Nanostructures formed by displacement of porous silicon with copper: from nanoparticles to porous membranes

ABSTRACT: The application of porous silicon as a template for the fabrication of nanosized copper objects is reported. Three different types of nanostructures were formed by displacement deposition of copper on porous silicon from hydrofluoric acid-based solutions of copper sulphate: (1) copper nanoparticles, (2) quasi-continuous copper films, and (3) free porous copper membranes. Managing the parameters of porous silicon (pore sizes, porosity), deposition time, and wettability of the copper sulphate solution has allowed to achieve such variety of the copper structures. Elemental and structural analyses of the obtained structures are presented. Young modulus measurements of the porous copper membrane have been carried out and its modest activity in surface enhanced Raman spectroscopy is declared.     

Comparative study of initial stages of copper immersion deposition on bulk and porous silicon

Initial stages of Cu immersion deposition in the presence of hydrofluoric acid on bulk and porous silicon were studied. Cu was found to deposit both on bulk and porous silicon as a layer of nanoparticles which grew according to the Volmer-Weber mechanism. It was revealed that at the initial stages of immersion deposition, Cu nanoparticles consisted of crystals with a maximum size of 10 nm and inherited the orientation of the original silicon substrate. Deposited Cu nanoparticles were found to be partially oxidized to Cu₂O while CuO was not detected for all samples. In contrast to porous silicon, the crystal orientation of the original silicon substrate significantly affected the sizes, density, and oxidation level of Cu nanoparticles deposited on bulk silicon.     

Effect of chloride ions on immersion plating of copper onto porous silicon from a methanol solution

The effect of chloride ions (Cl⁻) during the immersion plating of copper onto porous silicon (PS) from a methanol (MeOH) solution has been studied. The presence of Cl⁻ in the Cu²⁺ solution was found to slow down the rate of copper deposition, as confirmed by inductively coupled argon plasma emission spectroscopy and X-ray photoelectron spectroscopy measurements. The threshold concentration of Cl⁻ at which the deposition of copper is very severely diminished was found to be 0.1 M. The inhibition effect is discussed on the basis of the rest potential values of PS and polarization curve measurements. They revealed that the rest potential of PS upon dipping in these solutions appears to direct the metal deposition. Current density-potential curves show that at Cl⁻ concentrations higher than 0.1 M, the reduction of Cu ions proceeds in two steps; the reduction of Cu(II) to Cu(I) followed by the reduction of Cu(I) to Cu(0). This suggests that Cu(I) species in MeOH solution can be stable over a certain potential range and this stability of Cu(I) is responsible for the inhibition of metal deposition. Fourier transform infrared spectroscopy and scanning electron microscopy (SEM) were also performed to investigate the structural changes and characterizations of PS samples after the plating process.     

Electrochemical deposition of zinc oxide on a thin nickel buffer layer on silicon substrates

Electrochemical deposition of ZnO from aqueous nitrate solutions on nickel and platinum electrodes was investigated using the voltammetry technique to determine the optimal regimes in both potentiostatic and galvanostatic modes for acquiring polycrystalline ZnO films. Scanning electron microscopy, X-ray diffractometry, and X-ray microanalysis of the formed ZnO films are presented, showing a polycrystalline structure of the ZnO films with a preferable orientation in the (0 0 0 2) direction and an exact stoichiometric composition. The deposited ZnO films demonstrate a strong visible yellow-greenish photoluminescence at room temperature with a maximum at 600 nm that can be referred to crystal lattice oxygen defects. The maximum of the photoluminescence excitation spectrum at 370 nm corresponds to the band gap of ZnO (3.3–3.35 eV) confirming that band-to-band excitation mechanism takes place.     

Immersion plating of copper onto porous silicon with different thickness

This work aims to detail the mass change of a porous silicon sample during copper immersion plating. Gravimetric measurements and quantification of the deposited copper by induced coupled plasma spectroscopy (ICP) permit to separate the contributions to the mass change. The results indicate that immersion plating proceeds independently of the porous layer thickness at short immersion time. However, after long immersion duration, the deposition stops and thick porous layers are not fully oxidised. The oxidation of the porous layer is homogeneous and proceeds in depth with time, down to several micrometers.     

Electroless deposition and silicidation of Ni contacts into p-type Porous Silicon

Porous Silicon (PS) has attracted much attention since the discovery of its photo luminescent behavior. It has also been used for various other applications such as electroluminescent light emitting-diodes (LEDs), photodetectors and solar cells. For such devices, it is important to make good metallic Ohmic contacts to the PS in order to maximize the efficiency. In order to produce buried contacts, barrier layers, Schottky devices, etc. in PS, it is advantageous to deposit metal that covers not only the surface of the porous layer, but also the inside walls and the bottom of the pores. In this work experiments were performed to examine the morphology and properties of electroless deposition of Nickel into p-type PS and subsequent formation of Nickel silicide after heat treatment. Circular PS samples of 6 mm diameter were produced by anodizing p-type Silicon wafers for 15 min and were subsequently plated with Ni using three different plating baths. The pores are on average 20 μm deep and 4 μm wide. Two samples of each type were heat treated in an nitrogen atmosphere for one hour at 400 and 600°C respectively to produce Nickel silicide. Reference samples were made by means of electron beam evaporation of Ni. SEM micrographs show that the best pore coverage was achieved using the Ni plating bath containing hypophosphite. I–V characterization shows that different rectifying and Ohmic contacts can be formed between electroless deposited Ni and PS depending on the conditions of the heat treatment. XRD and EDX characterizations show that both the NiSi and Ni₂Si phases exist in the sample at the same time.      

Transient surface photovoltage studies of bare and Ni-filled porous silicon performed in different ambients

Mesoporous silicon and porous silicon/Ni nanocomposites have been investigated in this work employing light-dark surface photovoltage (SPV) transients to monitor the response of surface charge dynamics to illumination changes. The samples were prepared by anodization of a highly n-doped silicon wafer and a subsequent electrodepositing of Ni into the pores. The resulting pores were oriented towards the surface with an average pore diameter of 60 nm and the thickness of the porous layer of approximately 40 μm. SPV was performed on a bare porous silicon as well as on a Ni-filled porous silicon in vacuum and in different gaseous environments (O₂, N₂, Ar). A significant difference was observed between the ‘light-on’ and ‘light-off’ SPV transients obtained in vacuum and those observed in gaseous ambiences. Such behavior could be explained by the contribution to the charge exchange in gas environments from chemisorbed and physisorbed species at the semiconductor surface.

PACS

81.05.Rm; 73.20.-r; 75.50.-y; 82.45.Yz     

Observation of initial deposition process of electroless nickel plating by quartz crystal microbalance method and microscopy

The initial deposition process of electroless nickel plating was investigated by combining a quartz crystal microbalance (QCM) method with microscopy. The authors found an anomalous deposition rate in the initial deposition and four stages were noted: an induction period before the initiation of deposition, an acceleration period with an increase in the deposition rate, a deceleration period with a decrease in the deposition rate and a stationary period at a constant deposition rate. The practical surface area of the deposits increased until the deposits became continuous and reached a constant value. On the other hand, the deposition rate per unit practical surface area decreased monotonously as the deposition proceeded. As a result, an anomalous initial deposition rate was observed. The four periods also appeared in the deposition when the catalyzation process was repeated 4 times. In this case, the number of grains at the initial stage was greater, and nucleation still continued until the deposits became continuous. The initial deposits, therefore, became continuous at lower thickness.     

Optical characterization of porous silicon monolayers decorated with hydrogel microspheres

The optical response of porous silicon (pSi) films, covered with a quasi-hexagonal array of hydrogel microspheres, to immersion in ethanol/water mixtures was investigated. For this study, pSi monolayers were fabricated by electrochemical etching, stabilized by thermal oxidation, and decorated with hydrogel microspheres using spin coating. Reflectance spectra of pSi samples with and without deposited hydrogel microspheres were taken at normal incidence. The employed hydrogel microspheres, composed of poly-N-isopropylacrylamide (polyNIPAM), are stimuli-responsive and change their size as well as their refractive index upon exposure to alcohol/water mixtures. Hence, distinct differences in the interference pattern of bare pSi films and pSi layers covered with polyNIPAM spheres could be observed upon their immersion in the respective solutions using reflective interferometric Fourier transform spectroscopy (RIFTS). Here, the amount of reflected light (fast Fourier transform (FFT) amplitude), which corresponds to the refractive index contrast and light scattering at the pSi film interfaces, showed distinct differences for the two fabricated samples. Whereas the FFT amplitude of the bare porous silicon film followed the changes in the refractive index of the surrounding medium, the FFT amplitude of the pSi/polyNIPAM structure depended on the swelling/shrinking of the attached hydrogel spheres and exhibited a minimum in ethanol-water mixtures with 20 wt% ethanol. At this value, the polyNIPAM microgel is collapsed to its minimum size. In contrast, the effective optical thickness, which reflects the effective refractive index of the porous layer, was not influenced by the attached hydrogel spheres.

PACS

81.05.Rm; 81.16.Dn; 83.80Kn; 42.79.Pw     

Impedance model of electrolyte-insulator-semiconductor structure with porous silicon semiconductor

We present a generic impedance model for the porous silicon|electrolyte structure that is valid for a range of interfacial layers and bias in these structures. The model is validated using three widely different porous structures: short irregular silicon columns and pores, long cylindrical silicon columns and pores; and branched interconnected silicon microchannels and voids in a mesh structure. The model incorporates appropriate RC or constant phase elements for the different parts of the porous structure, namely, the top of the silicon columns (channels)|electrolyte, the column (channel) walls|electrolyte in the pores/channels, and the electrolyte|semiconductor interface at the base of the pores/channels. This physical model underscores the effects of column/channel depletion and accumulation, either due to applied bias or change of surface charge, to the impedance spectra of the device. The model helps to explain why the porosity needs to be optimized for specific applications and helps as a measurement tool for optimization.     

Morphological and structural studies of nanoporous nickel oxide films fabricated by anodic electrochemical deposition techniques

Porous nickel oxide films are directly deposited onto conducting indium tin oxide coated glass substrates by cyclic voltammetric (CV), galvanostatic, and potentiostatic strategies in a plating bath of sodium acetate, nickel sulfate, and sodium sulfate. By tuning the deposition parameters, it is possible to prepare nickel oxide films with various morphologies and structures. Film formation relies on the oxidation of dissolved Ni²⁺ to Ni³⁺, which further reacts with the available hydroxide ions from a slightly alkaline electrolyte to form insoluble nickel oxide/hydroxide deposits on the substrate. A compact film with particularly small pores is obtained by CV deposition in a potential range of 0.7-1.1 V. A galvanostatically deposited film is structurally denser near the surface of the substrate, and becomes less dense further away from the surface. Interestingly, a potentiostatically deposited film has pores distributed uniformly throughout the entire film. Therefore, for obtaining a uniform film with suitable pore size for electrolyte penetration, potentiostatic deposition technique is suggested. In addition, except for CV deposition, the deposited films resemble closely to cubic NiO when the annealing temperature exceeds 200 °C.     

Electrochemical synthesis of nickel hexacyanoferrate nanoarrays with dots, rods and nanotubes morphology using a porous alumina template

Transition metal hexacyanoferrate (MeHCF) have attracted extensive attention because of their outstanding properties including, electrocatalysis, molecular magnetism, biosensing and ion-exchange. This paper describes an approach for fabrication of ordered nanoarrays of Ni hexacyanoferrate (NiHCF) structures with different morphologies such as dots, rods and tubes in order to advance their properties and applications. The method is based on the conversion of Ni into NiHCF nanostructures by electrochemical oxidation in the presence of hexacyanoferrate ions, using nanoporous anodic alumina oxide (AAO) as a template. The structure and morphology of formed Ni and NiHCF nanoarrays were confirmed by scanning electron microscopy (SEM), showing agreement with the pore structures of the AAO template. The electrocatalytic activity of NiHCF nanorod array electrodes showed high catalytic properties for the detection of hydrogen peroxide and the potential to be used as a platform for direct biosensing applications. The ion-exchange ability of fabricated NiHCF nanostructures (nanorods and nanotubes) toward alkali cations such as Na⁺ has been successfully confirmed.     

A comparative electrochemical study of iron deposition onto n- and p-type porous silicon prepared from lightly doped substrates

Electrodeposition of iron from acidic sulfate solutions onto porous silicon (PS) prepared from n- and p-type (1 0 0) substrates is studied by electrochemical measurements. Results from current-potential curves show that deposition of iron on p-type PS can only be achieved under illumination and cathodic polarization, whereas the deposition is found to proceed on n-type even in the dark. The measurements of the cathodic current efficiency indicate that the fraction of current used for iron deposition decreases with the applied potential due to hydrogen evolution reaction which is a competing reaction to metal deposition. Scanning electron microscopy shows that very fine iron crystallites with an average size of 40-70 nm are formed under double potential step conditions. The energy band diagrams of silicon-solution interfaces determined by electrochemical impedance measurements reveal that the iron deposition mechanism on both substrates is electron transfer from the conduction band.     

Electrochemical preparation of photosensitive porous n-type Si electrodes, modified with Pt and Ru nanoparticles

A novel electrochemical procedure for preparation of the very stable, thin modifying layer onto the n-type Si surface was elaborated. The modification consisted of platinum or/and ruthenium ultrafine particles etched into the porous Si film. A unique sequence of modifications was applied: at first the metal particles were evenly electrodeposited onto a flat silicon surface, and in the next electrochemical step the porous structure was produced. The platinum coverage and mean particle diameter were well controlled by the electrochemical programs. All the attempts and progress in modifications were monitored by scanning electron microscope (SEM) observations. Furthermore, the materials obtained were compared with the non-porous, Pt or/and Ru modified electrodes by testing them as anodes in the photoelectrochemical (PEC) cell with organic Br₂/2Br⁻ solution.In general, the porous photo-anodes gave higher output powers and the light-to-electricity conversion efficiencies. The best performance was observed for the PEC cell employing the porous anode with sequentially electrodeposited Ru and Pt particles, respectively (PS-Si/Ru/Pt).¹ This cell maintained good electrical parameter values during the 2-week tests, having a maximum output power equal to 0.23 mW/cm² and a cell conversion efficiency of 8.5%. The PS-Si/Pt photo-anode gained 0.21 mW/cm² and 7.8%, respectively.     

Electrophoretic deposition of titania nanostructured coatings with different porous patterns

Titania nanostructured coatings with different porous patterns were fabricated by electrophoretic deposition (EPD) in isopropanolic suspension including different concentrations of carbon active (CA) or carbon black (CB) particles as the porogen additives. Finer and negatively charged CA particles were electrostatically adsorbed on the coarser and positively charged titania particles and formed CA-titania particles. While, finer and positively charged titania particles were electrostatically adsorbed on the coarser and negatively charged CB particles to form titania-CB particles. Both CA-titania and titania-CB particles had the net positive surface charge and so cathodic EPD was applicable. EPD was carried out at optimized conditions of 60?V and 10?s. Thermogravimetry (TG) analysis showed that CA and CB burn out between 450?°C and 600?°C. The higher the carbon content in the suspension the higher was their content in the coating. The coatings were characterized by SEM, AFM, adhesion strength and bioactivity tests. Even coatings with interconnected fine pores and low roughnesses were obtained after the heat treatment of CA-titania coatings. While, rough coatings with coarse and isolated pores were obtained after the heat treatment of titania-CB coatings. The porosity of coating increased as the carbon content increased in the suspension. The hydroxyapatite layer grew on the coatings after their soaking in simulated body fluid for 1week at 37.5?±?1.5?°C.     

Template-directed synthesis of porous alumina particles with precise wall thickness control via atomic layer deposition

Highly porous alumina particles with precise wall thickness control were synthesized by atomic layer deposition (ALD) of alumina on highly porous poly(styrene-divinylbenzene) (PS-DVB) particle templates. Alumina ALD was carried out using alternating reactions of trimethylaluminum and water at 33 °C. The growth rate of alumina was ∼0.3 nm per coating cycle. The wall thickness can be precisely controlled by adjusting the number of ALD coating cycles. Thermo-gravimetric analysis, X-ray diffraction, nitrogen adsorption, scanning electron microscopy, and transmission electron microscopy were used to characterize the fabricated porous alumina particles. The effect of number of ALD coating cycles and calcination temperature on the mesoporous structure of the alumina particles was investigated. γ-Alumina was formed at temperature above 600 °C. Porous alumina particles with a surface area of 80-100 m²/g were obtained and thermally stable at 800 °C. The pore volume of the porous particles can be as high as 1 cm³/g after calcination at 800 °C. Such porous alumina particles may find wide application in nanotechnology and catalysis.     

Fabrication,microstructural characterization and gas permeability behavior of porous silicon nitride ceramics with controllable pore structures

Porous Si₃N₄ ceramics with monomodal and bimodal pore structure were prepared by cold isostatic pressing and freeze-casting, respectively. Both the pore structure and permeability behavior of the porous Si₃N₄ ceramics were tailored by altering the pressure of cold isostatic pressing and the composition and content of solvent during freeze-casting. The specimens obtained by cold isostatic pressing exhibited smaller Darcian and non-Darcian permeability than those of freeze-casted samples due to their lower open porosity, smaller pore size and higher tortuosity. On the other hand, compared with the ice-templated specimens having the same solvent volume in the ceramic slurries as them during freeze-casting, the emulsion-ice templated samples showed smaller open porosity, macropore size and Dacian permeability, but the similar non-Darcian permeability because of their larger micropores and better pore interconnectivity.     

Catalytic Activity of Noble Metals for Metal-Assisted Chemical Etching of Silicon

ABSTRACT: Metal-assisted chemical etching of silicon is an electroless method that can produce porous silicon by immersing metal-modified silicon in a hydrofluoric acid solution without electrical bias. We have been studying the metal-assisted hydrofluoric acid etching of silicon using dissolved oxygen as an oxidizing agent. Three major factors control the etching reaction and the porous silicon structure: photoillumination during etching, oxidizing agents, and metal particles. In this study, the influence of noble metal particles, silver, gold, platinum, and rhodium, on this etching is investigated under dark conditions: the absence of photogenerated charges in the silicon. The silicon dissolution is localized under the particles, and nanopores are formed whose diameters resemble the size of the metal nanoparticles. The etching rate of the silicon and the catalytic activity of the metals for the cathodic reduction of oxygen in the hydrofluoric acid solution increase in the order of silver, gold, platinum and rhodium.