₂O₇ the surface deposit becomes clear and was found to consist of an insoluble passive solid-phase of K₂SiF₆ which increases the film impedance and blocks the porous structure formation. The use of higher concentration [>22 M] of HF in the etching electrolyte is accompanied by an increase in the dissolution rate of the insoluble K₂SiF₆ layer and a decrease in the PSL passivity. The experimental impedance data were fitted to theoretical data according to a proposed equivalent circuit model which accounts for the mechanism of the porous film formation at the Si/electrolyte interface.     

Effect of a GDL based on carbon paper or carbon cloth on PEM fuel cell performance

A commercially available GDL based on carbon paper or carbon cloth as a macroporous substrate was characterized by various physical and electrochemical measurements: mercury porosimetry, surface morphology analysis, contact angle measurement, water permeation measurement, polarization techniques, and ac-impedance spectroscopy. SGL 10BB based on carbon paper demonstrated dual pore size distribution and high water flow resistance owing to less permeable macroporous substrate, and more hydrophobic and compact microporous layer, as compared to ELAT-LT-1400 W based on carbon cloth. The membrane-electrode-assembly fabricated using SGL 10BB showed an improved fuel cell performance when air was used as an oxidant. The ac-impedance response indicated that a microporous layer which has high volume of micropores and more hydrophobic property allows oxygen to readily diffuse towards the catalyst layer due to effective water removal from the catalyst layer to the gas flow channel.     

Effect of transition metal catalysts on the microstructure of carbide-derived carbon

Carbon materials with different microstructure can be produced by a carbide-derived carbon (CDC) approach varying the carbide precursor and the reaction conditions for the selective etching of the metal. CDC was produced using biomorphic TiC and SiC ceramics derived from paper preforms by a chemical vapor infiltration and reaction technique. In this work the effect of transition metal salt catalysts such as Ru(III), Fe(II), Fe(III) or Ru(III)/Fe(III) on the chlorination process at temperatures in the range 600-1200 °C as well as on the microstructure of the resulting carbon was investigated. The produced CDC was characterized by its degree of order and pore structure using Raman spectroscopy, high resolution transmission electron microscopy and low temperature nitrogen adsorption. A higher etching rate as well as a higher degree of order at lower reaction temperatures was observed if a catalytically active metal was present during the chlorination process. This effect was mostly pronounced in the case of a Ru(III)/Fe(III) bimetallic catalyst. The higher degree of order of the carbon is associated with an increased amount of mesopores and with a decrease in specific surface area. Therefore, the CDC processing in the presence of catalysts offers another way to produce ordered carbon structures at lower temperatures.     

In situ EC-STM studies of n-Si(1 1 1):H in 40% NH4F solution at pH 10

In situ electrochemical-scanning tunneling microcopy (EC-STM) was employed to investigate the etching dynamics of the moderately doped n-Si(1 1 1) electrode during cyclic voltammetric perturbation and at the seven different potentials including the open circuit potential (OCP) in 40% NH₄F solution at pH 10, which was prepared from 40% NH₄F and concentrated NH₄OH solution. The etching rate was significant at OCP and showed an exponential dependence on the potential applied to the silicon substrate electrode. Although some triangular pits were generated at the Si(1 1 1) surface, at the potentials more negative than OCP the site dependence in the removal of surface silicon atoms prevailed and led to the atomically flat Si(1 1 1):H surfaces with sharply defined steps of the step height 3.1 Å, where the interatomic distance of 3.8 Å was observed with a three-fold symmetry. At the potentials sufficiently more positive than OCP, macroporous hole was formed to limit further in situ EC-STM study. The results were compared with in situ EC-STM studies of the etching reaction of n-Si(1 1 1):H in the aqueous solution of dilute ammonium fluoride at pH 5, 40% NH₄F at pH 8, and 1 M NaOH reported in the literature.     

Formation of porous silicon at elevated temperatures

The features of electrochemical formation process of porous silicon (PS) at the temperatures above the room temperature have been studied. It was found that besides electrochemical dissolution, chemical etching takes part in the formation process of PS even for concentrated HF electrolyte. The role of chemical etching increases with temperature causing an increase of the porosity and the crater depth. The temperature dependence of chemical etching rate has been established. Obtained results enable to conclude that OH⁻ ions play a major role in the chemical etching. Electrochemical etching allows to fabricate PS with good surface quality at the temperatures at least below 65 °C provided that HF electrolyte is concentrated.