Optical properties of acceptor-exciton complexes in ZnO/SiO2 quantum dots

The binding energy E_b of the acceptor-exciton complex (A⁻,X) as a function of the radius (or of the impurity position of the acceptor) and the normalized oscillator strength of (A⁻,X) in spherical ZnO quantum dots (QDs) embedded in a SiO₂ matrix are calculated using the effective-mass approximation under the diagonalzation matrix technique, including a three-dimensional confinement of the carrier in the QD and assuming a finite depth. Numerical results show that the binding energy of the acceptor-exciton complexes is particularly robust when the impurity position of the acceptor is in the center of the ZnO QDs. It has been clearly shown from our calculations that these physical parameters are very sensitive to the quantum dot size and to the impurity position. These results could be particularly helpful, since they are closely related to experiments performed on such nanoparticles. This may allow us to improve the stability and efficiency of the semiconductor quantum dot luminescence which is considered critical.     

Sensitizing effects of ZnO quantum dots on red-emitting Pr-doped SiO2 phosphor

In this study, red cathodoluminescence (CL) (λ_emission=614 nm) was observed from Pr³⁺ ions in a glassy (amorphous) SiO₂ host. This emission was enhanced considerably when ZnO quantum dots (QDs) were incorporated in the SiO₂:Pr³⁺ suggesting that the ZnO QDs transferred excitation energy to Pr³⁺ ions. That is, ZnO QDs acted to sensitize the Pr³⁺ emission. The sol–gel method was used to prepare ZnO–SiO₂:Pr³⁺ phosphors with different molar ratios of Zn to Si. The effects of the ZnO QDs concentration and the possible mechanisms of energy transfer from ZnO to Pr³⁺ are discussed. In addition, the electronic states and the chemical composition of the ZnO–SiO₂:Pr³⁺ phosphors were analyzed using X-ray photoelectron spectroscopy (XPS).     

Luminescence studies and formation mechanism of symmetrically dispersed ZnO quantum dots embedded in SiO2 matrix

Surface effects significantly influence the functionality of semiconductor nanocrystals. In the current work we present synthesis of ZnO quantum dots (QD) vis-a-vis symmetrically dispersed ZnO quantum dots embedded in SiO₂ matrix and discussed their optical properties to understand the role of the surface effects. These nanomaterials were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), fourier transform infrared (FTIR), absorption (UV-visible) and photoluminescence (PL) spectroscopy. TEM studies confirm the formation of ZnO nanophosphors inside the SiO₂ matrix in highly symmetrical manner. These symmetrically dispersed ZnO@SiO₂ nanophosphors exhibited enhanced stable emission over uncoated sample and would permit the conjugation of the nanocrystals to biological entities after functionalization. Furthermore, the mechanism behind the formation of symmetrically dispersed ZnO quantum dots embedded in SiO₂ matrix was discussed in detail.     

Effect of As doping on the photoluminescence of nanocrystalline Ge embedded in SiO2 matrix

Samples of nanocrystalline ⁷⁴Ge embedded in amorphous SiO₂ film were prepared by ⁷⁴Ge ion implantation and subsequent primary thermal annealing. These samples were irradiated by neutron flux in a nuclear reactor then the second annealing followed. Irradiation with thermal neutrons leads to doping of nanocrystalline ⁷⁴Ge with As impurities due to nuclear transmutation of isotope ⁷⁴Ge into ⁷⁵As. Transmission electron microscope, X-ray fluorescence, X-ray photoelectron spectroscopy, laser Raman scattering and photoluminescence of the obtained samples were measured. It was observed that with the increase in As-donors concentration, photoluminescence intensity first increased but then significantly decreased. An explanatory model of this non-monotonic behavior was discussed.     

The origin of photoluminescence in Ge-implanted SiO2 layers

Ge ions were implanted at 100 keV with 3×10¹⁶ cm⁻² into a 300  nm thick SiO₂ layer on Si. Visible photoluminescence (PL) around 2.1 eV from an as-implanted sample is observed, and faded out by subsequent annealing at 900°C for 2 h. However, PL shows up again after annealing above 900°C at the same peak position. Compared with the as-implanted sample, significant increase of Ge–Ge bonds is measured in X-ray photoelectron spectroscopy, and the formation of Ge nanocrystals with a diameter of 5 nm are observed in transmission electron microscopy from the sample annealed at 1100°C. We conclude that the PL peak from the sample annealed above 900°C is caused by the quantum confinement effects from Ge nanocrystals, while the luminescence from the as-implanted sample is due to some radiative defects formed by Ge implantation.     

Quantum cascade multi-electron injection into Si-quantum-dot floating gates embedded in SiO2 matrices

The use of silicon-quantum-dots (Si-QDs) as floating gates in metal-oxide-semiconductor-field-effect-transistors (MOSFETs) has been attracting great attention. It has been reported that large decreases in drain current are observed within a very short time in Si-QDs memories, indicating that the collective motion of electrons occurs during electron injection into Si-QDs. In this study, we present a theoretical report which indicates that the interaction length between QDs is about 5-10 nm. From these results, we propose a mechanism for “quantum cascade multi-electron injection”.     

Photoluminescence quenching of CdTe/CdS core-shell quantum dots in aqueous solution by ZnO nanocrystals

Photoluminescence (PL) properties of 3-mercaptopropionic acid (MPA) coated CdTe/CdS core-shell quantum dots (QDs) in aqueous solution in the presence of ZnO colloidal nanocrystals were studied by steady-state and time-resolved PL spectroscopy. The PL quenching of CdTe/CdS core-shell QDs with addition of purified ZnO nanocrystals resulted in a decrease in PL lifetime and a small red shift of the PL band. It was found that CdTe(1.5 nm)/CdS type II core-shell QDs exhibited higher efficiency of PL quenching than the CdTe(3.0 nm)/CdS type I core-shell QDs, indicating an electron transfer process from CdTe/CdS core-shell QDs to ZnO nanocrystals. The experimental results indicated that the efficient electron transfer process from CdTe/CdS core-shell QDs to ZnO nanocrystals could be controlled by changing the CdTe core size on the basis of the quantum confinement effect.     

The studies of Ge quantum dots on strained Si0.7Ge0.3 layer by photoluminescence and deep level transient spectroscopy

Systematic studies of Ge quantum dots (QDs) grown on strained Si_0.3Ge_0.7 layer have been carried out by photoluminescence (PL) and deep level transient spectroscopy (DLTS). In PL measurements, two peaks around 0.7 eV are distinguished, which are assigned to two types of QDs observed by atomic force microscopy (AFM). Large blueshifts of the PL peaks from small QDs with the increase of excitation power are observed and attributed to the band bending effects typical for type-II band alignment. From DLTS measurements, the energy levels of holes in both types of QDs are derived, which shift with the change of the number of holes in QDs due to their charge energy. By comparing results from PL and DLTS measurements, further understanding of band alignment with the increase of the number of excitons in QDs is deduced.     

The influence of the annealing conditions on the photoluminescence of ion-implanted SiO2:Si nanosystem at additional phosphorus implantation

The influence of P ion doping on the photoluminescence (PL) of the system of nanocrystals in SiO₂ matrix (SiO₂:Si) both without annealing and after annealing at various temperatures (provided before and after additional P implantation) is investigated. The Si and P implantation was carried out with ion energies of 150 keV and doses Φ_Si=10¹⁷ cm⁻² and Φ_P=(0.1–300)×10¹⁴ cm⁻² (current density j3 μAcm⁻²). The system after Si implantation was formed at 1000°C and 1100°C (2 h). For the case of SiO₂:Si system as-implanted by P, the intensity of PL was drastically quenched, but partially retained. As for the step-by-step annealing (at progressively increased temperatures) carried out after P implantation, the sign and degree of doping effect change with annealing temperature. The possible mechanisms of these features are discussed.     

Annealing of In0.45Ga0.55As/GaAs quantum dots overgrown with large monolayer (11 ML) coverage for applications in thermally stable optoelectronic devices

The effects of thermal annealing on the large monolayer (11 ML) coverage of In_0.45Ga_0.55As/GaAs quantum dots (QDs) is being investigated in this study. Low temperature (8 K) photoluminescence (PL) spectra exhibits suppressed blueshift of the strongest PL emission peak even at high temperature annealing (800 °C). TEM and DCXRD characterizations showed the existence of the dots with good crystalline quality at annealing temperatures of 800-850 °C. The physics of annealing induced compositional modification of the InGaAs QDs with various monolayer coverage has been studied by a theoretical model and simulation. All our studies establish the thermal stability of large ML coverage InGaAs QDs, which is desirable for optoelectronic devices required for selective wavelength tuning in specific applications.     

Synthesis and photoluminescence properties of aqueous CdWO4 quantum dots with WO6 luminescence center

Aqueous CdWO₄ QDs were synthesized by the reaction of CdCl₂ and Na₂WO₄ in the presence of mercaptoacetic acid (TGA) as capping reagent. The crystal morphology, particle size and its distribution of as-prepared products were characterized by transmission electron microscopy (TEM, SAED) atomic force microscopy (AFM), high-resolution transmission electron microscopy (HRTEM), and photon correlation spectroscopy (PCS), respectively. Qualitative assays for functional groups on the QDs’ surface were measured by fourier transform infrared spectroscopy (FTIR). Photoluminescence properties of QDs were studied by photoluminescence spectroscopy (PL). The results showed that the single QD with diameter of about 8 ± 2 nm was single-crystal. The particle size distribution of QDs was normal. Infrared absorption bands of carboxylic group on the surface of CdWO₄ QDs were observed around 1610-1550 cm⁻¹ (nonsymmetrical vibration of -COO⁻) and 1400 cm⁻¹ (symmetric vibration of C-O). With reaction-time going, PL peak position shifted from 498 to 549 nm and intensity of PL increased first and then decreased. PL peak position of QDs was blue-shift compared with 570 nm WO₆⁶⁻ luminescence center of bulk CdWO₄.     

Improvement of photoluminescence mechanism of CTA-treated Si-implanted SiO2 films by using RTA

In this paper, a shift in the photoluminescence (PL) peak from blue to near-infrared region was observed in the Si⁺-implanted 400-nm-thick SiO₂ films with the rapid thermal annealing (RTA) method only. As the Si⁺-fluence was 1×10¹⁶ ions/cm², a blue band was observed in the films after RTA at 1050 °C for 5 s in dry-N₂ atmosphere; then, the band shifted from blue to orange upon increasing the holding temperature of RTA to 1250 °C in the films after the isochronal RTA in dry N₂. Furthermore, while the fluence was increased to 3×110¹⁶ ions/cm² and the holding temperature was at the same range between 1050 and 1250 °C, the PL peak occurred between red and near-infrared regions. Although the RTA and conventional thermal annealing (CTA) methods produce a similar mechanism, the CTA method needs a much longer annealing-time and a higher Si⁺-implanted dose than the RTA method for producing the same shift and intensity of PL peak from the as-implanted sample. Therefore, the RTA method can produce the mechanism in the Si⁺-implanted sample with the PL energy between blue and near-infrared band in place of the CTA method.     

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.     

Synthesis and optical characterization of vertically grown ZnO nanowires in high crystallinity through vapor-liquid-solid growth mechanism

The gas-phase growth and optical characteristics of 1-dimensional ZnO nanostructure have been investigated. The ZnO nanowires (NWs) were grown vertically on Au coated silicon substrates by vapor-liquid-solid (VLS) growth mechanism using chemical vapor deposition (CVD). The ZnO NWs were grown in the crystal direction of [0 0 0 1]. The ZnO NWs exhibit the uniform size of less than 100 nm in diameter and up to 5 μm in length. Photoluminescence (PL) spectrum of ZnO NWs shows the strong band-edge emission at ∼380 nm (∼3.27 eV) without significant deep-level defect emission. The exciton lifetime of ZnO NWs was measured to be approximately 150 ± 10 ps.     

Crystal structure and thermal behavior of two new organic monosulfates NH3(CH2)5NH3SO4 1.5H2O and NH3(CH2)9NH3SO4 H2O

The chemical preparation, the calorimetric studies and the crystal structure are given for two new organic sulfates NH₃(CH₂)₅NH₃SO₄ 1.5H₂O (DAP-S) and NH₃(CH₂)₉NH₃SO₄·H₂O (DAN-S). DAP-S is monoclinic P2₁/n with unit cell dimensions: a=11.9330(2) Å; b=10.9290(2) Å; c=17.5260(2) Å; β=101.873(1)°; V=2236.77(6) Å³; and Z=8. Its atomic arrangement is described as inorganic layers of units and water molecules separated by organic chains. DAN-S is monoclinic P2₁/c with unit cell parameters: a=5.768(2) Å; b=25.890(10) Å; c=11.177(5) Å; β=115.70(4)°; V=1504.0(11) Å³ and Z=4. Its structure exhibits infinite chains, parallel to the [100] direction where the organic cations are interconnected. In both structures a network of strong and weak hydrogen bonds connects the different components in the building of the crystal.     

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.     

Elaboration and characterization of TiO2 nanoparticles incorporated in SiO2 host matrix

Nanometer-scale TiO₂ particles have been synthesized by sol-gel method. It was incorporated in a glass-based silica aerogel. The composite was characterized by various techniques such as particle size analysis, scanning electron microscopy (SEM), atomic force microscopy (AFM), transmission electron microscopy (TEM), X-ray diffraction (XRD), infrared spectroscopy (IR) and photoluminescence (PL). The bulk glass presents a strong luminescence at wavelengths ranging from 750 to 950 nm. This PL was attributed to various non-bridging oxygen hole centers (NBOHCs) defects resulting from thermal treatment and crystallization of TiO₂ at the interface between titania nanoparticles and silica host matrix.     

Growth and optical properties of Ge/Si quantum dots formed on patterned SiO2/Si(0 0 1) substrates

Single and stacked layers of Ge/Si quantum dots were grown in SiO₂ windows patterned by electron-beam lithography on oxidized Si (0 0 1) substrates. The growth of a silicon buffer layer prior to Ge deposition is found to be an additional parameter for adjusting the Ge-dot nucleation process. We show that the silicon buffer layer evolves towards [1 1 3]-faceted pyramids, which reduces the area of the topmost (0 0 1) surface available for Ge nucleation. By controlling the top facet area of the Si buffer layers, only one dot per circular window and a high cooperative arrangement of dots on a striped window can be achieved. In stacked layers, the dot homogeneity can be improved through the adjustment of the Ge deposited amount in the upper layers. The optical properties of these structures measured by photoluminescence spectroscopy are also reported. In comparison with self-assembled quantum dots, we observed, both in single and stacked layers, the absence of the wetting-layer component and an energy blue shift, confirming therefore the dot formation by selective growth.     

Effects of Na2CO3 flux addition on the structure and photoluminescence properties for Eu-doped YVO4 phosphor

The luminescence properties of (Y_0.9Eu_0.1)VO₄ phosphor with Na₂CO₃ flux prepared using the solid-state reaction were investigated. The XRD patterns show that all of the peaks are attributed to the YVO₄ phase. The best crystallinity was obtained with 2 wt% Na₂CO₃ flux addition. The surface morphology of (Y_0.9Eu_0.1)VO₄ phosphor changed from fluffy to a bar shape structure after Na₂CO₃ flux addition due to the tetragonal crystal system of YVO₄. The calcined powders emit bright red luminescence centered at 618 nm due to the ⁵D₀→⁷F₂ electric dipole transition under an excitation wavelength of 318 nm; its intensity was increased about 15% with 2 wt% Na₂CO₃ flux addition. Red shift behavior was observed for the charge transfer state (CTS) absorption, which was due to the grain size of (Y_0.9Eu_0.1)VO₄ phosphor increasing with increasing flux content. For 2 wt% Na₂CO₃ flux addition, the red emission of the (Y_0.9Eu_0.1)VO₄ phosphor had CIE chromaticity coordinates of (0.66, 0.34), which are very close to the NTSC system standard red chromaticity coordinates of (0.67, 0.33).     

In-situ XAS study on the Cu and Ce local structural changes in a CuO-CeO2/Al2O3 catalyst under propane reduction and re-oxidation

The redox behaviour of a CuO-CeO₂/Al₂O₃ catalyst is studied under propane reduction and re-oxidation. The evolution of the local Cu and Ce structure is studied with in-situ transmission X-ray absorption spectroscopy (XAS) at the Cu K and Ce L₃ absorption edges.CuO and CeO₂ structures are present in the catalyst as such. No structural effect on the local Cu structure is observed upon heating in He up to 873 K or after pre-oxidation at 423 K.Exposure to propane at reaction temperature (600-763 K) fully reduces the Cu²⁺ cations towards metallic Cu⁰. Quick EXAFS spectra taken during reduction show a small amount of intermediate Cu¹⁺ species. Parallel to the CuO reduction, CeO₂ is also reduced in the same temperature range. About 25% of the Ce⁴⁺ reduces rapidly to Ce³⁺ in the 610-640 K temperature interval, while beyond 640 K a further slower reduction of Ce⁴⁺ to Ce³⁺ occurs. At 763 K, Ce reduction is still incomplete with 32% of Ce³⁺.Re-oxidation of Cu and Ce is fast and brings back the original oxides.The propane reduction of the CuO-CeO₂/Al₂O₃ catalyst involves both CuO and CeO₂ reduction at similar temperatures, which is ascribed to an interaction between the two compounds.