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.     

Effect of noble metal catalyst species on the morphology of macroporous silicon formed by metal-assisted chemical etching

Macroporous silicon with ordered pore intervals was fabricated by the site-selective chemical etching of a Si substrate using patterned noble-metal thin films as a catalyst. The morphology of the etched silicon surface and the etching rate was affected by the shape of deposits and metal catalyst species such as Pt-Pd, Au, and Pt. The etching rate increased in the following order: Au < Pt ≤ Pt-Pd. The pores of macroporous silicon prepared by using Pt-Pd catalyst were conical in shape because of the chemical dissolution of the surface of the macropores. On the other hand, by using Au catalyst, relatively straight pores with uniform diameter were formed in the direction of pore depth. The morphology of macroporous silicon was assumed to be affected by the difference in the shape of metal catalysts and the diffusion behaviour of injected positive holes at the silicon/metal interface.     

Anodic electrode reaction of p-type silicon in 1-ethyl-3-methylimidazolium fluorohydrogenate room-temperature ionic liquid

The anodic electrode behavior for a p-type silicon single crystal electrode ((1 0 0), ρ = 0.01-0.02 Ω cm, boron doped) was examined in the 1-ethyl-3-methylimidazolium fluorohydrogenate, EtMeIm(FH)_2.3F, room-temperature ionic liquid (RTIL). The electrochemical behavior was very similar to that in conventional HF aqueous solution. After the anodic electrode reaction, the Si electrode was uniformly covered with a mesoporous Si layer having a pore size of ∼25 nm. The mesoporous layer did not exhibit a photoluminescence spectrum in the visible region due to the lack of Si-H termination. However, after chemical treatment with an ethanolic HF solution, a subset of the porous Si samples showed a very weak photoluminescence.     

Pore diameter control of anodic aluminum oxide with ordered array of nanopores

Highly uniform, self-ordered anodic aluminum oxide (AAO) with an ordered nanoporous array can be effectively formed from industrially pure (99.5%) aluminum sheets through an anodizing program in a mixture solution of sulfuric and oxalic acids. The influences of anodizing variables, such as applied voltage, solution temperature, oxalic acid concentration, agitation rate, and sulfuric acid concentration, on the average pore diameter of AAO were systematically investigated using fractional factorial design (FFD). The applied voltage, and sulfuric acid concentration were found to be the key factors affecting the pore diameter of AAO films in the FFD study. The pore diameter of AAO is regularly increased from ca. 50 to 150 nm when the applied voltage and the concentration of sulfuric acid are gradually increased from 53 to 80 V and from 3.5 to 8 M, respectively. Fine tuning of the pore diameter for AAO films with an ordered, nanoporous, arrayed structure from industrially pure aluminum sheets can be achieved.     

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.     

Resorcinol-formaldehyde based porous carbon as an electrode material for supercapacitors

Porous carbon materials were prepared using resorcinol and formaldehyde catalyzed by KOH in a sol-gel process followed by carbonization, during which the KOH serves as an activating agent and generates pores mainly located in the micropore range. With an increase of mass ratio of KOH to resorcinol from 1 to 4, both the specific surface area and the pore volume of the carbons increased, from 522 to 2760 m²/g and 0.304 to 1.347 cm³/g, respectively, but the average pore diameter decreased from 4.4 to 2.5 nm. Samples were investigated as electrode materials in supercapacitors and the relevant electrochemical behavior was characterized by cyclic voltammetry, electrochemical impedance spectroscopy and constant current charge-discharge experiments using 30% KOH aqueous solution as electrolyte. The highest specific capacitance of up to 294 F/g was obtained at a current density 1 mA/cm² for the sample with mass ratio of KOH to resorcinol of 2. Only a slight decrease in capacitance for the same sample, from 294 to 242 F/g, was observed when the current density increased from 1 to 30 mA/cm². The specific capacitance only decayed 3% at a current density 30 mA/cm² after 1000 cycles, which indicates that the sample possesses excellent power property and cycle durability.     

In situ photoelectrochemistry and Raman spectroscopic characterization on the surface oxide film of nickel electrode in 30 wt.% KOH solution

The oxide films of nickel electrode formed in 30 wt.% KOH solution under potentiodynamic conditions were characterized by means of electrochemical, in situ PhotoElectrochemistry Measurement (PEM) and Confocal Microprobe Raman spectroscopic techniques. The results showed that a composite oxide film was produced on nickel electrode, in which aroused cathodic or anodic photocurrent depending upon polarization potentials. The cathodic photocurrent at −0.8 V was raised from the amorphous film containing nickel hydroxide and nickel monoxide, and mainly attributed to the formation of NiO through the separation of the cavity and electron when laser light irradiates nickel electrode. With the potential increasing to more positive values, Ni₃O₄ and high-valence nickel oxides with the structure of NiO₂ were formed successively. The composite film formed in positive potential aroused anodic photocurrent from 0.33 V. The anodic photocurrent was attributed the formation of oxygen through the cavity reaction with hydroxyl on solution interface. In addition, it is demonstrated that the reduction resultants of high-valence nickel oxides were amorphous, and the oxide film could not be reduced completely. A stable oxide film could be gradually formed on the surface of nickel electrode with the cycling and aging in 30 wt.% KOH solution.     

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.     

Effects of micropore development on the physicochemical properties of KOH-activated carbons

Effects of micropore development through varying the KOH/char ratio on the porous, electrochemical, electronic, and adsorptive properties for corncob-derived activated carbons (ACs) prepared by means of the KOH activation method were systematically compared. The pore properties of ACs, including BET surface area, total pore volume, micropore volume ratio, bulk density, and product yield based on the raw material were investigated to gain an understanding for the influence of KOH dosage on the pore development. Element analysis and temperature-programming desorption (TPD) were used to obtain the information of chemical composition and surface oxygen functional groups on ACs in order to propose the reaction mechanism of KOH activation. Based on the pore development, KOH-activated carbons can be classified into two groups: a combination of physical activation and chemical KOH etching at low KOH/char ratios (0.5-2) as well as chemically uniform etching at high KOH/char ratios (≥3.0). From the adsorption study for five organics with molecular weights varying from 129 to 466 g/mol, the specific adsorption capacity of ACs for organics is independent of their specific surface area. The specific capacitance of ACs reached a maximum as the KOH/char ratio was equal to 3, attributed to a compromise between the specific surface area and electronic resistance of ACs.     

Formation of porous anodic films on Ti-Si alloys in hot phosphate-glycerol electrolyte

Porous anodic films, with pore size of ∼10 nm, have been developed by anodizing of magnetron sputtered Ti-25 at.% Si alloy at constant formation voltages in glycerol electrolyte containing dibasic potassium phosphate at 433 K. The films, of amorphous structure, contain titanium and silicon species, as units of TiO₂ and SiO₂, throughout the film thicknesses, with negligible amounts of phosphorus species. The silicon is enriched in the film relative to the composition of the alloy, the level of enrichment suggesting that anion migration is increased in comparison with amorphous film growth at ambient temperature. In contrast to the behaviour of the alloy, essentially barrier films were formed on commercially pure titanium in the glycerol electrolyte, when a main anodic reaction was generation of oxygen, which was probably promoted by the development of anatase.     

Cylindrical pore arrays in silicon with intermediate nano-sizes: A template for nanofabrication and multilayer applications

An electrochemical technique for the fabrication of intermediate nano-sized pores in silicon (50-200) nm in aqueous HF solution is reported. Attempts to achieve similar nano-sized pores in the presence of organic solvents are also presented. Mesopore formation beginning with pore sizes <50 nm followed by pore widening in alkaline etch solution is also attempted. The desired pore size is obtained with a KMnO₄ oxidizing agent in the presence of surfactant. Our findings reveal that the applied current density during the fabrication process is a decisive factor. The concentration of HF and KMnO₄ should be controlled within appropriate ranges. A multilayer with two different pore morphologies is fabricated on the same substrate using the same electrolyte simply by changing the applied anodic current. Application of such cylindrical pore arrays as templates for polymer nanofabrication is demonstrated. By selective dissolution of the silicon membranes, we successfully obtained nanowires of polypyrrole (PPy) with ∼100 nm diameter size. The fabrication process, the electrochemical measurements, the formation mechanism and the different pore morphologies are investigated in detail.     

Preparation and electrochemistry of NiO/SiNW nanocomposite electrodes for electrochemical capacitors

This paper studies nickel oxide/silicon nanowires (NiO/SiNWs) as composite thin films in electrodes for electrochemical capacitors. The SiNWs as backbones were first prepared by chemical etching, and then the Ni/SiNW composite structure was obtained by electroless plating of nickel onto the surface of the SiNWs. Next, the NiO/SiNW nanocomposites were fabricated by annealing Ni/SiNW composites at different temperatures in an oxygen atmosphere. Once the electrodes were constructed, the electrochemical behavior of these electrodes was investigated with cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). In 2 M KOH solution, the electrode material was found to have novel capacitive characteristics. Finally, when the NiO/SiNW composites were annealed at 400 °C, the maximum specific capacitance value was found to be as high as 681 F g⁻¹ (or 183 F cm⁻³), and the probing of the cycling life indicated that only about 3% of the capacity was lost after 1000 charge/discharge cycles. This study demonstrated that NiO/SiNW composites were the optimal electrode choice for electrochemical capacitors.     

Bias voltage dependent electrochemical impedance spectroscopy of p- and n-type silicon substrates

For a comprehensive interpretation of the electrochemical processes occurring at a semiconductor/electrolyte interface, an accurate value of the flatband potential versus the reference electrode is needed together with the current/voltage response. The present work is mainly devoted to the analysis of impedance diagrams recorded with n- and p-type silicon electrodes in the dark, in a pure diluted HF solution under different bias values, the potential range being chosen so as the dc current is maintained at a low value, e.g. less than 5 μA cm⁻², and even less than 10 nA cm⁻² in the case of p-type Si under cathodic polarization.Two series of impedance diagrams were recorded. Firstly, the bias value was settled in the potential range where the depletion layer was generated within the semiconductor substrate. In this condition, the high resistance of the space charge region and the resulting low value of the dc current permitted to obtain well-defined semicircles leading to the derivation of both R and C values equivalent to the depletion layer charge distribution. The method based on the analysis of the voltage dependent R-value was compared to the usual Mott-Schottky plot treatment, and proved to be efficient for the determination of a reliable value of the flatband potential versus the reference electrode.In the second series, the analysis of the impedance diagrams was focused on the range of potentials corresponding to the onset of an accumulation layer within the semiconductor. In the case of p-Si, this condition corresponds to the rapid anodic etching of the silicon substrate. At a particular value of the bias, an important induction loop was observed in addition to the usual capacitive behaviour. A Fourier transform treatment demonstrated that the impedance components were interrelated to the time dependent current response under constant bias potential. Then, simultaneous experiments based on chronoamperometry measurements suggested that the electrochemical processes involved in the reaction of Si substrate with HF solution was correlated to a two-step charge transfer mechanism. This interpretation is valid for both the inductive loop obtained in electrochemical impedance spectroscopy and the rise of current versus time observed in chronoamperometry.     

Influence of chemical additives on the surface reactivity of Si in KOH solution

It is known that the electrochemistry of silicon in alkaline solution is closely linked to the anisotropic etching of the semiconductor. In this work the influence of two commonly used additives, hydrogen peroxide and isopropyl alcohol, on the surface chemistry of silicon in KOH solution was investigated by electrochemical methods. The results allow us to draw conclusions regarding the role of the additives in the chemical and electrochemical reactions.     

Superparamagnetic iron oxide nanoparticle attachment on array of micro test tubes and microbeakers formed on p-type silicon substrate for biosensor applications

A uniformly distributed array of micro test tubes and microbeakers is formed on a p-type silicon substrate with tunable cross-section and distance of separation by anodic etching of the silicon wafer in N, N-dimethylformamide and hydrofluoric acid, which essentially leads to the formation of macroporous silicon templates. A reasonable control over the dimensions of the structures could be achieved by tailoring the formation parameters, primarily the wafer resistivity. For a micro test tube, the cross-section (i.e., the pore size) as well as the distance of separation between two adjacent test tubes (i.e., inter-pore distance) is typically approximately 1 μm, whereas, for a microbeaker the pore size exceeds 1.5 μm and the inter-pore distance could be less than 100 nm. We successfully synthesized superparamagnetic iron oxide nanoparticles (SPIONs), with average particle size approximately 20 nm and attached them on the porous silicon chip surface as well as on the pore walls. Such SPION-coated arrays of micro test tubes and microbeakers are potential candidates for biosensors because of the biocompatibility of both silicon and SPIONs. As acquisition of data via microarray is an essential attribute of high throughput bio-sensing, the proposed nanostructured array may be a promising step in this direction.     

A transmission electron microscopy study of hard anodic oxide layers on AlSi(Cu) alloys

Transmission electron microscopy (TEM) has been employed to examine anodic oxide film formation on 99.8 wt.% aluminium, Al-10 wt.%Si and Al-10 wt.%Si-3 wt.%Cu alloys under conditions relevant to hard anodizing. In particular, anodic oxidation of silicon particles proceeded at a significantly reduced rate compared with that of the adjacent aluminium matrix. This gave rise to alumina film encroachment beneath the particles with development of tortuous porosity and, eventually, occlusion of partially anodized particle in the anodic film. Additional effects included the presence of gas-filled cavities above the silicon particles, associated with oxygen generation above the anodizing particle. The presence of such particles and the corresponding gas-filled voids across the anodic film thickness and at the alloy/film interface is considered responsible for the continuous voltage rise during anodizing of the Al-10 wt.%Si alloy, effectively blocking electrolyte access to the pore base and providing local region of high resistance at the alloy/film interface. A direct consequence of the voltage rise was a thickening of the barrier layer at the base of the porous anodic film. For the ternary alloy, with the additional presence of copper and the CuAl₂ particles, the latter appear to have undergone complete oxidation, with copper detected in local film regions.     

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.     

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.     

Relationship between the nanoporous texture of activated carbons and their capacitance properties in different electrolytes

A series of activated carbons (ACs) with progressively changing nanotextural characteristics was obtained by heat-treatment of a bituminous coal at temperatures ranging from 520 to 1000 °C, and subsequent activation by KOH at 700 °C or 800 °C. As the pre-treatment temperature increases, the total pore volume V_T decreases from 1.28 to 0.30 cm³ g⁻¹, and the BET specific surface area from 3000 to 800 m² g⁻¹. The specific capacitance determined for each series of ACs using symmetric two electrode cells in 6 mol L⁻¹ KOH varies almost linearly with the BET surface area, suggesting that the charge accumulation is controlled primarily by the surface area development. A further analysis of the electrochemical behaviour in different electrolytic media—aqueous and organic—shows that an adequate pore size is more important than a high surface area in order to obtain high values of capacitance. Theoretical values of volumetric capacitance could be evaluated without considering the size of ions, which is always uncertain in solution, and compared with the experimental data as a function of the pore width. The efficiency of pore filling, i.e., of double layer formation, is optimal when the pore size is around 0.7 nm in aqueous media and 0.8 nm in organic electrolyte. A study of the performance of the positive and negative electrodes during the charge/discharge of the capacitor, reveals an additional pseudo-faradaic contribution due to oxygenated functionalities within the working potential window of the negative electrode. This effect is more pronounced for the ACs series obtained at 700 °C, because of their higher oxygen content.     

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.