Structural Characteristics of p-Type Porous Silicon and their Relation to the Nucleation and Growth of Pores

The influence of the anodization time on some structural characteristics (dissolved mass, maximum porous layer thickness, porosity, crystallite size, etc.) of p-type porous silicon has been investigated. It is shown that chemical dissolution of the porous layer during the anodization must be taken into account in order to correct some of the experimental data. Measurements of the anode potential have allowed to distinguish an early stage of the porous layer formation due to nucleation of pores. Equations based on pore nucleation and growth processes explain well the evolution of the maximum layer thickness with anodization time.     

Cathodoluminescence from Implanted and Anodized Polycrystalline Silicon Films

Luminescence emission of LPCVD polycrystalline silicon films has been studied by cathodoluminescence (CL) in the scanning electron microscope. As-deposited films show visible luminescence with dominant blue band. The relative intensity of blue emission is enhanced by implantation and by slight anodization treatments. Our investigations are consistent with previous PL results and indicate that the origin of blue emission is related to quantum confinement effects. On the other hand, the effect of annealing in these samples is a reduction of the CL signal that could be related to the increase of the nanocrystals size.     

未抛光多晶硅表面阳极氧化后的可见光发射

用制备发光多孔硅的常规电化学方法。在未抛光多晶硅表面备了均匀发射可见光的样品。光致发光实验表明：多晶硅表面上的样品可以产生多孔硅特征光致发光。用扫描电镜对此样品及常规多孔硅的微结构做了研究，结果表明：两种样品的微结构有很大差别，多晶硅表面上的样品只有两层结构，即表面层和多晶硅衬底，而没有形成多孔层。     

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     

Current improvement of porous silicon photovoltaic devices by using double layer porous silicon structure: applicable in porous silicon solar cells

The photoluminescence (PL) phenomena of porous silicon (PS) samples with different etching times were examined to find out a relationship between PL emission energy (experimental value of PS band gap energy) and the etching time for fabrication of double (two) layer porous silicon sample on one silicon substrate. The dependence of PL Peak energy with etching time was discussed. A double layer PS structure was formed by using two electrochemical reactions with different etching times of 20 and 10 min, respectively. The photovoltaic (PV) properties of mono layer and double layer porous silicon PV devices were examined and compared. The main result is the enhanced short-circuit current (I_sc) of double layer PS structure compared to monolayer ones.     

Effect of nonaqueous anodic oxidation on the intensity of photoluminescence of porous silicon

Porous silicon (PS) was anodized for short periods in 0.02m KNO₃–ethylene glycol electrolyte to improve the maximum intensity of its photoluminescence (PL) by changing surface –Si–H bonds to –Si–OH or –Si–O-related compounds. A PS sample prepared in 1:1 (49% HF:99.5% EtOH) electrolyte gave 15-fold PL intensity as well as stabilized luminescence with 5min anodization. Prolonged anodization, however, peeled off the nano-ordered silicon particles and resulted in a decrease in PL intensity. The PL intensity of the PS sample prepared in 1:2 electrolyte decreased with 1min anodization but increased with 30s anodization. During anodization, the nano-ordered silicon particles reacted with water, an impurity in ethylene glycol, to give Si–OH and Si–O-related compounds. Ethylene glycol proved to be the best anodization solvent for nano-ordered silicon particles because of its high resistivity, high viscosity, and good electrochemical stability. However, ethylene glycol had to be removed completely from the PS surface by rinsing with pure water, because polyhydroxy alcohols such as ethylene glycol behaved as quenchers for excited electrons formed in Si–OH-related compounds on the nano-ordered silicon as a result of illumination.     

Optical properties of porous silicon coated with ultrathin gold film by RF-magnetron sputtering

Optical properties of porous silicon (PS) with ultrathin gold (Au) coatings were investigated. The gold films were deposited by using an RF-sputter-deposition technique on PS prepared by electrochemical anodization of P-type (1 0 0) Si. Photoluminescence (PL) spectroscopy and UV/VIS photospectroscopy analyses were performed to investigate the PL and optical transmittance properties of the Au-coated PS samples. Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron emission spectroscopy (XPS) analyses were also performed to investigate the origin of the PL enhancement by Au deposition. The PL intensity of PS is 6.4% increased by depositing 5.3 nm Au film using an RF-sputtering technique, but it is decreased 28.4% by postannealing. FTIR, spectrophotometry and XPS analysis results suggest that the PL enhancement by Au film deposition is attributed to the oxidation inhibiting effect of the Au film. However, it is not desirable to deposit an Au film thicker than 5.3 nm on PS as the PL intensity is decreased rather than increased owing to a significant decrease in the transmittance. Deterioration in the PL of the Au-coated PS by postannealing is ascribed to oxidation of the PS layer occurring at the high annealing temperature in spite of the Au passivation.     

Correlation of Photoluminescence and Bandgap Energies with Nanocrystal Sizes in Porous Silicon

We have measured the crystallite sizes, the bandgap energies, and the photoluminescence (PL) energies in porous silicon (PSi) samples having a wide range of porosities and kept in different ambient conditions. The dependence of the bandgap energy on the crystallite size agrees with theory. For PSi samples exposed to air and containing crystallites smaller than 5 nm, the PL intensity increases by several orders of magnitude and the PL peak energy shifts from the near infrared to the red, in agreement with the quantum confinement model for the PL. For crystallites smaller than 3 nm, there is a Stokes shift between the excitonic bandgap and PL energies, which increases to several hundreds of meV for sizes 2 nm, indicating that, in PSi exposed to air, the PL is not due to free excitons. Before exposure to air, very high porosity PSi samples emit at shorter wavelengths than after exposure to air, suggesting that the Stokes shift depends on the surface chemistry.     

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

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

Ba-doped ZnO nanostructure: X-ray line analysis and optical properties in visible and low frequency infrared

In this work, X-ray diffraction analysis and optical properties of pure and Ba-doped ZnO nanoparticles prepared by the precipitation method were investigated. X-ray analysis was employed to evaluate the micro structural parameters of ZnO nanoparticles in terms of crystallite sizes and lattice strain by the Williamson–Hall method. The average crystallite size of Ba-doped ZnO nanoparticles estimated by the Williamson–Hall method varied as the doping concentration increased. The effect of Ba doping on the photoluminescence (PL) emission spectrum of ZnO was also investigated. The temperature dependence of the PL emissions was also studied, and it was found that at low temperature, the samples show stronger emissions than those at room temperature in both UV and visible regions. As a final point, the FT–IR reflection spectrum along with Kramers–Kronig (K–K) method and classical dispersion theory was applied to obtain optical properties of the samples at low frequency infrared regime.     

Photoluminescence properties of porous silicon layers prepared by electrochemical etching in extremely dilute HF solutions

Dilute HF solutions with concentrations down to 0.03% have been used to obtain luminescent porous silicon (PSi) layers on p-type Si wafers. The experimental results show that with a constant etching time of 30 min, PSi layers with sufficient luminescence efficiencies can be formed for HF concentrations as low as 0.1%. Because of a significantly lowered critical current density, only very low etching current densities of  ≤0.1 mA cm⁻² can result in the formation of luminescent PSi samples in 0.1% HF solutions. A notable result is that these low etching current densities cannot be used to form luminescent PSi layers in concentrated ( ≥1%) HF solutions. The behavior of PL intensity as a function of etching current density has been analyzed over a wide range of HF concentration. The PL intensity is determined by the ratio of the etching current density to the critical current density, suggesting that the presence of silicon oxides plays an important role in the formation of luminescent Si nanostructures in PSi layers.     

Electro-, Photo- and Scanning Tunneling—Luminescence Studies of Efficient Light-Emitting Porous Silicon

Porous silicon films as used in efficient blue-green electroluminescent devices (internal efficiency about 0.1%) were studied by scanning tunneling microscopy light emission spectroscopy (STMLES) as well as photoluminescence (PL) and electroluminescence (EL) spectroscopy. Areas of the n-type porous Si surfaces with small particles of about 5 nm dimensions gave STMLE, but areas with larger structures gave no emission. Clear STMLE spectra gave a peak at 630 nm, quite different from the EL peak at 500 nm. Whereas the PL peak at 700 nm was consistent with the STM indication of quantised entities, the EL seemed more readily explicable in terms of defects at the metal contact barrier.     

Porous silicon microcavities: synthesis, characterization, and application to photonic barcode devices

ABSTRACT: We have recently developed a new type of porous silicon we name as porous silicon colloids. They consist of almost perfect spherical silicon nanoparticles with a very smooth surface, able to scatter (and also trap) light very efficiently in a large-span frequency range. Porous silicon colloids have unique properties because of the following: (a) they behave as optical microcavities with a high refractive index, and (b) the intrinsic photoluminescence (PL) emission is coupled to the optical modes of the microcavity resulting in a unique luminescence spectrum profile. The PL spectrum constitutes an optical fingerprint identifying each particle, with application for biosensing.In this paper, we review the synthesis of silicon colloids for developing porous nanoparticles. We also report on the optical properties with special emphasis in the PL emission of porous silicon microcavities. Finally, we present the photonic barcode concept.     

A study on the formation of titania nanopillars during porous anodic alumina through-mask anodization of Ti substrates

The formation of anodic titania during porous anodic alumina (PAA) through-mask anodization has been analysed for varying anodization conditions on mechanically polished bulk Ti surfaces. Titania nanopillars were formed through the porous masks in both oxalic and phosphoric acid electrolytes. For applied potentials above 40 V the titania formed along narrow channels through the alumina pore bottoms resulting in root-like attachments of the titania pillars to the Ti substrate. We further demonstrated that high-field anodization can be used for PAA through-mask anodization. The formation of titania changed with increased current density which resulted in more efficient oxide growth through the alumina pores. When the Al/Ti samples were immersed in the electrolyte without exclusively exposing the Al surface to the electrolyte the titania formed solely on top of the alumina pore bottoms which resulted in that the titania structures were detached from the Ti substrates during selective removal of the PAA templates.     

Sensitivity of Porous Silicon Photoluminescence to Low Concentrations of CH4 and CO

In this paper we report the sensitivity of porous silicon photoluminescence (PL) to diluted mixtures of methane and carbon monoxide in synthetic air. We also investigate the separate effect of synthetic air, purified nitrogen and relative humidity on both photoluminescence and conductance (G). Porous silicon samples have been prepared from n-type silicon substrates. We find that PL intensity and G decrease in synthetic air with respect to their values in N₂. Presence of carbon monoxide reduces the PL intensity while methane provokes the opposite behaviour. The dependence of the PL spectra on methane and carbon monoxide concentrations has been investigated. The observed effects can be related to gas induced modifications in porous surface and suggest that porous silicon can be employed in gas sensor technology.     

In3+离子在多孔SiO2干凝胶中的发光

采用常规的Sol-gel工艺合成了In^3 掺杂的多孔SiO2干凝胶，In^3 离子作为间隙离子存在于SiO2网络中，展示了一种新颖的发光现象，改变了多孔SiO2干凝胶的发射光谱。这种掺杂的多孔SiO2干凝胶的激发和发射光谱均由2个带组成，短波长的发光峰在440nm(λex=380nm），其相对荧光强度约是未掺杂的多孔SiO2干凝胶的4倍；长波长的发光峰（In^3 离子在多孔SiO2干凝胶的特征发射）在600nm(λex=476nm），其相对荧光强度约是In^3 掺杂ZnS纳米晶的10倍。由此可以看出：掺杂的多孔SiO2干凝胶是一种高效的发光材料。     

Study of Porous Silicon Prepared Using Metal-Induced Etching (MIE): a Comparison with Laser-Induced Etching (LIE)

Porous silicon (p-Si), prepared by two routes (metal induced etching (MIE) and laser induced etching (LIE)) have been studied by comparing the observed surface morphologies using SEM. A uniformly distributed smaller (submicron sized) pores are formed when MIE technique is used because the pore formation is driven by uniformly distributed metal (silver in present case) nanoparticles, deposited prior to the porosification step. Whereas in p-Si, prepared by LIE technique, wider pores with some variation in pore size as compared to MIE technique is observed because a laser having gaussian profile of intensity is used for porosification. Uniformly distribute well-aligned Si nanowires are observed in samples prepared by MIE method as seen using cross-sectional SEM imaging. A single photoluminescence (PL) peak at 1.96 eV corresponding to red emission at room temperature is observed which reveals that the Si nanowires, present in p-Si prepared by MIE, show quantum confinement effect. The single PL peak confirms the presence of uniform sized nanowires in MIE samples. These vertically aligned Si nanowires can be used for field emission application.     

Porous Co/Co–Ni–Pt nanostructures prepared by galvanic replacement towards methanol electro-oxidation

The nanostructured Co/Co–Ni–Pt catalyst were synthesized by electrodeposition process and galvanic replacement reaction. The alloy prepared on a copper electrode (Cu/Co/Co–Ni–Zn) was dipped in platinum containing alkaline solution to produce a porous Cu/Co/Co–Ni–Pt catalyst. The catalyst was characterized by energy dispersive X-ray and scanning electron microscopy techniques and its electrocatalytic properties were evaluated using cyclic voltammetry, electrochemical impedance spectroscopy and chronoamperometry techniques. The results showed that the Co/Co–Ni–Pt coatings are porous, and composed of discrete Pt nanoparticles with the crystallite size of about 66 nm. It was shown from cyclic voltammograms in alkaline solutions that the oxidation current of methanol on the nanostructured Cu/Co/Co–Ni–Pt electrode was much higher than that on flat platinum. Electrochemical impedance spectra on the Co/Co–Ni–Pt electrode reveal that the charge transfer resistance decreases with the increase of anodic potentials. All results show that the Co/Co–Ni–Pt catalysts can be potential anode catalysts for the direct methanol fuel cell.     

Synthesis and Photoluminescence Properties of Porous Silicon Nanowire Arrays

Herein, we prepare vertical and single crystalline porous silicon nanowires (SiNWs) via a two-step metal-assisted electroless etching method. The porosity of the nanowires is restricted by etchant concentration, etching time and doping lever of the silicon wafer. The diffusion of silver ions could lead to the nucleation of silver nanoparticles on the nanowires and open new etching ways. Like porous silicon (PS), these porous nanowires also show excellent photoluminescence (PL) properties. The PL intensity increases with porosity, with an enhancement of about 100 times observed in our condition experiments. A “red-shift” of the PL peak is also found. Further studies prove that the PL spectrum should be decomposed into two elementary PL bands. The peak at 850 nm is the emission of the localized excitation in the nanoporous structure, while the 750-nm peak should be attributed to the surface-oxidized nanostructure. It could be confirmed from the Fourier transform infrared spectroscopy analyses. These porous SiNW arrays may be useful as the nanoscale optoelectronic devices.     

Fabrication of plasmonic Au/TiO2 nanotube arrays with enhanced photoelectrocatalytic activities

Uniformly dispersed Au nanoparticles (NPs) deposited on the surface of highly ordered TiO₂ nanotube arrays (Au/TiO₂ NTs) were synthesized through a two-step process including anodization method and microwave-assisted chemical reduction route. The investigation indicated that Au NPs grew uniformly on the walls of TiO₂ NTs. Au/TiO₂ NTs exhibited excellent visible light absorption due to the LSPR effect of Au NPs. Au/TiO₂ NTs exhibited much higher photocurrent density and the photoconversion efficiency of Au decorated TiO₂ NTs was about 2.05 times greater than that of bare TiO₂ NTs. Besides, the PL intensity of Au/TiO₂ NTs was much lower than that of TiO₂ NTs, revealing a decrease in charge carrier recombination. The prepared Au/TiO₂ NTs exhibited superior photoelectrocatalytic activity and stability in the degradation of MB under simulated solar light irradiation. The synergy effect between nanotubular structures of TiO₂ and uniformly dispersed Au nanoparticles, as well as the small bias potential and strong interaction between Au and TiO₂, facilitated the Au plasmon-induced charge separation and transfer, which lead to highly efficient and stable photoelectrocatalytic activity.