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.     

Hybrid nanostructure of polypyrrole and porous silicon prepared by galvanostatic technique

Nanostructured porous silicon (PS) layer is prepared in a lightly doped p-type substrate (with pores < 5 nm) and used as a working electrode to deposit conducting polypyrrole (PPy) by the electrochemical oxidative polymerization technique in an organic liquid phase. Three distinguishable stages of PPy deposition are observed and recorded under constant applied current: nucleation of polymer at the pore bottom, unidirectional growth of PPy inside the pores, and polymerization outside the PS surface. The hybrid nanostrucutre of PS/PPy shows a significant improvement of electrical conductivity as opposed to the unmodified PS layer. The improved conductivity is observed in spite of the formation of insulating layer of silicon oxides as detected by X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) measurements. Systematic study of fabrication and characterization of this organic-inorganic heterosystem, quantification of the PPy in the PS matrix, and the mechanism of filling the nanopores with polymer are presented and thoroughly discussed.     

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.     

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.     

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.     

Metal-assisted etching of p-type silicon under anodic polarization in HF solution with and without H2O2

Pore formation under anodic polarization of a lightly doped p-type Si wafer previously loaded with Pt, Pd and Ag nanoparticles was investigated in HF solution with and without H₂O₂. In HF solution without H₂O₂, a microporous layer was formed in p-Si loaded with Pt or Pd. However, Ag metal nanoparticles yielded pores due to their intrusion in the Si wafer. The addition of H₂O₂ to the etching solution leads to different pore morphologies depending on the metals. Particles of Ag were found at the bottom of most pores. In the presence of Pt nanoparticles, cone-shaped macropores were produced, and the pore depth and diameter increased with increasing H₂O₂ content. Current density influenced the pore morphology. For a sample loaded with Pt or Ag, an increase in applied current density widened the pore diameter. The mechanism of the metal-assisted pore formation was discussed by considering a competitive process between the formation of a microporous layer under polarization and metal-assisted chemical oxidation of the microporous layer by a dissolved oxidizing agent.     

Enhanced electrochemical performance of nano-sized LiFePO4/C synthesized by an ultrasonic-assisted co-precipitation method

A simple and effective method, the ultrasonic-assisted co-precipitation method, was employed to synthesize nano-sized LiFePO₄/C. A glucose solution was used as the carbon source to produce in situ carbon to improve the conductivity of LiFePO₄. Ultrasonic irradiation was adopted to control the size and homogenize the LiFePO₄/C particles. The sample was characterized by X-ray powder diffraction, field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM). FE-SEM and TEM show that the as-prepared sample has a reduced particle size with a uniform size distribution, which is around 50 nm. A uniform amorphous carbon layer with a thickness of about 4-6 nm on the particle surface was observed, as shown in the HRTEM image. The electrochemical performance was demonstrated by the charge-discharge test and electrochemical impedance spectra measurements. The results indicate that the nano-sized LiFePO₄/C presents enhanced discharge capacities (159, 147 and 135 mAh g⁻¹ at 0.1, 0.5 and 2 C-rate, respectively) and stable cycling performance. This study offers a simple method to design and synthesis nano-sized cathode materials for lithium-ion batteries.     

Highly crystalline macroporous β-MnO2: Hydrothermal synthesis and application in lithium battery

A highly crystalline macroporous β-MnO₂ was hydrothermally synthesized using stoichiometric reaction between KMnO₄ and MnCl₂. The as-prepared material has a pore size of ca. 400 nm and a shell thickness of 300-500 nm. The formation of the macroporous morphology is related to self-assembling from nanowires of α-MnO₂, and could be obtained at high reactant concentrations (e.g., 0.8 M KMnO₄) but not at low ones (e.g., below 0.04 M KMnO₄). Compared to conventional bulk β-MnO₂ processing very low capacity, our macroporous material exhibits good electrochemical activity, e.g., obtaining an initial discharge capacity of 251 mAh g⁻¹ and sustaining as ca. 165 mAh g⁻¹ at 10 mA g⁻¹. The electrochemical activity of the as-prepared β-MnO₂ is related to its macroporous morphology and small shell thickness; the former leads to that electrolyte can flood pore of the material and its inner surface is available for lithium ion diffusion, while the latter helps to release the stress from phase transformation during the initial discharging. The X-ray diffraction characterizations of the macroporous β-MnO₂ electrodes suggest that, upon initial discharging, such a β-MnO₂ will be irreversibly transformed to an orthorhombic Li_xMnO₂ and then cycled within the new developed phase in the subsequent lithium insertion/extraction processes.     

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.     

Effect of heat treatment on 7Na2O-23B2O3-70SiO2 glass

Porous 7Na₂O-23B₂O₃-70SiO₂ glass was successfully fabricated by acid leaching treatment and phase-separation. The 2 mol/l hydrochloric acid (HCl) solution treatment was used for 24 h. Thermal analysis and X-ray diffraction were used to identify the temperature range of heat-treatment. The average pore size and the pore volume were investigated by a nitrogen adsorption instrument, and SEM was used to characterize the appearance of the porous glass. The results show that the average size of pores changed from 3.75 nm to 3.03 nm when heat treated at 640-680 °C for 6 h. In addition, when heat treated at 640 °C for 6-24 h, the pore size fell from 3.75 nm to 3.66 nm. The surface area and pore volume become larger with the increase in both temperature and heat treatment time.     

Fabrication of CaSiO3 bioceramics with open and unidirectional macro-channels using an ice/fiber-templated method

Porous CaSiO₃ bioceramics with open and unidirectional macro-channels of pore size more than 200 μm are of particular interest for biomedical applications. An ice/fiber-templated method was employed for the fabrication of CaSiO₃ bioceramics with interconnected lamellar pores and macro-channels of pore size more than 200 μm. The pores formed by ice crystals transformed from cellular to lamellar, while the pores formed by fibers were aligned macro-channels, which were also in alignment with the lamellar pores. Keeping the initial slurry concentration constant and increasing the packing density of fibers, the volume fraction of macro-channels and open porosity increased, and the compressive strength decreased. Maintaining the packing density of fibers and increasing the initial slurry concentration, the pore sizes of lamellar pores and open porosity decreased, and the compressive strength increased. The results indicated that it was possible to manufacture porous CaSiO₃ bioceramics with the macro-channels of 250–350 μm, lamellae spacing of 50–100 μm, open porosity of 71.12–83.94% and compressive strength of 0.87–3.59 MPa, indicating the suitability for tissue engineering.     

Cyclic CO2 capture behavior of KMnO4-doped CaO-based sorbent

This study examines the CO₂ capture behavior of KMnO₄-doped CaO-based sorbent during the multiple calcination/carbonation cycles. The cyclic carbonation behavior of CaCO₃ doped with KMnO₄ and the untreated CaCO₃ was investigated. The addition of KMnO₄ improves the cyclic carbonation rate of the sorbent above carbonation time of 257 s at each carbonation cycle. When the mass ratio of KMnO₄/CaCO₃ is about 0.5-0.8 wt.%, the sorbent can achieve an optimum carbonation conversion during the long-term cycles. The carbonation temperature of 660-710 °C is beneficial to cyclic carbonation of KMnO₄-doped CaCO₃. The addition of KMnO₄ improves the long-term performance of CaCO₃, resulting in directly measured conversion as high as 0.35 after 100 cycles, while the untreated CaCO₃ retains conversion less than 0.16 at the same reaction conditions. The addition of KMnO₄ decreases the surface area and pore volume of CaCO₃ after 1 cycle, but it maintains the surface area and pores between 26 nm and 175 nm of the sorbent during the multiple cycles. Calculation reveals that the addition of KMnO₄ improves the CO₂ capture efficiency significantly using a CaCO₃ calcination/carbonation cycle and decreases the amount of the fresh sorbent.     

Facile electrochemical preparation of three-dimensional porous Cu films by potential perturbation

A 3-dimentional (3D) micro-nano hierarchical porous Cu film was fabricated by surface rebuilding of smooth Cu substrates in a blank solution of 1 M NaOH with square wave potential perturbation. The potential step from 0.4 to −2.5 V (vs. SCE) and a frequency of 50 Hz were chosen for the fabrication. The pore formation and Cu nanostructure evolution were characterized by scanning electron microscopy. The fabrication process involved fast Cu electrochemical oxidation-reduction and suitable rate of H₂ releasing. During the repeated Cu oxidation-reduction, the Cu atoms were removable, forming dendrite-like structures. At the same time, the formed H₂ bubbles acted as a dynamic template to shape the formation of micropores. The effect of H₂ bubble as a template on the size of the formed micropores was demonstrated by adding a small amount of surfactant (cetyltrimethylammonium bromide, CTAB) into the basic solution to adjust the size of the bubbles. The as-prepared 3D porous Cu showed high electrocatalytic activity toward the reduction of NO₃⁻ and H₂O₂. The present in situ preparation method was green, convenient and required neither Cu(II) species and additives in solution nor post-treatment for template removal.     

Crystallinity and order of poly(ethylene oxide)/lithium triflate complex confined in nanoporous membranes

The confinement of poly(ethylene oxide), PEO, electrolyte in pores of 13, 35, 55 and 100 nm in diameter in nanoporous alumina membranes was seen to have effects on the ionic conduction properties. Specific conductivity values for the PEO/lithium triflate complex in the 13 and 35 nm pores, for temperatures below the melt temperatures, were increased by a factor of four compared to the non-confined polymer and the 55 and 100 nm pore systems. Thermal analysis data indicate the melting temperature for the PEO electrolyte in the pores is directly proportional to the pore size such that as the pore size of confinement is decreased, the T_m decreases as well. The same behavior is seen for the amount of crystallinity, with less crystallinity being observed as the pores become smaller. Perhaps the observed conduction behavior could be attributed to less crystallinity. However, it is known that confinement of polyethers in pores results in stretching and ordering of the backbone and that such ordering can increase ion conduction. This ordering would seem to be the major factor involved in these results. The enhanced conduction only being seen in the 13 and 35 nm pores and not the 55 and 100 nm pores is attributed to the larger size for the latter which allows a more bulk-like behavior with less ordering.     

Influence of grain size on the corrosion behavior of a Ni-based superalloy nanocrystalline coating in NaCl acidic solution

The effects of grain size on the electrochemical corrosion behavior of a Ni-based superalloy nanocrystalline (NC) coating fabricated by a magnetron sputtering technique, has been investigated in 0.5 M NaCl + 0.05 M H₂SO₄ solution. Coatings with grain sizes 10 nm, 50 nm and 100 nm were fabricated on glass and the superalloy substrates. The results indicate that a passive film with porous property, n-type semiconductive property and incorporation of chloride ions formed on the NC coating with 100 nm grain size, which increased the susceptibility to pitting corrosion. The NC coatings with 10 nm and 50 nm grain size formed compact, non-porous and p-type passive films without chloride ions, which improved resistance to pitting corrosion. The smaller grain size of the material decrease the amount of chloride ions adsorbed on the surface and promoted the formation of compact passive film, which significantly increased the material's resistance to pitting corrosion in acidic solution.     

Template-free fabrication of silicon micropillar/nanowire composite structure by one-step etching

A template-free fabrication method for silicon nanostructures, such as silicon micropillar (MP)/nanowire (NW) composite structure is presented. Utilizing an improved metal-assisted electroless etching (MAEE) of silicon in KMnO₄/AgNO₃/HF solution and silicon composite nanostructure of the long MPs erected in the short NWs arrays were generated on the silicon substrate. The morphology evolution of the MP/NW composite nanostructure and the role of self-growing K₂SiF₆ particles as the templates during the MAEE process were investigated in detail. Meanwhile, a fabrication mechanism based on the etching of silver nanoparticles (catalyzed) and the masking of K₂SiF₆ particles is proposed, which gives guidance for fabricating different silicon nanostructures, such as NW and MP arrays. This one-step method provides a simple and cost-effective way to fabricate silicon nanostructures.     

Controlled growth of porous networks in phosphide semiconductors

Pore networks in InP, as well as its ternary alloy with GaP, lattice matched to GaAs, are studied using scanning, transmission and high resolution electron microscopy techniques. The pores were grown by the electrochemical dissolution method along specific crystallographic directions. The applied etching current in galvanostatic and voltage in potentiostatic conditions are the key factors for the pore formation and direction, given a certain sample orientation and type of doping. Pores can be either crystallographically oriented (CO) in low current or current-like oriented (CLO) for increasing voltage and current densities. Scanning electron microscopy revealed that the CLO pores in InP tend to self-organized structures just below the nucleation layer, formed at about 50–80 nm from the free surface. Electron diffraction experiments showed that CO pores are readily formed along various crystallographic directions that depend linearly on the applied current value, resulting in a fully controllable pore formation mechanism. A three-dimensional pore network is thus feasibly accomplished in InP by periodically cutting off the dissolution process during the CLO pore formation or switching between CLO and CO pores, along with the organization of the CO pores on the basal (100) plane. High resolution observations showed that the single crystalline structure of InP is preserved in the vicinity of pores, illustrating the non-destructive nature of electrochemical dissolution. The formation of pores in Ga_0.49In_0.51P/GaAs heteroepitaxial layers takes place almost along the two [11] and [11] directions.     

Preparation of mesoporous NiO with a bimodal pore size distribution and application in electrochemical capacitors

Mesoporous nickel oxide with a porous structure exhibiting a bimodal pore size distribution (2.6 and 30.3 nm diameter pores) has been synthesized in this paper. Firstly, a mesoporous precursor of coordination complex Ni₃(btc)₂·12H₂O (btc = 1,3,5-benzenrtricarboxylic acid) is synthesized based on the metal-organic coordination mechanism by a hydrothermal method. Then mesoporous NiO with a bimodal size distribution is obtained by calcining the precursor in the air, and characterized by transmission electron microscopy and N₂ adsorption measurements. Such unique multiple porous structure indicates a promising application of the obtained NiO as electrode materials for supercapacitors. The electrochemical behavior has been investigated by cyclic voltammogram, electrochemical impedance spectra and chronopotentiometry in 3 wt.% KOH aqueous electrolyte. The results reveal that the prepared NiO has high-capacitance retention at high scan rate and exhibits excellent cycle-life stability due to its special mesoporous character with bimodal size distribution.     

Highly Porous SiOC Bulk Ceramics with Water Vapor Assisted Pyrolysis

Micro/mesoporous SiOC bulk ceramics with the highest surface area and the narrowest pore size distribution were prepared by water‐assisted pyrolysis of polysiloxane in argon atmosphere at controlled temperatures (1100°C–1400°C) followed by etching in hydrofluoric acid (HF) solution. Their pyrolysis behaviors, phase compositions, and microstructures were investigated by DSC, FTIR, XRD, and BET. The Si–O–Si bonds, SiO₂‐rich clusters, and SiO₂ nanocrystals in the pyrolyzed products act as pore‐forming species and could be etched away by HF. Water injection time and pyrolysis temperature have important effects on phase compositions and microstructures of the porous SiOC bulk ceramics, which have a maximum‐specific surface area of 2391.60 m²/g and an average pore size of 2.87 nm. The porous SiOC ceramics consist of free carbon phase, silicon carbide, and silicon oxycarbide.     

Impedance spectroscopy study of saturated mortar samples

Mortar samples saturated with different solutions (deionised water, 0.5 M NaCl and 1 M NaCl) are studied to quantify microstructural changes induced by weathering of concrete in near-neutral solutions containing chlorides. The study is based on physical and electrochemical techniques. Mercury intrusion porosimetry is employed to quantify porosity and pore size distribution, and impedance spectroscopy as a non-destructive technique able to give information on structural changes. SEM imaging, XRD, and EDX characterisation allow elucidating the causes of the observed structural changes.Portlandite leaching tends to increase porosity. Nevertheless, the leaching process towards near-neutral solutions makes resistivity to increase. The presence of chlorides induces Friedel's salt formation, a slow process associated to the development of small size pores (around 10 nm).Impedance spectroscopy in the frequency range 10⁻² to 10² MHz is successfully employed to follow Friedel's salt formation and pore network development in mortars.