Anneal temperature dependence of Si/SiO2 superlattices photoluminescence

Photoluminescence spectroscopy, Fourier transform infrared spectroscopy, X-ray reflectometry and high resolution electron microscopy have been used to interpret the photoluminescence properties of annealed (3/19 nm) Si/SiO₂ multilayers grown by reactive magnetron sputtering. The multilayers show an emission in the visible and near-infrared range after heat treatment from 900°C which tends to decrease from 1200°C. Three different origins for the photoluminescence activity have been found. An anneal temperature of 1200°C is necessary to optimise the silicon crystallisation within the silicon sublayers.     

Substrate temperature dependence of the photoluminescence efficiency of co-sputtered Si/SiO2 layers

Si particles embedded in an SiO₂ matrix were obtained by co-sputtering of Si and SiO₂ at various deposition temperatures T_d (200–700°C) and annealing at different temperatures T_a (900–1100°C). The systems were characterized by X-ray photoelectron, Raman scattering, infrared absorption and photoluminescence spectroscopy techniques. The results show that the photoluminescence efficiency is strongly dependent on the degree of phase separation between the Si nanocrystals and the SiO₂ matrix. This is likely connected with the Si/SiO₂ interface characteristics, together with the features indicating the involvement of quantum confinement.     

Excess Si concentration dependence of the photoluminescence of Si nanoclusters in SiO2 fabricated by ion implantation

A method for the fabrication of luminescent Si nanoclusters in an amorphous SiO₂ matrix by ion implantation and annealing, and the detailed mechanisms for the photoluminescence are reported. We have measured the implanted ion dose, annealing time and excitation energy dependence of the photoluminescence from implanted layers. The samples were fabricated by Si ion implantation into SiO₂ and subsequent high-temperature annealing. After annealing, a photoluminescence band below 1.7 eV has been observed. The peak energy of the photoluminescence is found to be independent of annealing time and excitation energy, while the intensity of the luminescence increases as the annealing time and excitation energy increase. Moreover, we found that the peak energy of the luminescence is strongly affected by the dose of implanted Si ions especially in the high dose range. These results indicate that the photons are absorbed by Si nanoclusters, for which the band-gap energy is modified by the quantum confinement effects, and the emission is not simply due to direct electron–hole recombination inside Si nanoclusters, but is related to defects probably at the interface between Si nanoclusters and SiO₂, for which the energy state is affected by Si cluster–cluster interactions. It seems that Si nanoclusters react via a thin oxide interface and the local concentrations of Si nanoclusters play an important role in the peak energy of the photoluminescence.     

Structural and photoluminescence properties of ZrO2:Eu @ SiO2 nanophosphors as a function of annealing temperature

The synthesis, morphology and luminescence properties of two systems comprising luminescent Eu³⁺-doped zirconium oxide nanocrystals embedded in an amorphous silica matrix are reported. The two systems, prepared with the same overall wt% composition of silica (75%) and Eu_xZr_(1−x)O_(2−x/2) solid solution (25%), have been annealed in the range 135–1000 °C and subsequently functionalized with (3-aminopropyl)triethoxysilane. Detailed X-ray diffraction analyses and transmission electron micrographs, combined with infrared spectroscopy and luminescence spectroscopy data, have been used to demonstrate the influence of annealing temperature on the: (i) nanostructure, (ii) luminescence properties and (iii) availability of superficial –OH groups for efficient surface functionalization. The optimum calcination temperature was found to be 700 °C for each series in terms of luminescence lifetime efficiency and post-functionalization efficiency with (3-aminopropyl)triethoxysilane.     

Defect versus nanocrystal luminescence emitted from room temperature and hot-implanted SiO2 layers

Silicon nanocrystals have been synthesized in SiO₂ matrix using Si ion implantation. Si ions were implanted into 300-nm-thick SiO₂ films grown on crystalline Si at energies of 30–55 keV, and with doses of 5×10¹⁵, 3×10¹⁶, and 1×10¹⁷ cm⁻². Implanted samples were subsequently annealed in an N₂ ambient at 500–1100°C during various periods. Photoluminescence spectra for the sample implanted with 1×10¹⁷ cm⁻² at 55 keV show that red luminescence (750 nm) related to Si-nanocrystals clearly increases with annealing temperature and time in intensity, and that weak orange luminescence (600 nm) is observed after annealing at low temperatures of 500°C and 800°C. The luminescence around 600 nm becomes very intense when a thin SiO₂ sample is implanted at a substrate temperature of 400°C with an energy of 30 keV and a low dose of 5×10¹⁵ cm⁻². It vanishes after annealing at 800°C for 30 min. We conclude that this luminescence observed around 600 nm is caused by some radiative defects formed in Si-implanted SiO₂.     

Si/SiO2 multilayers: synthesis by reactive magnetron sputtering and photoluminescence emission

This paper relates a complete study of Si/SiO₂ multilayer (ML) structures. First, we suggest an original way of synthesis based on reactive magnetron sputtering of a pure silica target. The photoluminescence spectra of these MLs consist of two Gaussian bands in the visible-near infrared spectral region. The stronger one (I band) is fixed at about 780 nm and probably due to interface states. The weaker one (Q band) is tuneable with the Si sublayer thickness and originates from a radiative recombination within the nanosized Si layers. For this latter band the peak position is a function of the Si sublayer thickness and shows a discontinuity at 30 Å. This corresponds to an Si phase change. For thicknesses above 30 Å, the sublayers are composed of nanocrystalline silicon whereas below 30 Å the sublayers are made of amorphous silicon. We develop a model based on a quantum well to which we have added an interfacial region between Si and SiO₂. It is characterised by an interfacial potential of 0.3 eV. This model depicts the simultaneous behaviour of Q and I bands for an Si sublayer thickness below 30 Å.     

Visible light emission from Si/SiO2 superlattices in optical microcavities

Bright quantum confined luminescence due to band-to-band recombination can be obtained from Si/SiO₂ superlattices. Placing them in a one-dimensional optical microcavity results in a pronounced modulation of the photoluminescence (PL) intensity with emission wavelength, as a consequence of the standing wave set up between the substrate and top interfaces. For a Si substrate, absorption of light reduces the PL efficiency, but for an Al-coated glass substrate the PL intensity is twice that of a quartz substrate case. The addition of a broad-band high reflector to the superlattice surface results in enhanced narrow-band emission. These results show that a suitably designed planar microcavity can not only considerably increase the external efficiency of luminescence in Si/SiO₂ superlattices but can also be used to decrease the bandwidth and selectively tune the peak wavelength.     

Electric-field-controlled photoluminescence of CdSe nanocrystal-doped SiO2 on Si

Dense-packed CdSe nanoclusters synthesized by sequential ion implantation of Cd⁺ and Se⁺ in thermally grown SiO₂ are subjected to high electric field strengths in a metal oxide semiconductor (MOS) structure. The nanocrystal-containing device shows efficient CdSe band-edge photoluminescence (PL) when excited by a cw-HeCd laser operating at a wavelength of 442 nm at room temperature. An effective PL quenching and enhancement has been observed. Depth-resolved μ-PL measurements reveal an exponential decrease, which is depth-correlated with a layer of nanoparticles near the surface, whereas the optical non-linearity of the PL increases in parallel. The PL spectra and particle size distribution suggest an energy transfer from the nanoscopic to adjacent large particles. It can be concluded from these results that charge injection into the near-surface region of the nanocluster/SiO₂ system might be the reason for the asymmetric and hysteretic electro-optic response.     

Size-dependent visible photoluminescence from ZnO nanoparticles prepared via SiO2 network

This study reports a simple method for the synthesis of different size of wurtzite ZnO nanoparticles in assistance of tetraethyl orthosilicate (TEOS). With the increase of the amount of TEOS added, the average size of ZnO nanoparticles was found decreased from ∼14.6 to ∼1.9 nm by characterization of X-ray diffraction (XRD) and high-resolution electron microscopy (HRTEM). The growth of ZnO nanoparticles is proposed to be controlled by the density of the SiO₂ chain mesh which is determined by TEOS amount in precursor. Ultraviolet–visible (UV–VIS) absorption and photoluminescence (PL) spectra show both shift to higher energy in cut-off edge and in visible emission bands respectively. The electron transition process in the mechanism of the visible emission shift was described and related to quantum size effect in ZnO nanoparticles.     

Mechanism and enhancement of photoluminescence from silicon nanocrystals implanted in SiO2 matrix

Photoluminescence (PL) spectra of Si nanocrystals (NCs) prepared by 130 keV Si ions implantation onto SiO2 matrix were investigated as a function of annealing temperature and implanted ion dose. PL spectra consist of two PL peaks, originated from smaller Si NCs due to quantum confinement effect (QCE) and the interface states located at the surface of larger Si NCs. The evolution of number of dangling bonds (DBs) on Si NCs was also investigated. For hydrogen-passivated samples, a monotonic increase in PL peak intensity with the dose of implanted Si ions up to 3×1017 ions /cm2 is observed. The number of DBs on individual Si NC, the interaction between DBs at the surface of neighbouring Si NCs and their effects on the efficiency of PL are discussed.     

Study on morphology and photoluminescence of Au/SiO2 nanocomposite films

Au/SiO₂ nanocomposite films were fabricated on Si (111) substrates by radio frequency (RF) magnetron sputtering technique and annealing at different temperature for 20 min (mode A) and at 1000 °C for different annealing time (mode B). The nanocomposite films were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and photoluminescence (PL). SEM results demonstrate that the size of Au crystallites in mode A first increases and then decreases, on increasing annealing temperature, according to the results of XRD spectra. Analysis of PL spectra in mode B shows that the intensity of the emission peak at 440 nm and 523 nm early increases and late decreases, with increasing annealing time at 1000 °C. The origin of the emission peak at around 440 nm was related to the size and quantity of Au particles and one of the emission peak at around 523 nm was related to the nanostructure of films in agreement with SEM imagines. Experimental results indicated that morphology, microstructure and luminescence of Au/SiO₂ nanocomposite films showed close affinity with annealing temperature and annealing time.     

Continuous nano-coating of Y2O3:Eu phosphor shell on SiO2 core particles and its photoluminescence properties

In order to investigate the effects of the crystallite size on the photoluminescence (PL) properties of a phosphor, monodisperse spherical SiO₂/Y₂O₃:Eu³⁺ phosphor core/shell particles were synthesized. On the surface of the core particles prepared by the Stöber method, the phosphor shell was continuously coated by a heterogeneous precipitation method. Because the growth of the crystallite was restricted by the shell thickness, the crystallite size could be successfully controlled at the same firing conditions. The PL intensity, the asymmetric ratio and thus the color purity were significantly decreased with the decrease of the crystallite size. In addition, the position of charge transfer band in the PL excitation spectrum was red-shifted with the decrease of the crystallite size.     

Enhanced photoluminescence of ZnO-SiO2 nanocomposite particles and the analyses of structure and composition

Stable blue-green photoluminescent ZnO-SiO₂ nanocomposite particles exhibiting quantum efficiency as high as 34.8% under excitation at 360 nm were prepared using a spray-drying process from a feed solution that contained both luminescent ZnO nanoparticles synthesized by a sol-gel method and commercially-available SiO₂ nanoparticles. The effects of silica nanoparticle size and SiO₂-to-ZnO concentration ratio on the PL properties of the composite particles were investigated. The internal structure and chemical composition were investigated in detail using elemental mapping, which revealed that ZnO nanoparticles were well-dispersed within silica nanoparticle matrix. At a LiOH concentration of 0.23 M, the predicted ZnO crystallite diameter before and after spray drying was approximately constant at 3.3 and 3.6 nm, respectively. This result indicates that ZnO particle growth was inhibited and therefore the PL property of ZnO nanoparticles was stably preserved in the composite.     

Observation of room temperature photoluminescence in proton irradiated SrTiO3 single crystal

We have irradiated SrTiO₃ single crystal with 3 MeV-proton (H⁺) beam and found that blue -, green - and infrared - frequency photoluminescence (PL) are induced simultaneously at room temperature. TEM and EELS analyses show that an oxygen-deficient amorphous layer is formed at the crystal surface by the proton irradiation. Possible origin of the PL-effect is discussed.     

Stimulated photoluminescence emission and trap states in Si/SiO2 interface formed by irradiation of laser

Stimulated photoluminescence （PL） emission has been observed from an oxide structure of silicon when optically excited by a radiation of 514nm laser. Sharp twin peaks at 694 and 692nm are dominated by stimulated emission, which can be demonstrated by its threshold behaviour and linear transition of emission intensity as a function of pump power. The oxide structure is formed by laser irradiation on silicon and its annealing treatment. A model for explaining the stimulated emission is proposed, in which the trap states of the interface between an oxide of silicon and porous nanocrystal play an important role.     

Irradiation induced germanium lone pair centers in Ge-doped sol-gel SiO2: Luminescence lifetime and temperature dependence

We studied the temperature dependence of the emission profile and of the lifetime, measured at 4.3 eV, related to the germanium lone pair centers (GLPC) induced by gamma ray at 5 MGy in a Ge-doped silica sample and in an analogous sample irradiated at 10 MGy, in which by a successive thermal treatment up to 415 °C the induced GLPC has been modified (named residual GLPC in the following). The measurements were recorded in the temperature range 10-300 K using an excitation of ∼5.2 eV. The data show that the energy level scheme of the induced and the residual GLPC is very similar to that of the native defects generated during the synthesis, and the intersystem crossing process (ISC) of the induced GLPC is similar to that of the native centers, whereas it changes for the residual GLPC. Moreover, we have found that the efficiency of the singlet-singlet transition is similar for the three GLPC types. We suggest that the observed differences are due to the pre-exponential factor of the Arrhenius law describing this type of phonon assisted process and it can be attributed to changes in the entropic or the structural contributions to the ISC.     

Continuous photoluminescence, time resolved photoluminescence and optically detected magnetic resonance measurements of PbI2 nanometer-sized particles, embedded in SiO2 films

The nanometer sized particles of PbI₂ were embedded in SiO₂ films. X-ray diffraction and the TEM pictures showed the preservation of the bulk layered structure and symmetry. The PL spectrum of the nano-particles exhibited a pronounced blue shift of the exciton band due to quantum size effect. The Lead Iodide represents an exceptionally small exciton Bohr radius (a_B = 19 Å) and a special case in which m_e m_h. The prepared samples contained particles with mean radii, a, in the range a_B < a < 3a_B. Within this limit (with m_e m_h), the experimental results suggest that the electron is localized nearly at the center of the particle, enabling the hole to move around it. Thus, the size confinement permits the creation of an acceptor-like exciton. The PL spectrum revealed additional states, associated with stoichiometric defects either at the interior or surface sites of the nano-particles. These defects act either as donor or acceptor states. The dynamics of the various recombination processes has been investigated by measuring the time resolved PL spectra. The results show a multiexponential behavior of the various recombination emission bands, indicating the occurrence of trapping and detrapping processes. Analysis of these results suggests that the existence of surface states give rise to these complex radiative decay processes. The correlation between donor-acceptor recombination emission bands in the aforementioned samples and lattice imperfections was examined, utilizing optically detected magnetic resonance (ODMR) spectroscopy. The results identified the following imperfection sites: an acceptor site associated with an isotropic Lead vacancy defect, [V⁻]_pb²⁺ and a donor site, associated with an anisotropic Iodine vacancy, [V⁰]_Iodine.     

Tunable photoluminescence and electroluminescence of size-controlled silicon nanocrystals in nanocrystalline-Si/SiO2 superlattices

We present photoluminescence and electroluminescence of silicon nanocrystals deposited by plasma-enhanced chemical vapor deposition (PECVD) using nanocrystalline silicon/silicon dioxide (nc-Si/SiO₂) superlattice approach. This approach allows us to tune the nanocrystal emission wavelength by varying the thickness of the Si layers. We fabricate light emitting devices (LEDs) with transparent indium tin oxide (ITO) contacts using these superlattice materials. The current-voltage characteristics of the LEDs are measured and compared to Frenkel-Poole and Fowler-Nordheim models for conduction. The EL properties of the superlattice material are studied, and tuning, similar to that of the PL spectra, is shown for the EL spectra. Finally, we observe the output power and calculate the quantum efficiency and power conversion efficiency for each of the devices.     

Ar irradiation of Si nanocrystal-doped SiO2: Evolution of photoluminescence

We report the evolution of photoluminescence (PL) of Si nanocrystals (nc-Si) embedded in a matrix of SiO₂ during Ar⁺ ion bombardment. The integrated intensity of nc-Si PL falls down drastically before the Ar⁺ ion fluence of 10¹⁵ ions cm⁻², and then decreases slowly with the increasing ion fluence. At the meantime, the PL peak position blueshifts steadily before the fluence of 10¹⁵ ions cm⁻², and then changes in an oscillatory manner. Also it is found that the nc-Si PL of the Ar⁺-irradiated sample can be partly recovered after annealing at 800 °C in nitrogen, but can be almost totally recovered after annealing in oxygen. The results confirm that the ion irradiation-induced defects are made up of oxygen vacancies, which absorb light strongly. The oscillatory peak shift of nc-Si can be related to a size-distance distribution of nc-Si in SiO₂.     

Synthesis and properties of magnetic and luminescent Fe3O4/SiO2/Dye/SiO2 nanoparticles

A simple and reproducible method was developed to synthesize a novel class of Fe₃O₄/SiO₂/dye/SiO₂ composite nanoparticles. As promising candidates for use in bioassays, the obtained nanoparticles have an average diameter of 30 nm, and the thickness of the outer shell of silica could be tuned by changing the concentration of the silicon precursor tetraethyl orthosilicate during the synthesis. These multifunctional nanoparticles were found to be highly luminescent, photostable and superparamagnetic. The luminescence intensity of the nanoparticles was increased as the dye concentration was increased in the preparation process. The color of the luminescence was successfully tuned by incorporating different dyes into the nanoparticles. The measurements of the emission spectra indicated that relative to the dye molecules dissolved in ethanol, the emission of the dye-doped nanoparticles exhibited either a red shift or a blue shift, to which a tentative explanation was given.