Fine structure on the excitonic emission in AgI nanoparticles embedded in silica glass

Stable photoluminescence (PL) from AgI nanoparticles embedded in silica glass was investigated at room temperature. The Z_1,2 excitonic emission of AgI exhibits fine structure with spacing of ∼0.20 eV (1610 cm⁻¹), which is assigned to the frequency of vibration in interfacial water species. The PL excitation spectrum displays two newly observed bands at 3.45 and 4.35 eV associated with AgI-silica interaction. We suggest that the excitons in AgI are localized in the AgI/SiO₂ interface region before radiative recombination.     

Study of photophysical properties of capped CdS nanocrystals

Here, we have examined the role of capping agent on the optical properties of CdS nanoparticles by steady-state and time-resolved photoluminescence (PL) spectroscopy. The estimated particles sizes are 3.45, 2.5 and 2.39 nm for uncapped, capped with silica (SiO₂) and thiosalicylic acid (TSA), respectively. The absorption and emission spectra show a clear blue shift to shorter wavelengths in presence of TSA- and SiO₂-capped nanoparticles. It is found that the average decay time 〈τ〉 are 6.24, 4.54 and 2.84 ns for uncapped, capped with SiO₂ and TSA nanoparticles, respectively. Our analysis suggests that the hole or the electron is trapped on thiol molecule of TSA or hydroxyl group of SiO₂, then radiative recombination of the electron and hole is delayed, resulting in strong quenching of PL efficiency.     

Surface acoustic phonon modes of Ge nanocrystals embedded in SiO2

Ge nanocrystals (NCs) embedded in SiO₂ are synthesized by ion implantation, and the surface vibrational modes of the Ge NCs are investigated using the low-frequency Raman scattering (LFRS) technique. LFRS studies show distinct low-frequency Raman modes in the range 6.5-21.2 cm⁻¹ for the Ge NCs depending on the implant dose and annealing temperature. These low-frequency Raman modes are attributed to the confined surface acoustic phonon modes of Ge NCs with (0,0) spheroidal mode and (0,3) torsional modes. Our results are in excellent agreement with the recent theoretical predictions of surface vibrational modes in Ge NCs.     

Luminescence of dense, octahedral structured crystalline silicon dioxide (stishovite)

It is obtained that, as grown, non-irradiated stishovite single crystals possess a luminescence center. Three excimer pulsed lasers (KrF, 248 nm; ArF, 193 nm; F₂, 157 nm) were used for photoluminescence (PL) excitation. Two PL bands were observed. One, in UV range with the maximum at 4.7±0.1 eV with FWHM equal to 0.95±0.1 eV, mainly is seen under ArF laser. Another, in blue range with the maximum at 3±0.2 eV with FWHM equal to 0.8±0.2 eV, is seen under all three lasers. The UV band main fast component of decay is with time constant τ=1.2±0.1 ns for the range of temperatures 16-150 K. The blue band decay possesses fast and slow components. The fast component of the blue band decay is about 1.2 ns. The slow component of the blue band well corresponds to exponent with time constant equal to 17±1 μs within the temperature range 16-200 K. deviations from exponential decay were observed as well and explained by influence of nearest interstitial OH groups on the luminescence center. The UV band was not detected for F₂ laser excitation. For the case of KrF laser only a structure less tail up to 4.6 eV was detected. Both the UV and the blue bands were also found in recombination process with two components having characteristic time about 1 and 60 μs. For blue band recombination luminescence decay is lasting to ms range of time with power law decay ∼t⁻¹.For the case of X-ray excitation the luminescence intensity exhibits strong drop down above 100 K. such an effect does not take place in the case of photoexcitation with lasers. The activation energies for both cases are different as well. Average value of that is 0.03±0.01 eV for the case of X-ray luminescence and it is 0.15±0.05 eV for the case of PL. So, the processes of thermal quenching are different for these kinds of excitation and, probably, are related to interaction of the luminescence center with OH groups.Stishovite crystal irradiated with pulses of electron beam (270 kV, 200 A, 10 ns) demonstrates a decrease of luminescence intensity excited with X-ray. So, irradiation with electron beam shows on destruction of luminescent defects.The nature of luminescence excited in the transparency range of stishovite is ascribed to a defect existing in the crystal after growth. Similarity of the stishovite luminescence with that of oxygen deficient silica glass and induced by radiation luminescence of α-quartz crystal presumes similar nature of centers in those materials.     

Correlation between optical properties and Si nanocrystal formation of Si-rich Si oxide films prepared by plasma-enhanced chemical vapor deposition

We have investigated the phase separation and silicon nanocrystal (Si NC) formation in correlation with the optical properties of Si suboxide (SiO_x, 0 < x < 2) films by thermal annealing in high vacuum. The SiO_x films were deposited by plasma-enhanced chemical vapor deposition at different nitrous oxide/silane (N₂O/SiH₄) flow ratios. The as-deposited films show increased Si concentration with decreasing N₂O/SiH₄ flow ratio, while the deposition rate and surface roughness have strong correlations with the flow ratio in the N₂O/SiH₄ reaction. After thermal annealing at temperatures above 1000 °C, Fourier transform infrared spectroscopy, Raman spectroscopy, and transmission electron microscopy manifest the progressive phase separation and continuous growth of crystalline-Si (c-Si) NCs in the SiO_x films with increasing annealing temperature. We observe a transition from multiple-peak to single peak of the strong red-range photoluminescence (PL) with increasing Si concentration and annealing temperature. The appearance of the single peak in the PL is closely related to the c-Si NC formation. The PL also redshifts from ∼1.9 to 1.4 eV with increasing Si concentration and annealing temperature (i.e., increasing NC size). The good agreements of the PL evolution with NC formation and the PL peak energy with NC size distribution support the quantum confinement model.     

Carrier decay process of nanoscaled SiGe particles embedded in SiO2 matrix

Nanoscaled SiGe particles (NPs) are formed by ions implantation and annealing treatment methods. For any sample, the total dose of Si and Ge dopants is 3×10¹⁶ cm⁻². Strong photoluminescence (PL) peaks centered around red emission region are observed. This PL peak red shifts from 653 nm–695 nm with the increase of Ge-doping dose, which is ascribed to the quantum confinement effect. The PL lifetime spectra exhibit a stretched exponential decay with characteristic decay time τ varying from 50.2–23.1 μs and dispersion factor β in the range of 0.67–0.86.     

Photoluminescence of Si from Si nanocrystal-doped SiO2/Si multilayered sample

A multilayered Si nanocrystal-doped SiO₂/Si (or Si-nc:SiO₂/Si) sample structure is studied to acquire strong photoluminescence (PL) emission of Si via modulating excess Si concentration. The Si-nc:SiO₂ results from SiO thin film after thermal annealing. The total thickness of SiO layer remains 150 nm, and is partitioned equally into a number of sublayers (N = 3, 5, 10, or 30) by Si interlayers. For each N-layered sample, a maximal PL intensity of Si can be obtained via optimizing the thickness of Si interlayer (or d_Si). This maximal PL intensity varies with N, but the ratio of Si to O is nearly a constant. The brightest sample is found to be that of N = 10 and d_Si = 1 nm, whose PL intensity is ∼5 times that of N = 1 without additional Si doping, and ∼2.5 times that of Si-nc:SiO₂ prepared by co-evaporating of SiO and Si at the same optimized ratio of Si to O. Discussions are made based on PL, TEM, EDX and reflectance measurements.     

Room temperature photoluminescence from amorphous silicon nanoparticles in SiOx thin films

Amorphous SiO_x thin films with four different oxygen contents (x=1.15, 1.4, 1.5, and 1.7) have been prepared by thermal evaporation of SiO in vacuum and then annealed at 770 or 970 K in argon for various times ?40 min. The influence of annealing conditions and the initial film composition on photoluminescence (PL) from the annealed films has been explored. Intense room temperature PL has been observed from films with x?1.5, visible with a naked eye. It has been shown that PL spectra of most samples consists of two main bands: (i) a ‘green’ band centered at about 2.3 eV, whose position does not change with annealing conditions and (ii) an ‘orange-red’ band whose maximum moves from 2.1 to 1.7 eV with increasing annealing time and temperature and decreasing initial oxygen content. These observations have been explained assuming recombination via defect states in the SiO_x matrix for the first band and emission from amorphous Si nanoparticles for the second one.     

Modulation of the photoluminescence of Si quantum dots by means of CO2 laser pre-annealing

Si quantum dots (QDs) embedded in SiO₂ can be normally prepared by thermal annealing of SiO_x (x < 2) thin film at 1100 °C in an inert gas atmosphere. In this work, the SiO_x thin film was firstly subjected to a rapid irradiation of CO₂ laser in a dot by dot scanning mode, a process termed as pre-annealing, and then thermally annealed at 1100 °C for 1 h as usual. The photoluminescence (PL) intensity of Si QD was found to be enhanced after such pre-annealing treatment. This PL enhancement is not due to the additional thermal budget offered by laser for phase separation, but attributed to the production of extra nucleation sites for Si dots within SiO_x by laser irradiation, which facilitates the formation of extra Si QDs during the subsequent thermal annealing.     

Characterization of semiconductor nanostructures formed by using ultrathin Si oxide technology

We present a method to form semiconductor nanodots on Si substrates by using ultrathin Si oxide technology and the results on their optical properties. We can form ultra-small semiconductor nanodots with the size of ∼5 nm and ultra-high density of ∼10¹² cm⁻² on Si surfaces covered with ultrathin SiO₂ films of ∼0.3 nm thickness. We focus on photoluminescence and electroluminescence properties of Ge nanodots embedded in Si films. These structures exhibit intense luminescence in the energy region of about 0.8 eV.     

Dependence of photoluminescence from a-Si nanoparticles on the annealing time and exciting wavelength

Thin films of SiO_x having thickness of 0.2 μm and oxygen content x=1.5 or 1.7 are prepared by thermal evaporation of SiO in vacuum. Then some samples are furnace annealed for various times (in the range ) at 770 and 970 K and some others are rapid thermal annealed at 970 K for 30 and 60 s. Photoluminescence (PL) measurements are carried out at room temperature using the 442 nm line of a He-Cd laser and the 488 nm of an Ar laser for excitation. The effect of the annealing conditions and wavelength of the exciting light on the shape of the PL from these films is explored. The deconvolution of the PL spectra measured with the 442 nm line from samples annealed at 770 K for reveals two distinct PL bands peaked at around 2.3 and 2.5 eV, which do not shift appreciably with increasing annealing time. In addition, at longer annealing times, a weak third band is resolved centred in the range 2.0-2.1 eV. It exists in the spectra of all samples annealed at 970 K being more prominent in the samples with x=1.5. The intensity of this band shows different dependences on the annealing time in the films with different initial composition. The results obtained are discussed in terms of radiative recombination via defect states in the SiO_x matrix (the 2.5 eV band) or at the a-Si-SiO_x interface (the 2.3 eV band). The band centred in the 2.0-2.1 eV range is related to recombination in amorphous silicon nanoparticles grown upon annealing.     

A combined approach to fabricating Si nanocrystals with high photoluminescence intensity

This work demonstrates that by combining three methods with different mechanisms to enhance the photoluminescence (PL) intensity of Si nanocrystals embedded in SiO₂ (or Si-nc:SiO₂), a promising material for developing Si light sources, a very high PL intensity can be achieved. A 30-layered sample of Si-nc:SiO₂/SiO₂ was prepared by alternatively evaporating SiO and SiO₂ onto a Si(1 0 0) substrate followed by thermal annealing at 1100 °C. This multilayered sample possessed a fairly high PL efficiency of 14% as measured by Greenham's method, which was 44 times that of a single-layered one for the same amount of excess Si content. Based on this multilayered sample, treatments of CeF₃ doping and hydrogen passivation were subsequently applied, and a high PL intensity which was 167 times that of a single-layered one for the same amount of excess Si content was achieved.     

On the origin of the 2.2-2.3 eV photoluminescence from chemically etched germanium

The photoluminescence (PL) at ∼2.2-2.3 eV from Ge-based nanocrystalline materials is described in the literature as nanocrystal size-independent. We have observed visible luminescence from two different types of stain-etched Ge samples, one prepared after Sendova-Vassileva et al. (Thin Solid Films 255 (1995) 282) in a solution of H₂O₂:HF at 50:1 volume ratio, and the other in a solution of HF:H₃PO₄:H₂O₂ at 34:17:1 volume ratio. Energy dispersive X-ray analysis (EDX), Raman and FTIR spectroscopy, and the near edge X-ray absorption structure (XANES), indicate that the chemically etched Ge layers of the former type of samples are composed of non-stoichometric Ge oxides, i.e. GeO_x (0<x<2), and free from any Ge nanoconstructions. It is also suggested from XANES that the latter type of chemically etched Ge samples comprise 8-9 nm nanocrystals of Ge, surface-covered with mainly oxygen. Photoluminescence occurred at ∼2.3 eV for all samples. The PL behavior of the latter type of chemically etched Ge on annealing in different chemical environments (air or H) allowed us to conclude that the PL from these materials, as well as that from those Ge-based nanocrystalline materials reported in the literature, is from GeO_xs.     

Visible luminescence of Al2O3 nanoparticles embedded in silica glass host matrix

This paper deals with the sol-gel elaboration and defects photoluminescence (PL) examination of Al₂O₃ nanocrystallites (size ∼30 nm) confined in glass based on silica aerogel. Aluminium oxide aerogels were synthesized using esterification reaction for hydrolysis of the precursor and supercritical conditions of ethyl alcohol for drying. The obtained nanopowder was incorporated in SiO₂ host matrix. After heating under natural atmosphere at 1150 °C for 2 h, the composite Al₂O₃/SiO₂ (AS) exhibited a strong PL bands at 400-600 and 700-900 nm in 78-300 K temperature range. PL excitation (PLE) measurements show different origins of the emission. It was suggested that OH-related radiative centres and non-bridging oxygen hole centres (NBOHCs) were responsible for the bands at 400-600 and 700-900 nm, respectively.     

Understanding the role of particle size on photophysical properties of CdS:Eu nanocrystals

Here, we report the role of particle size on the photoluminescence (PL) properties of CdS:Eu³⁺ nanocrystals by steady-state and time-resolved PL spectroscopy. It is found that the average decay time 〈τ〉 of undoped CdS nanocrystals increases with increasing the size. The fast component (nanosecond) is assigned due to trapping and slow component (above 10 ns) is due to defect-related emission. The decrease of fast component from 6.6 to 1.32 ns and the slow component from 20 to 14.6 ns of CdS (host) is observed in presence of Eu ions, indicating that the energy transfer occurs from CdS nanoparticles to Eu³⁺ ions. The decay time of Eu³⁺ in CdS shows two decay components (microsecond scale) and we believe that the fast component is attributed to surface-bound Eu³⁺ ions and slow component is due to lattice-bound Eu³⁺ ions. Analysis suggests that PL efficiency of Eu³⁺ ions depends on size of nanoparticles.     

Spectral probing of carrier traps in Si–Ge alloy nanocrystals

Photogenerated carriers in Si–Ge alloy nanocrystals (NCs) prepared by co‐sputtering method were investigated by mean of transient induced absorption. The carrier relaxation features multiple components, with three decay life times of τ ≈ 600 fs, 12 ps, and 15 ns, established for Si_0.2Ge_0.8 alloy NCs of a mean crystal size of 9 nm and standard deviation of 3 nm. Deep carrier traps, identified at the boundary between the NCs and the SiO₂ host with the ionization energy of about 1 eV, are characterized by a long‐range Coulombic potential. These are responsible for rapid depletion of free carrier population within a few picoseconds after the excitation, which explains the low emissivity of the investigated materials, and also sheds light on the generally low luminescence of Si/Ge and Ge NCs. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Microstructure and multiphoton luminescence of Au nanocrystals prepared by using glancing deposition method

Au crystal columns embedded in SiO₂ with an average length of 480 nm and diameter of 30 nm were prepared by radio frequency co-sputtering technique with glancing angle. The photoluminescence (PL) of the Au-SiO₂ crystal column film exhibited polarization characteristic. With an increase of the laser power, the slope ∂ log(PL intensity)/∂ log(laser power) changed from 2 to 3, which indicated that the PL of Au-SiO₂ crystal columns were induced by two- and three-photon absorption, respectively.     

Localized exciton dynamics in AlInGaN alloy

Carrier recombination dynamics in AlInGaN alloy has been studied by photoluminescence (PL) and time-resolved PL (TRPL) at various temperatures. The fast red-shift of PL peak energy is observed and well fitted by a physical model considering the thermal activation and transfer processes. This result provides evidence for the exciton localization in the quantum dot (QD)-like potentials in our AlInGaN alloy. The TRPL signals are found to be described by a stretched exponential function of exp[(−t/τ)^β], indicating the presence of a significant disorder in the material. The disorder is attributed to a randomly distributed QDs or clusters caused by indium fluctuations. By studying the dependence of the dispersive exponent β on temperature and emission energy, we suggest that the exciton hopping dominate the diffusion of carriers localized in the disordered QDs. Furthermore, the localized states are found to have 0D density of states up to 250 K, since the radiative lifetime remains almost unchanged with increasing temperature.     

Effect of the annealing environment on the optical properties of ZnO/GaAs grown by MOCVD

The optical properties of ZnO grown on (1 0 0) GaAs substrate using metalorganic chemical vapor deposition are investigated by photoluminescence (PL) spectroscopy. Postgrowth annealing in nitrogen and oxygen was performed for different times and temperatures in order to incorporate As from the substrate into the ZnO thin films. The PL spectra of the samples annealed in different ambients reveal that the effect of As diffusion into the ZnO thin films is more pronounced when the annealing is performed in oxygen at 550 °C. The 11 K PL spectra show the appearance of a transition at ∼3.35 eV after annealing in oxygen at 550 °C for 1 h. A further increase in the annealing temperature leads to the disappearance of this line, while for annealing times longer than 2 h at 550 °C, it is no longer prominent. The increase in intensity of this new transition is also accompanied by the enhancement of radiative centers related to structural defects, such as the stacking fault-related transition at 3.31 eV and the Y-line. Temperature dependent PL illustrates the excitonic nature of the new transition at ∼3.35 eV, which is therefore assigned to (A⁰, X) transition, where the acceptor is possibly the 2V_Zn-As_Zn complex, with an activation energy E_A in the range of 160-240 meV. Furthermore, the enhancement of the radiative centers related to structural defects is regarded as evidence that As atoms tend to segregate in the vicinity of structural defects to relieve local strain.     

Temperature dependent photoluminescence of PECVD a-SiOx:H (x<2)

The temperature dependent visible photoluminescence (PL) property of a-SiO_x:H (x<2) samples prepared in a PECVD system by using SiH₄+CO₂ gas mixture is investigated at a temperature range of 20 K-400 K. One of the two explicitly distinguished PL bands, with varying peak photon energies between 1.70 and 2.05 eV, can be detected at only low temperatures below 200 K, which is attributed to tail-to-tail radiative recombination. Thermal quenching parameter (T_L) of the tail-to-tail PL band is calculated as varying between 120 and 280 K as the atomic oxygen concentration ([O]at.%) of the samples increases. Stokes shift (ΔE_Stokes) of the tail-to-tail PL band is found to change from 85 meV to 420 meV due to band tail widening. The other PL band emerges at 2.1 eV and can be detected at higher temperatures with thermal activation behavior. The activation energies calculated about room temperature vary in the range of 8 meV-50 meV with oxygen concentration. Thermal activation of the 2.1 eV PL band is attributed to the behavior of thermally activated incoherent hopping migration of electrons. These electrons combine with self trapped holes (STHs) to form self trapped excitons (STEs). STEs are localized at intrinsic defects of SiO₂ structure such as oxygen vacancies (E′ centers) and non-bridging oxygen hole centers (NBOHC).