Recombination of self-trapped excitons in silicon nanocrystals grown in silicon oxide

The kinetics of photoluminescence (PL) and steady-state PL from silicon nanocrystals formed in the SiO₂ matrix by silicon ion implantation were studied experimentally for the first time in the temperature range from liquid-helium to room temperature. A dramatic increase in the photoluminescence decay time, accompanied by PL intensity quenching, is observed below 70 K. The results obtained indicate that the silicon nanocrystal PL arises from radiative recombination of excitons self-trapped at the silicon nanocrystal-SiO₂ interface.     

Kinetics of exciton photoluminescence in low-dimensional silicon structures

Time-resolved photoluminescence (PL) spectra have been measured at 90–300 K in the visible spectral range for porous nanocrystalline silicon films fabricated by laser deposition. The energy and time ranges in which the spectra were taken were 1.4–3.2 eV and 50 ns–10 µs, respectively. The correlation between PL characteristics (intensity, emission spectrum, relaxation times and their temperature dependence), structure, and dielectric properties (size and shape of Si nanocrystals, oxide phase of their coatings, porosity of films) has been studied. A model of photoluminescence is adopted, in which the absorption and emission of photons occur in quantum-size nanocrystals, and in which kinetically coupled subsystems of electron-hole pairs and excitons are involved in the radiative recombination. Possible mechanisms of the exciton Auger recombination in low-dimensional silicon structures are proposed.     

Exciton recombination in δ-doped type-II GaAs/AlAs superlattices

Radiative recombination of excitons in δ-doped type-II GaAs/AlAs superlattices (SLs) is studied experimentally. With an increase in the impurity density in δ-layers from 2×10¹⁰ to 7.5×10¹¹ cm^?2, the integrated intensity of SL photoluminescence (PL) decreases by a factor of 4–6; the intensity of excitonic PL drops considerably (up to 70–80 times), which is accompanied by an increase in the exciton radiative decay rate. Uniform doping of the SL does not result in the exciton PL quenching. Analysis of the temperature dependence and the kinetics of the PL indicate that impurity quenching of the excitonic PL in δ-doped structures is not related to a reduction in the exciton localization energy and cannot be explained by an increase in the density of nonradiative recombination centers. We conclude that the PL quenching is mainly caused by the appearance of built-in electric fields originating from ionized impurities, which hinders the formation of the excitons.     

Photoluminescent and electronic properties of nanocrystalline silicon doped with gold

Doping nanocrystalline silicon (nc-Si) films grown by laser ablation with gold leads to a considerable suppression of the nonradiative recombination of the charge carriers and excitons, an increase in the intensity and stability of the visible photoluminescence, and enhancement of the low-energy (1.5–1.6 eV) photoluminescence band. In Au-doped samples, the magnitude of the photovoltage and the rate of electron capture by traps in the film are reduced, and the density of boundary electron states and the concentration of deep electron traps at the single-crystal silicon (c-Si) substrate are decreased as well. The observed effect of doping on the photoluminescent and electronic properties of nc-Si films and nc-Si/c-Si structures is caused by the passivation of dangling Si bonds with Au and by the further oxidation of silicon at the surface of nanocrystals, which results in the formation of high-barrier SiO₂ layers.     

Luminescence properties of thin nanocrystalline silicon-carbide films fabricated by direct-beam ion deposition

Nanocomposite films containing nanocrystals of silicon and silicon carbide are fabricated by direct ion-beam deposition onto silicon substrates. The films obtained are by Raman spectroscopy and the photoluminescence method. It is found that the samples under study exhibit two photoluminescence bands, in the “red” and near-infrared (IR) (600–1000 nm) and “blue” (400–550 nm) spectral ranges, which are accounted for by, respectively, the radiative recombination of excitons in silicon nanocrystals and radiative transitions between levels related to local centers (defects) on the surface of silicon nanocrystals and in the surrounding matrix. Short-duration treatment of the films in a solution based on hydrofluoric acid leads to modification of the emission spectrum and to an increase in the intensity of the exciton band due to the passivation of defects on the surface of silicon nanocrystals.     

Photoluminescence and X-ray luminescence of Pb0.30Cd0.70I2 solid solutions. Comparative study

The nature and relative contributions (RCs) of various radiative recombination processes to the photoluminescence (PL) spectra for bulk nanostructured Pb_0.30Cd_0.70I₂ solid solutions have been established at different temperatures. The analysis indicates that the PL is caused by free, bound and self-trapped excitons as well as by donor-acceptor pairs emission with the participation of shallow and deep acceptor centers. It was shown that X-ray luminescence (XRL) spectra are also determined by these recombination processes. However, their RC and the temperature evolution are considerably different. Besides, XRL spectra contain an intense long-wavelength band associated with the emission of many LO-phonons. It was shown that the deep luminescence surface states, associated with the self-trapped excitons and deep intrinsic defects, mainly determine the intensity of XRL spectra both at 80 K and room temperature. The results obtained open the way to the optimization of the scintillator properties of the investigated materials.     

Optical and electrical properties of Al2O3 films containing silicon nanocrystals

Optical, electrical, and structural properties of Al₂O₃ films subjected to silicon-ion implantation and annealing were investigated by means of photoluminescence measurements, current-voltage measurements and transmission electron microscopy. Transmission electron microscopy revealed that silicon nanocrystals were epitaxially formed in ϑ-Al₂O₃. Visible photolum inescence was observed, for the first time, from Al₂O₃ films containing silicon nanocrystals. Observed visible photoluminescence seems to be related to quantum size effects in silicon nanocrystals as well as localized radiative recombination centers located at the interface between silicon nanocrystals and matrix, similar to porous Si and other Si nanostructures. The conduction mechanism in the samples was studied by using dc current-voltage measurements. The conduction properties depend on temperature and applied electric fields. The conduction behavior in low electric fields consists of thermally activated region dominated by the Schottky conduction and nonthermally activated region in which carrier transport is controlled by space-charge-limited currents. The conduction behavior under relatively high electric fields is almost independent of temperature and well fitted by space-charge-limited conduction.     

Characterization of Cd1−xZnxTe crystals grown from a modified vertical bridgman technique

Cd_1−xZn_xTe (CZT) crystals grown from a modified vertical Bridgman technique were characterized by means of an optical polarized transmission technique using the Pockels effect, low-temperature direct current (DC) photo-conductivity technique, low-temperature photoluminescence (PL) spectroscopy, room-temperature PL mapping technique, and detector performance measurements. Electric field mapping indicates that an approximation of a uniform electric field distribution approximation is generally satisfied for CZT detectors operated at room temperature under typical working conditions. A nonuniform electric field distribution is observed under intense infrared (IR) light illumination, and a model is proposed based on charge generation of defects, trapping, and space-charge effects. The largest hole mobility-lifetime product (μτ)_h of the CZT detector measured by DC photoconductivity is 7.0 × 10⁻⁴ cm²/V. The detector treated with 2% bromine in methanol chemical etch has a relatively small surface recombination velocity at room temperature, which was obtained from DC photocurrent and detector performance tests, as measured by irradiation of 5.5-MeV α particles and 59.6-keV γ-rays, respectively. We have clearly shown the equivalence of charge collection efficiency results measured by both DC photocurrent and α particle response. Low-temperature DC photocurrent measurements show that surface recombination velocity increases significantly with decreasing temperature from 300 K to 250 K. The effective electron mobility-lifetime product—combination effects of bulk and surface of CZT crystal—increases with increment of temperature. Room-temperature PL mapping measurements indicate uniformity of zinc concentration within CZT crystals. Low-temperature PL spectroscopy shows that the dominant emission peaks are excitons, which are bound to either shallow neutral donors (D⁰, X) or neutral acceptors (A⁰, X), depending on the temperature, concentration of donors and acceptors, and the incident light intensity. It was found that the luminescence of (D⁰, X) depends linearly on the incident laser intensity, while (A⁰, X) has a nonlinear dependence.     

High‐Temperature Photoluminescence of CsPbX3 (X = Cl,Br, I) Nanocrystals

Recent synthetic developments have generated intense interest in the use of cesium lead halide perovskite nanocrystals for light‐emitting applications. This work presents the photoluminescence (PL) of cesium lead halide perovskite nanocrystals with tunable halide composition recorded as function of temperature from 80 to 550 K. CsPbBr₃ nanocrystals show the highest resilience to temperature while chloride‐containing samples show relatively poorer preservation of photoluminescence at elevated temperatures. Thermal cycling experiments show that PL loss of CsPbBr₃ is largely reversible at temperatures below 450 K, but shows irreversible degradation at higher temperatures. Time‐resolved measurements of CsPbX₃ samples show an increase in the PL lifetime with temperature elevation, consistent with exciton fission to form free carriers, followed by a decrease in the apparent PL lifetime due to trapping. PL persistence measurements and time‐resolved spectroscopies implicate thermally assisted trapping, most likely to halogen vacancy traps, as the mechanism of reversible PL loss.     

Quantum-confinement effect in silicon-on-insulator films implanted with high doses of hydrogen ions

280-nm-thick silicon-on-insulator films are implanted with high doses of hydrogen with the energy 24 keV and the dose 5 × 10¹⁷ cm^?2. Peaks corresponding to optical phonons localized in the silicon nanocrystals 1.9?C2.5 nm in size are observed in the Raman spectra. The fraction of the nanocrystal phase is ??10%. A photoluminescence band with a peak at about 1.62 eV is detected. The intensity of the 1.62 eV band nonmonotonically depends on the measurement temperature in the range from 88 to 300 K. An increase in the radiative recombination intensity at temperatures <150 K is interpreted in the context of a two-level model for the energy of strongly localized electrons and holes. The activation energy of photoluminescence enhancement is 12.4 meV and corresponds to the energy of splitting of the excited state of charge carriers localized in the silicon nanocrystals.     

ESR studies of nanocrystalline silicon films obtained by pulsed laser ablation of silicon targets

Nanocrystalline silicon films formed using laser ablation of silicon targets were studied using electron spin resonance. The measurements were performed in the X band with modulation of the magnetic field at a frequency of ～100 kHz at temperatures of 300 and 77 K. Two types of spectra were observed. The first type of spectra is related to the high concentration of dangling silicon bonds in Si nanocrystals and SiO_x sheaths of nanocrystals and are inherent in nanocrystalline silicon (nc-Si) films that do not exhibit photoluminescence in the visible region of the spectrum. The second type of spectra is related to the presence of E′ centers, nonbridging oxygen hole centers (NBOHC), and peroxide radicals and is characteristic of films with photoluminescence in the visible region of the spectrum, which indicates that high-barrier SiO₂ layers exist in these films. An increase in the photoluminescence intensity and a decrease in the signal of electron spin resonance were observed in porous nc-Si films exposed to atmospheric air for a long time.     

Photoluminescence and recombination luminescence in amorphous molecular semiconductors doped with organic dyes

Photoconductivity, photoluminescence (PL), and thermally stimulated luminescence of photoconductive poly-N-epoxypropylcarbazole and poly-N-vinylcarbazole films and non-photoconductive polyvinylbutyral, polyvinyl alcohol, polystyrene, and polyethylene films doped with cationic, anionic, and neutral dyes are studied. It is found that the PL of cationic dyes in photoconductive polymer films is enhanced in comparison to nonphotoconductive ones. The PL enhancement correlates with an increase in photoconductivity, with the quenching effect of an external electric field on the PL intensity, and with an increase in the intensity of the recombination luminescence. It is assumed that this enhancement is related to the presence of predimer traps for holes in the vicinity of dye ions in the films of carbazolyl-containing polymers. A model describing the trap formation upon the photoexcitation of holes into predimer states is suggested.     

Efficient and Photostable ZnS‐Passivated CdS:Mn Luminescent Nanocrystals

Efficient and photostable ZnS‐passivated CdS:Mn (CdS:Mn/ZnS core/shell) nanocrystals were synthesized using reverse micelle chemistry. CdS:Mn/ZnS core/shell nanocrystals exhibited much improved luminescent properties (quantum yield and photostability) over organically (n‐dodecanethiol‐) capped CdS:Mn nanocrystals. This is the result of effective, robust passivation of CdS surface states by the ZnS shell and consequent suppression of non‐radiative recombination transitions. The dependence of photoluminescence (PL) intensity has been observed as a function of UV irradiation time for both organically and inorganically capped CdS:Mn nanocrystals. Whereas organically capped CdS:Mn nanocrystals exhibit a significant reduction of PL intensity, CdS:Mn/ZnS core/shell nanocrystals exhibit an increased PL intensity with UV irradiation. XPS (X‐ray photoelectron spectroscopy) studies reveal that UV irradiation of CdS:Mn/ZnS nanocrystals in air atmosphere induces the photo‐oxidation of the ZnS shell surface, leading to the formation of ZnSO₄. This photo‐oxidation product is presumably responsible for the enhanced PL emission, serving as a passivating layer.     

Strained Interface Defects in Silicon Nanocrystals

The surface of silicon nanocrystals embedded in an oxide matrix can contain numerous interface defects. These defects strongly affect the nanocrystals’ photoluminescence efficiency and optical absorption. Dangling‐bond defects are nearly eliminated by H₂ passivation, thus decreasing absorption below the quantum‐confined bandgap and enhancing PL efficiency by an order of magnitude. However, there remain numerous other defects seen in absorption by photothermal deflection spectroscopy; these defects cause non‐radiative recombination that limits the PL efficiency to <15%. Using atomistic pseudopotential simulations, we attribute these defects to two specific types of distorted bonds: Si‐Si and bridging Si‐O‐Si bonds between two Si atoms at the nanocrystal surface.     

Effect of implantation and annealing conditions on the photoluminescence emission of Si nanocrystals ion beam synthesised in SiO2

In this article, we present a systematic study of the evolution of photoluminescence (PL) emission of Si nanocrystals with elaboration conditions. Si nanocrystals synthesised in SiO₂ by ion implantation and annealing at 1100°C show a wide (0.3 eV) and a very intense PL emission centred at 1.5–1.7 eV, linked to the presence of the nanocrystals. The intensity of this emission shows a typical behaviour with the annealing time, with a fast transitory increase to reach an asymptotical saturation. There is a linear increase of the PL intensity at saturation with the dose. Two regimes are clearly observed for the evolution of the PL energy position as a function of the annealing time for different peak supersaturations (s): (i) for s<5%, there is a decrease transient followed by a saturation state of the maximum peak energy, and (ii) for s5% the PL energy presents an increase transient followed by a saturation state.     

Effect of adsorption of the donor and acceptor molecules at the surface of porous silicon on the recombination properties of silicon nanocrystals

The effect of adsorption of the donor and acceptor molecules on the spectra of photoluminescence and electron spin resonance (ESR) of microporous silicon is studied. It is found that photoluminescence of microporous silicon is quenched, the photoluminescence peak shifts to shorter wavelengths, and the intensity of the ESR signal increases after adsorption of molecules of nitrogen dioxide and pyridine. The results obtained are interpreted using a model of radiative excitonic recombination in porous silicon that takes into account the formation of both the charged (NO₂)^? and (C₅H₅N)⁺ complexes and defects (e.g., dangling bonds at the silicon surface) at the surface of silicon nanocrystals.     

Photoluminescence of amorphous and crystalline silicon nanoclusters in silicon nitride and oxide superlattices

The photoluminescence properties of silicon nitride and oxide superlattices fabricated by plasmaenhanced chemical vapor deposition are studied. In the structures annealed at a temperature of 1150°C, photoluminescence peaks at about 1.45 eV are recorded. The peaks are defined by exciton recombination in silicon nanocrystals formed upon annealing. Along with the 1.45-eV peaks, a number of peaks defined by recombination at defects at the interface between the nanocrystals and silicon-nitride matrix are detected. The structures annealed at 900°C exhibit a number of photoluminescence peaks in the range 1.3–2.0 eV. These peaks are defined by both the recombination at defects and exciton recombination in amorphous silicon nanoclusters formed at an annealing temperature of 900°C. The observed features of all of the photoluminescence spectra are confirmed by the nature of the photoluminescence kinetics.     

Luminescent properties of BexCd1−xSe thin films

We report photoluminescence (PL) study of Be_xCd_1−xSe epitaxial layers (x<0.21) grown by molecular beam epitaxy on InP substrates. Continuous wave PL spectra are taken within a 4.2-300 K temperature range. We observe an anomalous ‘s-shaped’ temperature dependence of emission energy and a severe decrease of emission intensity with the increase of temperature. We explain an ‘s-shaped’ temperature dependence of emission energy by exciton localization in the potential minima at low temperatures followed by thermal activation at higher temperatures. We attribute low emission intensity at high temperatures to exciton dissociation and electron/hole migration to non-radiative recombination centers.     

Effects of post-annealing treatment on the structure and photoluminescence properties of CdS/PS nanocomposites prepared by sol-gel method

CdS nanocrystals have been successfully grown on porous silicon (PS) by sol-gel method. The plan-view field emission scanning electron microscopy (FESEM) shows that the pore size of PS is smaller than 5 μm in diameter and the agglomerates of CdS are broadly distributed on the surface of PS substrate. With the increase of annealing time, the CdS nanoparticles grow in both length and diameter along the preferred orientation. The cross-sectional FESEM images of ZnO/PS show that CdS nanocrystals are uniformly penetrated into all PS layers and adhere to them very well. photoluminescence (PL) spectra demonstrate that the intensity of PL peak located at about 425 nm has almost no change after the annealing time increases. The range of emission wavelength of CdS/PS is from 425 nm to 455 nm and the PL intensity is decreasing with the annealing temperature increasing from 100 °C to 200 °C.     

Radiative recombination in modulation-doped GaAs/AlGaAs heterostructures in the presence of an electric field

The radiative recombination processes involving two dimensional (2D) carriers from the notch potential formed at the interface of modulation doped GaAs/AlGaAs heterostructures have been studied by means of photoluminescence (PL) and photoluminescence excitation spectroscopy in the presence of an external electric field applied perpendicular to the layers via a gate electrode. Two PL bands related to the 2D electron gas are interpreted as the radiative recombination between 2D electrons and holes from the valence band (HB1) and from residual acceptors (HB2), respectively. The band bending in the active layer, which determines the energy positions of these H-bands, can be controlled by applying an external electric field. However, also the separation between the Fermi edge, E_F, and the second 2D electron subband is deliberately varied by applying an electric field. At a sufficiently small separation, an efficient scattering path near k=0 is available for electrons at the Fermi energy. This can be observed in the PL spectra as a striking enhancement of the many-body excitonic transition, usually referred to as the Fermi edge singularity (FES). The enhancement of the FES is usually explained in terms of an efficient scattering for electrons at the Fermi edge via the nearly resonant adjacent subband. The efficiency of this process is dependent on the separation between the Fermi edge, E_F, and the next subband, which can be controlled via the applied field in our experiments.