Self-assembled formation of uniform InP nanopore arrays by electrochemical anodization in HCl based electrolyte

Attempts were made to optimize the electrochemical anodization process for the formation of high-density, regular and straight nanopore arrays on InP. The structure, shape and size of the pores were very sensitive to substrate orientations, electrolyte concentrations and anodization voltages. Among (1 1 1)A, (1 1 1)B and (0 0 1) substrate orientations, the most uniform and most straight nanopore arrays were obtained on (0 0 1) substrates at anodization voltages of 5-7 V by using 1.0-1.5 M HCl electrolyte containing HNO₃. The pore depth could be controlled up to 80 μm by the anodization time.     

Synthesis of Y-junction carbon nanotubes within porous anodic aluminum oxide template

Y-junction carbon nanotubes with the average diameter about 200 nm were successfully synthesized within porous anodic aluminum oxide template, which was prepared by anodic anodizing aluminum sheet in 1.0 mol/l H₃PO₄ solution at a constant anodization voltage 90 V.     

Physical bounds of metallic nanofingers obtained by mechano-chemical atomic force microscope nanolithography

To obtain metallic nanofingers applicable in surface acoustic wave (SAW) sensors, a mechano-chemical atomic force microscope (AFM) nanolithography on a metallic thin film (50 nm in thickness)/piezoelectric substrate covered by a spin-coated polymeric mask layer (50-60 nm in thickness) was implemented. The effective shape of cross-section of the before and after etching grooves have been determined by using the AFM tip deconvolution surface analysis, structure factor, and power spectral density analyses. The wet-etching process improved the shape and aspect ratio (height/width) of the grooves and also smoothed the surface within them. We have shown that the relaxed surface tension of the polymeric mask layer resulted in a down limitation in width and length of the lithographed nanofingers. The surface tension of the mask layer can be changed by altering the initial concentration of the polymer in the deposition process. As the surface tension reduced, the down limitation decreased. In fact, an extrapolation of the analyzed statistical data has indicated that by decreasing the surface tension from 39 to 10 nN/nm, the minimum obtainable width and length of the metallic nanofingers was changed from about 55 nm and 2 μm to 15 nm and 0.44 μm, respectively. Using the extrapolation’s results, we have shown that the future SAW sensors buildable by this nanolithography method possess a practical bound in their synchronous frequency (∼58 GHz), mass sensitivity (∼6125 MHz-mm²/ng), and the limit of mass resolution (∼4.88 × 10⁻¹⁰ ng/mm²).     

Oxidation of graphene on Ru(0 0 0 1) studied by scanning tunneling microscopy

The oxidation of graphene layer on Ru(0 0 0 1) has been investigated by means of scanning tunneling microscopy. Graphene overlayer can be formed by decomposing ethyne on Ru(0 0 0 1) at a temperature of about 1000 K. The lattice mismatch between the graphene overlayer and the substrate causes a moiré pattern with a superstructure in a periodicity of about 30 Å. The oxidation of graphene/Ru(0 0 0 1) was performed by exposure the sample to O₂ gas at 823 K. The results showed that, at the initial stage, the oxygen intercalation between the graphene and the Ru(0 0 0 1) substrate takes place at step edges, and extends on the lower steps. The oxygen intercalation decouples the graphene layer from the Ru(0 0 0 1) substrate. More oxygen intercalation yields wrinkled bumps on the graphene surface. The oxidation of graphene, or the removal of carbon atoms can be attributed to a process of the combination of the carbon atoms with atomic oxygen to form volatile reaction products. Finally, the Ru(0 0 0 1)-(2 × 1)O phase was observed after the graphene layer is fully removed by oxidation.     

Growth of Rh nanoclusters on TiO2(1 1 0): XPS and LEIS studies

Rhodium clusters were prepared by evaporation on a nearly stoichiometric TiO₂(1 1 0) surface. The growth of metal nanoparticles, as a function of rhodium coverage, could be followed by monitoring the Rh 3d_5/2 XP peak position and by low energy ion scattering spectroscopy (LEIS). The substrate temperature in the 160-300 K regime during evaporation significantly influences the cluster size, leading to smaller crystallites at low temperature. Annealing the surface results in the agglomeration of rhodium, which commenced at lower temperature for smaller clusters. At high temperatures (∼900 K) encapsulation of rhodium also occurred.     

Fabrication of Anodic Aluminum Oxide Templates with Small Interpore Distances

The influence of the electropolishing and anodization voltage on surface morphology has been carefully studied for fabrication of ordered anodic aluminum oxide （AAO） templates. In accordance with that in the anodization experiment, the size of small patterns on the foil surface formed from the electropolishing treatment increases with voltage. Using a combined method of small-voltage eleetropolishing and anodization, we have fabricated well ordered templates with much smaller interpore distances compared with that under normal-voltage fabrication conditions. The Ni nanowire arrays with two small diameters are eleetrodeposited through the above templates, exhibiting different magnetic properties. This also helps us to clarify the inner structure of this kind of templates.     

Nitric acid oxidation of Si (NAOS) method for low temperature fabrication of SiO2/Si and SiO2/SiC structures

We have developed low temperature formation methods of SiO₂/Si and SiO₂/SiC structures by use of nitric acid, i.e., nitric acid oxidation of Si (or SiC) (NAOS) methods. By use of the azeotropic NAOS method (i.e., immersion in 68 wt% HNO₃ aqueous solutions at 120 °C), an ultrathin (i.e., 1.3-1.4 nm) SiO₂ layer with a low leakage current density can be formed on Si. The leakage current density can be further decreased by post-metallization anneal (PMA) at 200 °C in hydrogen atmosphere, and consequently the leakage current density at the gate bias voltage of 1 V becomes 1/4-1/20 of that of an ultrathin (i.e., 1.5 nm) thermal oxide layer usually formed at temperatures between 800 and 900 °C. The low leakage current density is attributable to (i) low interface state density, (ii) low SiO₂ gap-state density, and (iii) high band discontinuity energy at the SiO₂/Si interface arising from the high atomic density of the NAOS SiO₂ layer.For the formation of a relatively thick (i.e., ≥10 nm) SiO₂ layer, we have developed the two-step NAOS method in which the initial and subsequent oxidation is performed by immersion in ∼40 wt% HNO₃ and azeotropic HNO₃ aqueous solutions, respectively. In this case, the SiO₂ formation rate does not depend on the Si surface orientation. Using the two-step NAOS method, a uniform thickness SiO₂ layer can be formed even on the rough surface of poly-crystalline Si thin films. The atomic density of the two-step NAOS SiO₂ layer is slightly higher than that for thermal oxide. When PMA at 250 °C in hydrogen is performed on the two-step NAOS SiO₂ layer, the current-voltage and capacitance-voltage characteristics become as good as those for thermal oxide formed at 900 °C.A relatively thick (i.e., ≥10 nm) SiO₂ layer can also be formed on SiC at 120 °C by use of the two-step NAOS method. With no treatment before the NAOS method, the leakage current density is very high, but by heat treatment at 400 °C in pure hydrogen, the leakage current density is decreased by approximately seven orders of magnitude. The hydrogen treatment greatly smoothens the SiC surface, and the subsequent NAOS method results in the formation of an atomically smooth SiO₂/SiC interface and a uniform thickness SiO₂.     

Large-area silica nanotubes with controllable geometry on silicon substrates

The synthesis of a highly uniform, large-scale nanoarrays consisting of silica nanotubes above embedded nanohole arrays in silicon substrates is demonstrated. In situ anodized aluminium oxide (AAO) thin film masks on Si substrates were employed, and the nanotubes were fabricated by Ar ion milling through the masks. The geometries of the nanoarrays, including pore diameter, interpore distance and the length of both nanopores and nanotubes could be controlled by the process parameters, which included that the outer pore diameter of silica tube was tuned from ∼80 nm to ∼135 nm while the inner tube diameter from ∼40 nm to ∼65 nm, the interpore distance of the nanotube arrays was from 100 nm to 180 nm and the length of silica tube changed from ∼90 nm to ∼250 nm. The presented nanostructure fabrication method has strong potential for application in intensity and frequency adjustable high luminescence efficiency optoelectronic devices.     

Characterization of MeWO4 (Me = Ba, Sr and Ca) nanocrystallines prepared by sonochemical method

Metal tungstates (MeWO₄, Me = Ba, Sr and Ca) were successfully prepared using the corresponding Me(NO₃)₂·2H₂O and Na₂WO₄·2H₂O in ethylene glycol by the 5 h sonochemical process. The tungstate phases with scheelite structure were detected with X-ray diffraction (XRD) and selected area electron diffraction (SAED). Their calculated lattice parameters are in accord with those of the JCPDS cards. Transmission electron microscopy (TEM) revealed the presence of nanoparticles composing the products. Their average sizes are 42.0 ± 10.4, 18.5 ± 5.1 and 13.1 ± 3.3 nm for Me = Ba, Sr and Ca, respectively. Interplanar spaces of the crystals were also characterized with high-resolution TEM (HRTEM). Their crystallographic planes are aligned in systematic array. Six different vibration wavenumbers were detected using Raman spectrometer and are specified as ν₁(A_g), ν₃(B_g), ν₃(E_g), ν₄(B_g), ν₂(A_g) and free rotation. Fourier transform infrared (FTIR) spectra provided the evidence of scheelite structure with W-O anti-symmetric stretching vibration of [WO₄]²⁻ tetrahedrons at 786-883 cm⁻¹. Photoluminescence emission of the products was detected over the range of 384-416 nm.     

InSb quantum dots and quantum rings on InAs-rich surface

We report a study of InSb nanoobjects (quantum dots and quantum rings) grown on InAs-rich surface by liquid phase epitaxy. Characterization of the sample surface was performed using atomic force microscopy (AFM). The bimodal formation of the uncapped InSb quantum dots (QDs) was observed for the growing on a binary InAs substrate. Uniform high-density (1 × 10¹⁰ cm⁻²) quantum dots with a height of 3 nm were obtained at T = 420-430 °C, whereas low-density (5 × 10⁸ cm⁻²) big quantum dots were 9 nm in height. As a buffer layer, lattice-matched InAsSb_0.12P_0.25 solid solution was deposed on InAs substrate using metal-organic vapour phase epitaxy. Deposition from the InSb melt on the buffer layer resulted in the formation of InSb nanoobjects with density as high as 3 × 10¹⁰ cm⁻².     

Structure and homoepitaxial growth of GaAs(6 3 1)

We have studied the surface atomic structure of GaAs(6 3 1), and the GaAs growth by molecular beam epitaxy (MBE) on this plane. After the oxide desorption process at 585 °C reflection high-energy electron diffraction (RHEED) showed along the [−1 2 0] direction a 2× surface reconstruction for GaAs(6 3 1)A, and a 1× pattern was observed for GaAs(6 3 1)B. By annealing the substrates for 60 min, we observed that on the A surface appeared small hilly-like features, while on GaAs(6 3 1)B surface pits were formed. For GaAs(6 3 1)A, 500 nm-thick GaAs layers were grown at 585 °C. The atomic force microscopy (AFM) images at the end of growth showed the self-formation of nanoscale structures with a pyramidal shape enlarged along the [5−9−3] direction. Transversal views of the bulk-truncated GaAs(6 3 1) surface model showed arrays of atomic grooves along this direction, which could influence the formation of the pyramidal structures.     

Preparation and characterization of C54 TiSi2 nanoislands on Si (1 1 1) by laser deposition of TiO2

We present the preparation of C54 TiSi₂ nanoislands on Si (1 1 1) with a method of the pulsed laser deposition of titanium oxide thin films. The TiO₂ thin films with nominal thicknesses of 1 nm on Si (1 1 1) were annealed at 850 °C for about 4 h in situ. The X-ray diffraction patterns and the X-ray photoelectron spectra indicate that the nanoislands are in C54 TiSi₂ phase. The characterization using a scanning tunneling microscope shows that the nanoislands with triangular, polygonal and rod-like shapes on Si (1 1 1) exhibit the Volmer-Weber growth mode. The sizes of the polygonal islands distribute in two separated ranges. For the small islands, they have a narrow lateral size distribution centered at 4 nm and a height range in 0.6-3.6 nm, while for the large islands, their lateral sizes are in the range of 12-40 nm and the heights in the range of 4-9 nm. The sizes of the well-shaped triangular islands are intermediate with the lateral sizes in range of 5-20 nm and the heights of 2-3.5 nm. The rod-like islands are about 50-200 nm in length, 5 nm in height and about 15-20 nm in width. The origination of the various shapes of the nanoislands is attributed to the symmetry of Si (1 1 1) substrate and the lattice mismatch between the C54 TiSi₂ and the Si (1 1 1) surface.     

Position-controlled synthesis of single-walled carbon nanotubes on a transparent substrate by laser-induced chemical vapor deposition

The synthesis of single-walled carbon nanotubes (SWCNTs) on a transparent substrate with multiple-catalyst layer (Fe/Al/Cr: 0.5/15/500 nm) using laser-induced chemical vapor deposition is reported. Ethylene (C₂H₄) mixed with hydrogen (H₂) and a continuous wave Nd:YVO₄ laser (532 nm) were used as the precursor gas and the irradiation source, respectively. It was found that the density and quality of the SWCNT dots varied sensitively to laser irradiance and chamber pressure. From subsequent micro-Raman analyses at different excitation sources (488, 514, 633, and 785 nm), the diameters of the SWCNTs were estimated to be within the range of 0.8-2 nm and that the SWCNT dots were composed of both semiconducting and metallic SWCNTs. It is demonstrated that an array of SWCNT dots can be fabricated at precisely controlled positions of a transparent substrate at room temperature with no need of catalysis patterning.     

Laser synthesis of semiconductor nanostructures with narrow band gap

Semiconductor nanostructures with narrow band gap were synthesized by means of laser chemical vapor deposition (LCVD) of elements from iron carbonyl vapors [Fe(CO)₅] under the action of Ar⁺ laser radiation (λ_L = 488 nm) on the Si substrate surface. The temperature dependence of the specific conductivity of these nanostructures in the form of thin films demonstrated typical semiconductor tendency and gave the possibility to calculate the band gap for intrinsic conductivity (E_g) and the band gap assigned for impurities (E_i), which were depended upon film thickness and applied electrical field. Analysis of deposited films with scanning electron microscopy (SEM) and atomic force microscopy (AFM) demonstrated their cluster structure with average size not more than 100 nm. Semiconductor properties of deposited nanostructures were stipulated with iron oxides in different oxidized phases according to X-ray photoelectron spectroscopy (XPS) analysis.These deposited nanostructures were irradiated with Q-switched YAG laser (λ_L = 1064 nm) at power density about 6 × 10⁷ W/cm². This irradiation resulted in the crystallization process of deposited films on the Si substrate surface. The crystallization process resulted in the synthesis of iron carbide-silicide (FeSi_2−xC_x) layer with semiconductor properties too. The width of the band gap E_g of the synthesized layer of iron carbide-silicide was less than for deposited films based on iron oxides Fe₂O_3−x (0 ≤ x ≤ 1).     

Nanostructures on SiC surface created by laser microablation

Silicon carbide (SiC), as it is well-known, is inaccessible to usual methods of technological processing. Consequently, it is important to search for alternative technologies of processing SiC, including laser processing, and to study the accompanying physical processes. The work deals with the investigation of pulsed laser radiation influence on the surface of 6H-SiC crystal. The calculated temperature profile of SiC under laser irradiation is shown. Structural changes in surface and near-surface layers of SiC were studied by atomic force microscopy images, photoluminescence, Raman spectra and field emission current-voltage characteristics of initial and irradiated surfaces. It is shown that the cone-shaped nanostructures with typical dimension of 100-200 nm height and 5-10 nm width at the edge are formed on SiC surface under nitrogen laser exposure (λ = 0.337 μm, t_p = 7 ns, E_p = 1.5 mJ). The average values of threshold energy density 〈W_thn〉 at which formation of nanostructures starts on the 0 0 0 1 and surfaces of n-type 6H-SiC(N), nitrogen concentration n_N ≅ 2 × 10¹⁸ cm⁻³, are determined to be 3.5 J/cm² and 3.0 J/cm², respectively. The field emission appeared only after laser irradiation of the surface at threshold voltage of 1000 V at currents from 0.7 μA to 0.7 mA. The main role of the thermogradient effect in the processes of mass transfer in prior to ablation stages of nanostructure formation under UV laser irradiation (LI) was determined. We ascertained that the residual tensile stresses appear on SiC surface as a result of laser microablation. The nanostructures obtained could be applied in the field of sensor and emitting extreme electronic devices.     

Electrochemical formation of porous superlattices on n-type (1 0 0) InP

The present work deals with the electrochemical formation of superlattice structures on n-type (1 0 0) InP in HCl solutions. The superlattices consist of a stack of two layers with alternating high and low porosity on n-type material obtained by changing the anodizing current or the potential periodically in HCl solutions. The superlattice structures were characterized by scanning electron microscopy. The pore morphology and structure depend strongly on the electrochemical conditions. For anodization with low currents (e.g., 1 or 10 mA) or at low potentials (e.g., 1.5 V_Ag/AgCl), a porous layer with a facet-like structure was formed. For higher currents or potentials, such as 50 or 100 mA or 3 V_Ag/AgCl, respectively, a tree-like structure with random and/or tangled branches was observed. Finally, samples anodized at 5 V_Ag/AgCl, show a porous layer with a regular array of straight pores. The morphology and structure of the stacks of the porous layers can be controlled in the nanometer range, depending on the electrochemical conditions.     

Replication of mold for UV-nanoimprint lithography using AAO membrane

A simple and highly effective method to the replication of soft mold based on the anodic aluminum oxide (AAO) membrane was developed. The soft mold with nanopillar arrays was composed of the toluene diluted PDMS layer supported by the soft PDMS. A water contact angle as high as 114° was achieved. The hexagonally well-order arrays of holes of nanometer dimensions, ∼100 nm pore diameter and 125 nm center-to-center pore, could be gained over large areas by UV-nanoimprint lithography (UV-NIL) with the replicated soft PDMS mold. It is expected that the developed soft mold would find applications in light emitting diodes devices.     

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

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

Laser synthesis of nanostructures based on transition metal oxides

Nanostructures based on iron oxides in the form of thin films were synthesized while laser chemical vapor deposition (LCVD) of elements from iron carbonyl vapors (Fe(CO)₅) under the action of Ar⁺ laser radiation (λ_L = 488 nm) on the Si substrate surface with power density about 10² W/cm² and vapor pressure 666 Pa. Analysis of surface morphology and relief of the deposited films was carried out with scanning electron microscopy (SEM) and atomic force microscopy (AFM). This analysis demonstrated their cluster structure with average size no more than 100 nm. It was found out that the thicker the deposited film, the larger sizes of clusters with more oxides of higher oxidized phases were formed. The film thickness (d) was 10 and 28 nm. The deposited films exhibited semiconductor properties in the range 170-340 K which were stipulated by oxide content with different oxidized phases. The width of the band gap E_g depends on oxide content in the deposited film and was varied in the range 0.30-0.64 eV at an electrical field of 1.6 × 10³ V/m. The band gap E_g was varied in the range 0.46-0.58 eV at an electrical field of 45 V/m. The band gap which is stipulated by impurities in iron oxides E_i was varied in the range 0.009-0.026 eV at an electrical field of 1.6 × 10³ V/m and was varied in the range 0-0.16 eV at an electrical field 45 V/m. These narrow band gap semiconductor thin films displayed of the quantum dimensional effect.     

A simple approach for synthesis of TiO2 nanotubes with through‐hole morphology

The present work reports a simple approach for fabrication of self‐standing titania (TiO₂) nanotube membranes with through‐hole morphology. The method is hydrofluoric acid free and the pore opening of TiO₂ nanotubes is performed by electrochemical thinning of the oxide barrier layer. A reduction of anodization voltage was applied at the end of the anodization process to cause a successful removal of the remaining barrier layer from the TiO₂ nanotubes during their detachment from the underlying titanium substrate. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)