Luminescence properties of Er in SiN/PS : Er

The decrease in luminescence from host porous silicon (PS) by thermal annealing prevents the optical activation of Er ions. We prepared a SiN layer on erbium-doped porous silicon (PS : Er) as the capping layer by photo-chemical vapor deposition (photo-CVD). After deposition of SiN, the sample was annealed in pure Ar atmosphere for optical activation. We observed an Er-related emission at 1532 nm with a full-width at half-maximum (FWHM) of 10 nm at 18 K from the sample with the SiN layer. In contrast, no emission was observed from the sample without the SiN layer. At 300 K, the peak intensity of Er³⁺-related photoluminescence (PL) for the sample annealed at 1100°C decreased to 40.0% of that observed at 18 K. From these results, it was found that the SiN layer on PS:Er is useful for both host PS and Er-related 1.5 μm luminescences.     

Structural and optical features of nanoporous silicon prepared by electrochemical anodic etching

Nanoporous silicon (NPS) samples were prepared by electrochemical anodic etching of p-type (0 0 1) silicon wafers in HF solution, and some of them were aged in air. The nanostructural, optical and chemical features of the NPS were investigated in terms of etching and aging conditions. The surface of the porous Si exhibits an etched layer with a thickness of 30–40 nm; this layer appears to consist of aggregates of 5–10 nm size nano-crystallites. The NPS exhibited broad photoluminescence (PL) spectra with its peak in the red light region (740 nm). After aging the porous samples for 4 weeks in air, we observed the PL intensity became approximately a fifth of that of the as-prepared one, along with a blue shift. It is very likely that the blue shift of the PL peak was caused by the shrinkage of the Si nano-crystallites due to the oxidation in the surface of the nano-crystallites.     

Microstructured silicon surfaces for field emission devices

Enhanced field emission of electrons from silicon surfaces was obtained by surface microstructuring, by means of electrochemical oxidation in organic solutions containing HF. Morphological characterisations showed the formation of cylindrical rods, randomly distributed with relative spacing of a few microns. They are originated at the top of silicon pyramids and have typical diameter in the 100 nm range. Variable length in the 1–50 μm range was obtained, by adjusting the process parameters. Electron field emission properties were characterised for several samples, prepared in different conditions: the emission threshold was found to be strongly correlated with the overall charge exchanged during electrochemical oxidation. In the most favourable conditions, the threshold field for the emission of an electron current I_th = 10⁻¹⁰ A was 11.1 V/μm.     

On the origin of 1.5 μm luminescence in porous silicon coated with sol–gel derived erbium-doped Fe2O3 films

Sol–gel derived Fe₂O₃ films containing about 10 wt% of Er₂O₃ were deposited on porous silicon by dipping or by a spin-on technique followed by thermal processing at 1073 K for 15 min. The samples were characterized by means of PL, SEM and X-ray diffraction analyses. They exhibit strong room-temperature luminescence at 1.5 μm related to erbium in the sol–gel derived host. The luminescence intensity increases by a factor of 1000 when the samples are cooled from 300 to 4.2 K. After complete removal of the erbium-doped film by etching and partial etching the porous silicon, the erbium-related luminescence disappears. Following this, luminescence at 1.5 μm originating from optically active dislocations (“D-lines”) in porous silicon was detected. The influence of the conditions of synthesis on luminescence at 1.5 μm is discussed.     

Comparative study of the oxidation of thin porous silicon layers studied by reflectometry, spectroscopic ellipsometry and secondary ion mass spectroscopy

We present a systematic study on ultrathin porous silicon (PS) layers (40–120 nm) of different porosities, formed by electrochemical etching and followed by thermal oxidation treatment (300°C and 600°C) and by electrochemical oxidation. The oxidised and non-oxidised PS layers have been analysed by spectroscopic reflectometry (SR), spectroscopic ellipsometry (SE) and secondary ion mass spectroscopy (SIMS). The SR and SE spectra were fitted by a multiparameter fit program and the composition and the thickness of the PS layers were evaluated by different optical models. PS layers, formed electrochemically in the outermost layer of a p/n⁺ monocrystalline silicon junction were successfully evaluated using a gradient porosity optical model. The non-oxidised PS, formed in p-type silicon, can be well described by a simple optical model (one-layer of two-components, silicon and voids). The spectra of the oxidised PS layers can be fitted better using an optical model with three interdependent components (crystalline-silicon, silicon-dioxide, voids). The SIMS results give a strong support for the optical model used for SR and SE.     

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.     

Molecular beam epitaxy growth and characterization of self-assembled InAs quantum dots on (1 0 0) InAlAs/InP substrates

Self-assembled InAs quantum dots (QDs) on In_0.52Al_0.48As layer lattice matched to (1 0 0) InP substrates have been grown by molecular beam epitaxy (MBE) and evaluated by transmission electron microscopy (TEM) and photoluminescence (PL). TEM observations indicate that defect-free InAs QDs can be grown to obtain emissions over the technologically important 1.3–1.55 μm region. The PL peak positions for the QDs shift to low energy as the InAs coverage increases, corresponding to increase in QD size. The room temperature PL peak at 1.58 μm was observed from defect-free InAs QDs with average dot height of 3.6 nm.     

Erbium-doped silicon epilayers grown by liquid-phase epitaxy

Liquid-phase epitaxy from an Si–In–Er solution at an average temperature of 950°C has been used to grow 2–4 μm thick epilayers of erbium-doped silicon onto CZ and FZ silicon substrates in an oxygen-free hydrogen atmosphere. Most of the samples grown on CZ substrates presented detectable, but feeble photoluminescence at 2 K in the spectral range of emission of the Er³⁺ manifold at 0.8 eV. However, some of the samples presented intense photoluminescence, characterized by two bands at 0.807 (at 10 K) and 0.873 eV, of which the first falls almost at the same energy of the Er³⁺ line, but whose intensity presents a quite remarkable persistence up to 250 K. From the energy position of the two bands, from their temperature dependence and from the levels found by deep level transient spectroscopy measurements, associated to TEM examinations, it was possible to attribute these bands, labelled D1 and D2, to dislocation luminescence. It will be shown in this paper that the presence of erbium enhances the D1 luminescence, possibly due to the fact that in these samples erbium is gettered at dislocations in an Er–O local configuration, as it results from EXAFS measurements. Apparently, also, a competition occurs with the Er-induced radiative recombination at dislocations, which is a fast process, and the indirect excitation of the Er manifold, which is the predominant process in dislocation-free materials.     

Time-resolved photoluminescence study of the red emission in nanoporous SiGe alloys

Porous Si_1−xGe_x (PSiGe) layers with efficient room temperature visible photoluminescence (PL) were elaborated by anodical etching from p-type doped epitaxial layers with Ge contents from 5 to 30%. The luminescence is characterised by a broad PL band centred at 1.8 eV. Time resolved photoluminescence decay is studied in porous silicon germanium as a function of germanium content, temperature, emission energies and surface passivation. The PL decay line shape is well described by a stretched exponential in all cases. The effective lifetime at low temperature in as prepared porous Si_1−xGe_x is 400 μs, i.e. an order of magnitude less than in porous silicon. After the formation of a 20 Å thick oxide surface layer we observe a decrease of the effective lifetime to 20 μs at T=4 K.     

A comparative infrared study of H2O reactivity on Si(1 0 0)-(2 × 1), (2 × 1)-H, (1 × 1)-H and (3 × 1)-H surfaces

The water adsorption on the bare and H-terminated Si(1 0 0) surfaces has been studied by the BML-IRRAS technique. It is found that H-terminated surfaces are much less reactive compared to the bare silicon surfaces. The (1 × 1)-H and (3 × 1)-H surfaces show similar and less reactivity pattern compared to the (2 × 1)-H surface. At higher exposures, the water reaction with coupled monohydride species provides an effective channel for oxygen insertion into the back bonds of dihydride species. It is not attributed to the H–Si–Si–H + H₂O → H–S–Si–OH + H₂, which could give rise to the characteristic Si–H and Si–OH modes, respectively at 2081 and 921 cm⁻¹. A more suitable reaction mechanism involving a metastable species, H–Si–Si–H + H₂O → H₂Si  HO–Si–H (metastable) explains well the bending modes of oxygen inserted silicon dihydride species which are observed relatively strongly in the reaction of water with H-terminated Si(1 0 0) surfaces.     

Crystalline silicon films sputtered on molybdenum: A study of the silicon–molybdenum interface

Polycrystalline silicon films were grown on molybdenum (Mo)-coated substrates at high deposition rate using the pulsed magnetron sputtering technique. Our study investigates the silicon–molybdenum interface of these films to elucidate stimulating mechanisms for an ordered crystalline silicon thin film growth. Both Auger electron spectroscopy and Rutherford backscattering reveal that at a substrate temperature as low as T_S=450 °C during the deposition process intermixing of Si and Mo at the Si–Mo interface takes place leading to a compositional ratio Mo:Si of about 1:2. By Raman spectroscopy hexagonal β-MoSi₂ could be identified as the dominant phase in this intermixed region. The dependence of the resulting thickness of the reacted interface layer on the deposition conditions is not fully understood yet.     

Electrochemically driven organic monolayer formation on silicon surfaces using alkylammonium and alkylphosphonium reagents

The functionalization of silicon surfaces with organic monolayers, bound through Si–C bonds, is an area of wide interest due to the technological promise of organosilicon hybrid devices, but also to investigate fundamental surface reactivity. In this paper, the use of alkylammonium and alkylphosphonium cations as sources of organic moieties to bind to hydrogen-terminated flat and porous silicon is demonstrated. Tetraalkylammonium, tetraalkyl/arylphosphonium reagents, and alkyl pyridinium salts can be utilized, but trialkylammonium salts cannot as they yield substantial surface oxidation. Under electrochemical conditions, either potentiostatic or galvanostatic modes, alkyl groups derived from the ammonium or phosphonium salts are grafted to the silicon surface and are bound through Si–C bonds. Covalent attachment of the organic monolayers to the surface was demonstrated by XPS, AFM scribing, and FTIR. The mechanism may proceed via reduction of the ammonium salt yielding alkyl radicals, R, which may be reduced to R⁻ and attack surface Si–Si bonds, leading to Si–C bonds, or the formation of silyl anions (≡Si⁻) under the cathodic conditions followed by nucleophilic attack on the trialkylammonium cation.     

Coating zinc oxide submicron crystals on poly(methyl methacrylate) chips and spheres via ultrasound irradiation

Ultrasound irradiation is used for anchoring zinc oxide submicron crystals with a main diameter and length of 280 nm and 470 nm, respectively, onto the surface of poly(methyl methacrylate) PMMA chips (2 mm diameter), and zinc oxide crystals with a mean diameter and length of 150 nm and 230 nm, respectively, onto the surface of the PMMA spheres (1–10 μm). The zinc oxide crystals were obtained by sonochemical irradiation of a mixture containing the PMMA, zinc (II) acetate dihydrate, ethanol, water, and 24 wt.% aqueous ammonia for 2 h, yielding a PMMA–zinc oxide composite. By controlling the atmosphere and reaction conditions, we could achieve well-adhered zinc oxide crystals on the surface of poly(methyl methacrylate). The resulting zinc oxide–PMMA composite was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), energy-dispersive X-ray analysis (EDX), high-resolution scanning electron microscopy (HRSEM), and photoluminescence (PL) spectroscopy. The zinc oxide-deposited PMMA chips (loaded with 0.03–1.0 wt.% ZnO) were successfully homogenized in melt by extrusion and then injection molded into small, disc-shaped samples. These samples were analyzed with respect to their directional spectral optical properties in UV, Vis and IR spectroscopy.     

The effect of annealing under hydrostatic pressure on the visible photoluminescence from si-ion implanted SiO2 films

We have studied the influence of the hydrostatic pressure during annealing on the intensity of the visible photoluminescence (PL) from thermally grown SiO₂ films irradiated with Si⁺ ions. Post-implantation anneals have been carried out in an Ar ambient at temperatures T_a of 400°C and 450°C for 10 h and 1130°C for 5 h at hydrostatic pressures of 1 bar–15 kbar. It has been found that the intensity of the 360, 460 and 600 nm PL peaks increases with rising hydrostatic pressure during low-temperature annealing. The intensity of the short-wavelength PL under conditions of hydrostatic pressure continues to rise even at T_a=1130°C. Increasing T_a leads to a shift in the PL spectra towards the ultraviolet range. The results obtained have been interpreted in terms of enhanced, pressure-mediated formation of ≡Si–Si≡ centres and small Si clusters within metastable regions of the ion-implanted SiO₂.     

Influence of alkali metallization (Li, Na and K) on photoluminescence properties of porous silicon

We present results for alkali metallization effects on photoluminescence (PL) properties of porous silicon (PS). The metallization of PS was realized by immersion plating in solutions containing 3 mM LiNO₃, KNO₃ and NaNO₃ metal salts. The surface bond configuration of PS was monitored by Fourier transmission infrared spectroscopy (FTIR) and it was found that the PS surface was oxidized after metallization. Surface properties of PS were investigated by field emission scanning electron microscopy (FE-SEM) and it was found that the PS surface was covered by alkali metals for short immersion times. The PL intensity increased for critical immersion times and PL spectrum shifted to high energy region with the metallization. The experimental results suggest a possibility that the metallization provides a relatively easy way to achieve an increase in the PL intensity and oxidation of the PS surface.     

Nanostructural and photoluminescence features of nanoporous silicon prepared by anodic etching

The nanostructural and photoluminescence (PL) features of nanoporous Si (NPS) were investigated in terms of various process parameters such as current density, etching time and oxidation conditions. The NPS was prepared by electrochemical anodic etching of p-type (0 0 1) Si wafers of 4 Ω cm resistivity in HF solution. The pores are of polygon-type columns with 5, 6 and 7 side walls. The average diameter of the column-shaped pores is critically determined by the current density, while the etching time plays an important role on the pore depth; in particular, when the current densities of 30 and 100 mA/cm² were applied, the pore diameters were 9 nm and 3.3 μm, respectively. The variation in the PL characteristics of the NPS with oxidation condition and etching current density was measured and then related with their structural changes. The aging and thermal treatments produce oxidation and lattice distortion in the NPS. The degree of deviation from the as-prepared NPS during aging or thermal treatment seems to depend on the nanostructure as well as morphology of the NPS. It is found in this study that etching current density plays an important role on such structural features of the NPS.     

The role of surface oxidation on luminescence degradation of porous silicon

This study reports a comparative analysis on time dependent degradation of photoluminescence (PL) spectra of porous silicon (PS) during dark-aging (DA) and photo-aging (PA). Fourier Transform Infrared (FTIR) spectroscopy studies have been performed to get an insight on possible chemical changes in the PS surface. It has been found that SiH_x bonds decrease progressively while SiO_x bonds increase. FTIR and PL measurements revealed presence of blue shifts in the PL spectra during the aging stages (PA and DA). While the PL intensity of dark aged PS shows a decrease during the first 3 weeks and an increase afterwards, the PL intensity decreases continuously for photo-aged PS. The change in the PL spectra has been investigated by overlapping of two different PL bands which are reflective of oxidation of PS surface and size of Si naonocrystallites. A possible bond configuration model about the oxidation of PS surface has also been proposed. The results are interpreted in terms of quantum size effects in PS and the influence of the surface composition.     

Kinetic aspects of aluminium titanate layer formation on titanium alloys by plasma electrolytic oxidation

The paper reports on a systematic investigation into the effects of process parameters on the growth kinetics and associated changes in the structure, phase composition and mechanical properties of surface layers formed on Ti–6Al–4V alloy by plasma electrolytic oxidation (PEO) treatment in 0.05–0.2 mol l⁻¹ solutions of sodium aluminate. Methods of gravimetric, SEM and XRD analysis, as well as microhardness and scratch testing, are employed to investigate mass transfer and phase-structure transformations in the surface layer. The probable mechanisms of layer formation are discussed, which comprise electrochemical oxidation of the Ti-electrode by OH⁻ anions, complimented by chemical precipitation of Al(OH)₃ and plasma-induced transformations in the surface discharges. Running with a total yield efficiency of 20–30%, these processes lead to the formation of predominantly the Al₂TiO₅ phase with heterogeneous precipitation of Al₂TiO₅·TiO₂ and 3Al₂TiO₅·Al₂O₃ eutectics. Al- and Ti-enriched constituents of this structure show hardnesses of 1050–1480 and 300–845 H_K, 0.02, respectively. The layer growth rate increases with increasing electrolyte concentration, providing a maximum thickness of over 60 μm and a surface roughness (R_a) of 3–4 μm. Increasing the electrolyte pH from 12.0 to 12.8 results in smoothing and thickening of the surface layer but a lower sample weight gain, associated with an enhancement of the Ti electro-oxidation process. Morphological changes during PEO formation of the surface layer include gradual transformation of the original fine grained but porous structure into a dense, fused morphology which is adversely affected by discharge-induced thermal stresses, causing a degradation of the layer adhesion strength.     

Cathodoluminescence properties of silicon nanocrystallites embedded in silicon oxide thin films

Cathodoluminescence (CL) spectra for the Si nanocrystallites embedded in a matrix of silicon oxide films are measured at room temperature. The CL spectra consist of two principal bands whose peak energies are in a near-infrared (NIR) region (<1.6 eV) and in a blue region (2.6 eV), respectively. The spectral feature of the NIR CL band is similar to the corresponding PL spectra. The strong correlation between the presence of Si nanocrystallites and the formation of the NIR CL band are found as well as the PL spectrum. The peak energy of the blue CL band is slightly lower than that of the luminescence band originating from oxygen vacancies (≡Si–Si≡) in SiO₂. Therefore, the blue CL band is considered to come from Si_n clusters with n3 in the oxide matrix. Under irradiation of electron beams, degradation of the intensity is observed for both the CL bands but the decay characteristics are different.     

Visible photoluminescence and its mechanisms from a-SiOx : H films with different stoichiometry

The photoluminescence (PL) properties of H-rich amorphous silicon oxide thin films prepared by dual-plasma chemical vapor deposition have been studied. The three commonly reported PL bands centered around 1.7, 2.1 and 2.9 eV have been detected from the same type of a-SiO_x : H material, only by varying the oxygen content (x≈1.35, 1.65, 2). In order to characterize the PL bands, the samples in as-prepared and annealed states up to 900°C have been analyzed by XPS, FT-IR, gas effusion, ESR and ellipsometry. Temperature quenching experiments are crucial to distinguish the 1.7 eV band, fully consistent with a bandtail-to-bandtail transition, from radiative defect luminescence mechanisms attributed either to defects related to Si–OH groups (2.9 eV) or to oxygen vacancy defects (2.1 eV).