The integration of nanoscale porous silicon light emitters: materials science, properties, and integration with electronic circuitry

The stability, efficiency, speed, and spectral range of light-emitting devices (LEDs) made of nanoscale porous silicon is improving. The first part of this paper discusses the preparation and properties of nanoscale silicon, with emphasis on porous silicon. In the second part, the properties of LEDs made of porous silicon are reviewed. In the third part, the integration of PSi LEDs with silicon microelectronic circuits is discussed. The paper ends with a short discussion of the prospects for realistic optoelectronic devices.     

Surface texturing of Si, porous Si and TiO2 by laser ablation

Excimer laser ablation at 308 nm has been used to texture the surfaces of a variety of materials of interest for optoelectronic and biotechnological applications. Using a range of pre- and post-processing methods, we are able to produce nano-, micro- and meso-scale features over large areas rapidly in materials such as crystalline Si, porous silicon and TiO₂. Texturing of porous silicon leads to the growth of crystalline dendritic structures, which distinguishes them dramatically from the conical pillars formed from crystalline silicon. Regular arrays of Si microdots are formed by irradiating a Si surface pre-covered with a Cr thin film grating. Nano-crystalline porous TiO₂ films are easily ablated or compacted with laser irradiation. However, at low enough laser fluence, surface roughening without complete loss of porosity is possible.     

Structure and magneto-optical properties of “porous silicon-cobalt” granular nanocomposites

The structural and magneto-optical properties of “porous silicon-cobalt” nanocomposites prepared through electrochemical deposition on silicon substrates of different porosities are investigated. It is revealed that, under galvanostatic conditions, cobalt micrograins are formed only in a surface layer of porous silicon. The greater the pores in silicon, the larger the mean size of the ferromagnetic micrograins. The nanocomposites thus fabricated possess ferromagnetic properties and, at specified compositions, are characterized by anomalously large magnitudes of the equatorial or transverse magneto-optical Kerr effect (TMOKE). The magneto-optical properties of the nanocomposites are simulated in the Bruggeman effective-medium approximation. It is shown that the anomalous negative transverse magneto-optical Kerr effect is associated with the oxidized state of porous silicon in the vicinity of the ferromagnetic metal micrograins.     

Annealing and amorphous silicon passivation of porous silicon with blue light emission

The photoluminescence (PL) of the annealed and amorphous silicon passivated porous silicon with blue emission has been investigated. The N-type and P-type porous silicon fabricated by electrochemical etching was annealed in the temperature range of 700-900 °C, and was coated with amorphous silicon formed in a plasma-enhanced chemical vapor deposition (PECVD) process. After annealing, the variation of PL intensity of N-type porous silicon was different from that of P-type porous silicon, depending on their structure. It was also found that during annealing at 900 °C, the coated amorphous silicon crystallized into polycrystalline silicon, which passivated the irradiative centers on the surface of porous silicon so as to increase the intensity of the blue emission.     

The effects of porous silicon on the crystalline properties of ZnO thin films

In the present work, ZnO was deposited on porous silicon substrates by sol-gel spin coating and rf magnetron sputtering. The porous silicon (PS) substrates were formed by electrochemical anodization on p-type (1 0 0) silicon wafer, and the starting material for ZnO was Zinc acetate dehydrate. Raman spectroscopy revealed the good quality of the porous silicon substrate. XRD analysis showed that highly (0 0 2) oriented ZnO thin films were formed. SEM, AFM and optical microscope have been used to understand the effects of the substrate on crystalline properties of the samples. The results indicated that the porous silicon substrate is beneficial to improve the crystalline quality in lattice mismatch heteroepitaxy due to its sponge-like structure.     

Characterization of thermal, optical and carrier transport properties of porous silicon using the photoacoustic technique

In this work, the porous silicon layer was prepared by the electrochemical anodization etching process on n-type and p-type silicon wafers. The formation of the porous layer has been identified by photoluminescence and SEM measurements. The optical absorption, energy gap, carrier transport and thermal properties of n-type and p-type porous silicon layers were investigated by analyzing the experimental data from photoacoustic measurements. The values of thermal diffusivity, energy gap and carrier transport properties have been found to be porosity-dependent. The energy band gap of n-type and p-type porous silicon layers was higher than the energy band gap obtained for silicon substrate (1.11 eV). In the range of porosity (50-76%) of the studies, our results found that the optical band-gap energy of p-type porous silicon (1.80-2.00 eV) was higher than that of the n-type porous silicon layer (1.70-1.86 eV). The thermal diffusivity value of the n-type porous layer was found to be higher than that of the p-type and both were observed to increase linearly with increasing layer porosity.     

A Method for Preparation of Ordered Porous Silicon Based on a 2D SiO_2 Template

A new method for fabricating ordered porous silicon is reported.A two-dimensional silica nanosphere array is used as a template with a hydrofluoric acid-hydrogen peroxide solution for etching the nanospheres.The initial diameter and distribution of the holes in the resulting porous silicon layer are determined by the size and distribution of the silica nanospheres.The corrosion time can be used to control the depths of the holes.It is found that the presence of a SiO_2 layer,formed by the oxidation of the rough internal surface of the hole,is the primary reason allowing the corrosion to proceed.Ultraviolet reflection and thermal conductivity measurements show that the diameter and distribution of the holes have a great influence on properties of the porous silicon.     

The porous silicon morphology effect on the growth of electrodeposited FeNi alloy

In this work, we report on cathodic deposition of FeNi thin films into porous silicon (PS) formed on n-type Si. Macroporous and mesoporous silicon layers were formed at constant potential or current density. The electrodeposited thin films were characterized by Energy Dispersive Spectroscopy (EDS) and X-Ray Diffraction (XRD). The magnetic properties of the FeNi layers were investigated by hysteresis loops measurements. SEM images of the FeNi films indicate that tubular and granular forms were obtained depending on the porous silicon surface morphology. Moreover, the FeNi films compositions are found to depend on the porous silicon microstructure. Finally, the XRD spectra of the deposited films show the presence of FeNi (111) and FeNi (220) peaks. The FeNi (111) peak has been shown for all polarization potentials, in agreement with results reported in the literature.     

Influence of Iodine-Containing Solutions on the Condition of a Porous Silicon Surface and Its Photoluminescent Properties

The influence of surface treatment of porous silicon in iodine-containing solutions on its photoluminescent properties has been investigated. The porous silicon samples were prepared by anodizing in HF-based electrolytes and placed in fluoride-hydrogen solutions with the addition of iodine immediately after their formation. The surface condition was controlled by IR Fourier spectroscopy methods in the 400–4000-cm^–1 range. It has been established that the result of the porous silicon treatment in iodine-containing solutions is a decrease in the intensity of Si–H _x -bonds without the appearance of additional vibrations in the range under investigation. At the same time, such a treatment substantially affects the spectrum and intensity of porous silicon photoluminescence and increases its stability in subsequent storage. The possible reasons for the revealed phenomena are discussed.     

Oxidation of the porous silicon surface under the action of a pulsed ionic beam: XPS and XANES studies

The changes in the electronic structure and phase composition of porous silicon under action of pulsed ionic beams have been studied by X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge spectroscopy (XANES) using synchrotron radiation. The Si 2p and O 1s core photoemission spectra for different photoelectron collection angles, valence band photoemission spectra, and X-ray absorption near-edge fine structure spectrain the region of Si L _2,3 edges of the initial and irradiated samples have been analyzed. It has been found that, as a result of the irradiation, a thin oxide film consisting predominantly of higher oxide SiO₂ is formed on the porous silicon surface, which increases the energy gap of the silicon oxide. Such film exhibits passivation properties preventing the degradation of the composition and properties of porous silicon in contact with the environment.     

Low refractive index contrast porous silicon omnidirectional reflectors

We report on the fabrication and characterization of a porous silicon omnidirectional reflector formed by periodic substructures stacked together. For these substructures, a low refractive index contrast has been used, resulting in substructures without omnidirectional reflectivity band. The use of a low refractive index contrast involves the reduction of the requirements to obtain omnidirectional reflectors. We demonstrate the existence of an omnidirectional reflectivity range with a high gap-to-midgap ratio by means of reflectivity spectra measurements for a range of incidence angles. The results are in good agreement with a theoretical model of the reflector. The fabricated structure is the first reported porous silicon reflector suitable for 1.55 μm applications.     

Electrochemical deposition of cerium on porous silicon to improve photoluminescence properties

In this work, we present results for Cerium (Ce) doping effects on photoluminescence (PL) properties of porous silicon (PS). Cerium was deposited using electrochemical deposition on porous silicon prepared by electrochemical anodization of P-type (100) Si. From the photoluminescence spectroscopy, it was shown that porous silicon treated with cerium can lead to an increase of photoluminescence when they are irradiated by light compared to the porous silicon layer without cerium. In order to understand the contribution of cerium to the enhanced photoluminescence, energy dispersive X-ray (EDX) spectroscopy, Fourier transmission infrared spectroscopy (FTIR), X-ray diffraction (XRD) and atomic force microscopy (AFM) were performed, and it was shown that the improved photoluminescence may be attributed to the change of Si–H bonds into Si–O–Ce bonds and to a newly formed PS layer during electrochemical Ce coating.     

Study on the thermal isolation properties of porous silicon photonic crystal

The thermal isolation properties of porous silicon photonic crystal structures have been designed and discussed theoretically. Excellent thermal isolation properties can be obtained on such a porous silicon photonic crystal, even better than that of porous silicon with high porosity. Due to the excellent thermal isolation properties of the porous silicon photonic crystal structures, they can be used as the thermal isolation substrates in infrared detectors     

Application of stain-etched porous silicon in light emitting diodes and solar cells

Porous silicon/c-Si heterostructures have been formed by the method of stain etching.The properties of light emitting diodes (LED) and solar cells have been studied. The transport mechanism of the diode has been investigated from the current–voltage characteristics measured at different temperatures (296–380 K). A model based on multi-step tunneling of carriers at reverse and low forward bias (<1 V) and on field tunneling across a narrow barrier at higher forward bias (>1.5 V) is proposed for the LED. In the case of the solar cells the porous silicon is formed in between the fingers of the front grid contact. Application of porous silicon in solar cells results in an increase of the short-circuit current and efficiency of the cells by about 30%.     

Photoluminescence studies of porous silicon microcavities

Narrow photoluminescence peaks with a full-width at half-maximum of 14–20 nm are obtained from porous silicon microcavities (PSM) fabricated by the electrochemical etching of a Si multilayer grown by molecular beam epitaxy. The microcavity structure contains an active porous silicon layer sandwiched between two distributed porous silicon Bragg reflectors; the latter were fabricated by etching a Si multilayer doped alternatively with high and low boron concentrations. The structural and optical properties of the PSMs are characterised by scanning electron microscopy and photoluminescence (PL). The wavelength of the narrow PL peaks could be tuned in the range of 700–810 nm by altering the optical constants.     

Anodic oxidation of porous silicon bilayers

This paper focuses on the study of the effect of anodic oxidation in porous silicon bilayers composed of two porous layers of different porosities. The order of the two types of layers has been alternated, and the thicknesses and refractive indices have been optically characterized by Fourier transform infrared spectroscopy. The results show that the refractive index of anodic oxidized porous silicon is reduced significantly with respect to just formed porous silicon. It is also observed that the quality of the oxidation is related to the porosity of the inner porous layer of the silicon bilayer structure. This effect is interpreted in terms of quantum size effects.     

Surface analysis of thermally annealed porous silicon

Quasi-monocrystalline porous silicon (QMPS) has high potential for photovoltaic application for its enhanced optical absorption compared to bulk silicon in the visible range of solar spectrum. In this study, QMPS was formed from low porosity (∼20-30%) porous silicon (PS) produced by electrochemical anodization, and thermal annealing in the temperature range 1050-1100 °C under pure hydrogen ambient for a duration of 30 min. We analyzed the material surface by grazing incidence X-ray diffraction (GIXRD), field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM) and dynamic secondary ion mass spectroscopy (SIMS) study. The crystallinity was confirmed by GIXRD while FESEM studies revealed that the surface layer is pore free with voids embedded inside the body. AFM studies indicated relatively smooth and uniform surface and the dynamic SIMS study showed the depth profiles of impurities present in the material.     

Peculiarities of the reflection spectra of PECVD nanocrystalline porous silicon films

Photoluminescent nanocrystalline porous silicon films have been formed on silicon substrates by plasma-enhanced chemical vapor deposition. In the visible spectral range, a nontrivial character of the reflection spectra (dependent on the film thickness) has been found. The sizes of crystallites and the root-mean-square roughness of the deposited film surface have been determined by X-ray diffraction and atomic force microscopy. It is shown that the significant decrease in the reflectance in the spectral range from 200 to 900 nm and the red shift of the characteristic peaks in the reflection spectra are related to the sizes of nanocrystallites in the films formed.     

Optical characterization of porous silicon films and multilayer filters

Porous silicon (PS) has a great potential in optical applications due to the tunability of its refractive index. However, the electrochemical formation parameters of porous silicon have a great influence both on porosity and pore morphology and, hence, on the optical properties of the PS layers. In the present work, the optical constants of PS layers are determined in the visible-wavelength range for different electrolyte compositions and for a wide range of formation-current densities. Thus, the interval of refractive indices that can be achieved for each electrolyte composition is studied, for the further development of interference filters. In particular, it is demonstrated that a higher ethanol concentration in the electrolyte leads to a considerably higher tunability of the refractive index of PS while reducing absorption losses. In addition, the performance of PS-based multilayer interference filters is shown to improve when formed with an electrolyte of higher ethanol concentration, especially in the blue region of the visible spectrum. PACS 78.20.Ci; 78.40.-q; 78.55.Mb     

Room temperature NO_2 gas sensing of Au-loaded tungsten oxide nanowires/porous silicon hybrid structure

In this work, we report an enhanced nitrogen dioxide(NO_2) gas sensor based on tungsten oxide(WO_3)nanowires/porous silicon(PS) decorated with gold(Au) nanoparticles. Au-loaded WO_3 nanowires with diameters of 10 nm–25 nm and lengths of 300 nm–500 nm are fabricated by the sputtering method on a porous silicon substrate. The high-resolution transmission electron microscopy(HRTEM) micrographs show that Au nanoparticles are uniformly distributed on the surfaces of WO_3 nanowires. The effect of the Au nanoparticles on the NO_2-sensing performance of WO_3 nanowires/porous silicon is investigated over a low concentration range of 0.2 ppm–5 ppm of NO_2 at room temperature(25℃). It is found that the 10-? Au-loaded WO_3 nanowires/porous silicon-based sensor possesses the highest gas response characteristic. The underlying mechanism of the enhanced sensing properties of the Au-loaded WO_3 nanowires/porous silicon is also discussed.