Time-dependent Photoluminescence Measurements Research Articles

Ligand-assisted reprecipitation synthesis of highly luminescent and stable CsPbBr3@SiO2 nanoparticles with formation kinetics analysis

Cesium lead bromide (CsPbBr3) perovskite nanocrystals are becoming a popular alternative to chalcogenide quantum dots because of their bright green fluorescence and high color purity. However, owing to the poor stability caused by their highly ionic nature and the dynamic binding of long-chain capping ligands, their practical applications are limited. Although (3-aminopropyl)triethoxysilane (APTES) is a frequently used insulating material for wrapping CsPbBr3nanocrystals, it often causes surface etching. To address this issue, we introduced oleic acid into the anti-solvent toluene to inhibit the etching effect of APTES using a modified room-temperature ligand-assisted reprecipitation process. We utilized in situ time-dependent photoluminescence measurements to study the formation kinetics of CsPbBr3nanocrystals and determine the optimal ligands ratio. This innovative approach enables precise control over CsPbBr3@SiO2nanoparticles synthesis, yielding uniformly shaped nanocrystals with a silica shell, a consistent size around 10.17 ± 1.6 nm, and enhanced photoluminescence quantum yields ranging from 90% and 100%. The photoluminescence lifetimes of our CsPbBr3@SiO2nanoparticles were significantly prolonged owing to a reduction in non-radiative recombination. This boosts their stability in thermal and polar solvent environments, making them superior candidates for use in photonic devices.

Double-Mesoscopic Hole-Transport-Material-Free Perovskite Solar Cells: Overcoming Charge-Transport Limitation by Sputtered Ultrathin Al2O3 Isolating Layer.

The electrically insulating space layer takes a fundamental role in monolithic carbon-graphite based perovskite solar cells (PSCs) and it has been established to prevent the charge recombination of electrons at the mp-TiO2/carbon-graphite (CG) interface. Thick 1 μm printed layers are commonly used for this purpose in the established triple-mesoscopic structures to avoid ohmic shunts and to achieve a high open circuit voltage. In this work, we have developed a reproducible large-area procedure to replace this thick space layer with an ultra-thin dense 40 nm sputtered Al2O3 which acts as a highly electrically insulating layer preventing ohmic shunts. Herewith, transport limitations related so far to the hole diffusion path length inside the thick mesoporous space layer have been omitted by concept. This will pave the way toward the development of next generation double-mesoscopic carbon-graphite-based PSCs with highest efficiencies. Scanning electron microscope, energy dispersive X-ray analysis, and atomic force microscopy measurements show the presence of a fully oxidized sputtered Al2O3 layer forming a pseudo-porous covering of the underlying mesoporous layer. The thickness has been finely tuned to achieve both electrical isolation and optimal infiltration of the perovskite solution allowing full percolation and crystallization. Photo voltage decay, light-dependent, and time-dependent photoluminescence measurements showed that the optimal 40 nm thick Al2O3 not only prevents ohmic shunts but also efficiently reduces the charge recombination at the mp-TiO2/CG interface and, at the same time, allows efficient hole diffusion through the perovskite crystals embedded in its pseudo-pores. Thus, a stable VOC of 1 V using CH3NH3PbI3 perovskite has been achieved under full sun AM 1.5 G with a stabilized device performance of 12.1%.

Interstitial Occupancy by Extrinsic Alkali Cations in Perovskites and Its Impact on Ion Migration.

Recent success in achieving highly stable Rb-containing organolead halide perovskites has indicated the possibility of incorporating small monovalent cations, which cannot fit in the lead-halide cage with an appropriate tolerance factor, into the perovskite lattice while maintaining a pure stable "black" phase. In this study, through a combined experimental and theoretical investigation by density functional theory (DFT) calculations on the incorporation of extrinsic alkali cations (Rb+ , K+ , Na+ , and Li+ ) in perovskite materials, the size-dependent interstitial occupancy of these cations in the perovskite lattice is unambiguously revealed. Interestingly, DFT calculations predict the increased ion migration barriers in the lattice after the interstitial occupancy. To verify this prediction, ion migration behavior is characterized through hysteresis analysis of solar cells, electrical poling, temperature-dependent conductivity, and time-dependent photoluminescence measurements. The results collectively point to the suppression of ion migration after lattice interstitial occupancy by extrinsic alkali cations. The findings of this study provide new material design principles to manipulate the structural and ionic properties of multication perovskite materials.

Controlled Gas Molecules Doping of Monolayer MoS2 via Atomic-Layer-Deposited Al2O3 Films.

MoS2 as atomically thin semiconductor is highly sensitive to ambient atmosphere (e.g., oxygen, moisture, etc.) in optical and electrical properties. Here we report a controlled gas molecules doping of monolayer MoS2 via atomic-layer-deposited Al2O3 films. The deposited Al2O3 films, in the shape of nanospheres, can effectively control the contact areas between ambient atmosphere and MoS2 that allows precise modulation of gas molecules doping. By analyzing photoluminescence (PL) emission spectra of MoS2 with different thickness of Al2O3, the doped carrier concentration is estimated at ∼2.7 × 1013 cm-2 based on the mass action model. Moreover, time-dependent PL measurements indicate an incremental stability of single layer MoS2 as the thicknesses of Al2O3 capping layer increase. Effective control of gas molecules doping in monolayer MoS2 provides us a valuable insight into the applications of MoS2 based optical and electrical devices.

Ab initio and experimental studies of polarization and polarization related fields in nitrides and nitride structures

Spontaneous and piezoelectric polarization in the nitrides is analyzed. The slab model was designed and proved to be appropriate to obtain the spontaneous polarization in AlN, GaN and InN. The spontaneous polarization and polarization related electric fields in AlN, GaN and InN were determined using DFT slab calculations. The procedure generates single value of spontaneous polarization in the nitrides. It was shown that Berry phase polarization may be applied to determination of spontaneous polarization by appropriate addition of polarization induced electric fields. The electric fields obtained from slab model are consistent with the Berry phase results of Bernardini et al. The obtained spontaneous polarization values are: 8.69*10-3 C/m2, 1.88*10-3 C/m2, and 1.96*10-3 C/m2 for AlN, GaN and InN respectively. The related Berry phase polarization values are 8.69*10-2 C/m2, 1.92*10-2 C/m2, and 2.86*10-2 C/m2, for these three compounds, respectively. The GaN/AlN multiquantum wells (MQWs) were simulated using ab intio calculations. The obtained electric fields are in good agreement with those derived from bulk polarization values. GaN/AlN MQWs structures, obtained by MBE growth were characterized by TEM and X-ray measurements. Time dependent photoluminescence measurements were used to determine optical transition energies in these structures. The PL obtained energies are in good agreement with ab initio data confirming overall agreement between theoretical and experimental data.

Exciton spin dynamics in GaSe

We analyze exciton spin dynamics in GaSe under nonresonant circularly polarized optical pumping with an exciton spin-flip rate-equation model. The model reproduces polarized time-dependent photoluminescence measurements in which the initial circular polarization approaches unity even when pumping with 0.15 eV excess energy. At T = 10 K, the exciton spin relaxation exhibits a biexponential decay with sub-20 ps and >500 ps time constants, which are also reproduced by the rate-equation model assuming distinct spin-relaxation rates for hot (nonequilibrium) and cold band-edge excitons.

Aggregation in a High-Mobility n-Type Low-Bandgap Copolymer with Implications on Semicrystalline Morphology

We explore the photophysics of P(NDI2OD-T2), a high-mobility and air-stable n-type donor/acceptor polymer. Detailed steady-state UV-vis and photoluminescence (PL) measurements on solutions of P(NDI2OD-T2) reveal distinct signatures of aggregation. By performing quantum chemical calculations, we can assign these spectral features to unaggregated and stacked polymer chains. NMR measurements independently confirm the aggregation phenomena of P(NDI2OD-T2) in solution. The detailed analysis of the optical spectra shows that aggregation is a two-step process with different types of aggregates, which we confirm by time-dependent PL measurements. Analytical ultracentrifugation measurements suggest that aggregation takes place within the single polymer chain upon coiling. By transferring these results to thin P(NDI2OD-T2) films, we can conclude that film formation is mainly governed by the chain collapse, leading in general to a high aggregate content of ~45%. This process also inhibits the formation of amorphous and disordered P(NDI2OD-T2) films.

Observation of temperature-independent internal Er3+ relaxation efficiency in Si-rich SiO2 films

Time-dependent photoluminescence measurements of low-temperature-annealed Er-doped Si-rich SiO2 were conducted at sample temperatures 15–300 K. The erbium internal relaxation efficiency from the second (I411/2) to the first (I413/2) excited state upon luminescence-center-mediated Er3+ excitation is investigated. Despite the observation of temperature-dependent relaxation rates, the erbium internal relaxation efficiency is found to be remarkably temperature independent, which suggests that the internal relaxation efficiency is near unity. Internal relaxation is shown to account for 50%–55% of the I413/2 excitation events in the entire temperature range. These results demonstrate that high pump efficiency and stable operation of devices based on this material will be possible under varying thermal conditions.

Exciton recombination dynamics in zinc selenide quantum dots

The time dependent photoluminescence measurements of three different sized zinc selenide quantum dots are carried out. The existence of biexponential decay is explained with the help of three level model [ground state, singlet (bright exciton) state, and triplet (dark exciton) state]. The exciton recombination time of ZnSe quantum dots decreases with the reduction in quantum dot size. The decrease in exciton recombination time is attributed to enhanced overlap integral of electron and hole wavefunctions. This also indicates the dominance of the radiative recombination over the nonradiative recombination process.

Spectroscopic observation of developing InAs quantum dots on GaAs ringlike-nanostructured templates

Spectroscopic study of the InAs quantum dot (QD) formation in GaAs ringlike nanostructures is carried out. Ga droplet epitaxy is used to form GaAs ringlike nanostructures. Subsequently InAs is deposited to obtain InAs QDs by self-assembly inside the holes of the nanostructures. Regularly spaced bands in the photoluminescence spectra exhibit state filling properties under increased excitation power. However, it is demonstrated that these bands do not represent excited states of a single ensemble of dots, but are separate ensembles with individual ground state energies, which are coupled through the GaAs ring structure on which they form. The most likely cause of these uniformly spaced ensemble energies is monolayer differences in the effective height of the dots. Temperature, excitation power density, and time dependent photoluminescence measurements are used to demonstrate the significance of the interdot coupling. The photoluminescent properties of these novel nanostructures make them candidates for optoelectronic applications.

Phonon Interaction in InGaAs/GaAs Quantum Dots

ABSTRACTThe carrier-phonon interaction in self-organized In(Ga)As/GaAs quantum dots is investigated under resonant excitation of the ground-state transition. Different phonon-coupled processes are observed. The distinction between Raman scattering and hot-luminescence process has been resolved by time-dependent photoluminescence measurements. The quantum dot LO (33.8 meV) as well as an interface (36.5 meV) phonon mode is observed by resonant Raman scattering. For the QD LO phonon mode, a very short radiative lifetime of 10 ps was found.

Growth and characterization of GaN single crystals

Up to 3 mm long GaN single crystals were grown by sublimation of cold pressed GaN pellets or evaporation of gallium (Ga) metal under an ammonia (NH 3) flow in a dual heater, high-temperature growth system. A growth rate of 500 μm/h along the [0 0 0 1] direction was achieved using a source temperature of 1200°C, a total pressure of 760 Torr, and an NH 3 flow rate of 50 sccm. The resulting crystals were transparent, possessed low aspect ratios and well-defined growth facets. The only impurity present at high concentrations was oxygen (3×10 18 atoms/cm 3). Photoluminescence studies conducted at 77 K showed a sharp emission peak centered at 359 nm. Time-dependent photoluminescence measurements revealed optical metastability in bulk GaN. Raman spectroscopy yielded narrow peaks representing only the modes allowed for the wurtzite structure. All characterization studies confirmed excellent crystalline and optical quality of the obtained single crystals.

Mechanisms of Optical Gain in Cubic GaN and InGaN

The epitaxial growth of zinc-blende (cubic) GaN and InGaN on GaAs with a common cleavage plane and readily high-quality, low-cost wafers may be considered as an alternative approach for the future realization of cleaved laser cavities. To obtain detailed information about the potential of cubic GaN and InGaN for device applications we performed optical gain spectroscopy accompanied by time-integrated and time-dependent photoluminescence measurements at 2 K and 300 K. From intensity-dependent gain measurements, the identification of the gain processes was possible. For moderate excitation levels, the biexciton decay is likely to be responsible for a gain structure at 3.265 eV in cubic GaN [10]. For the highest pump intensities, the electron- hole-plasma is the dominant gain process, providing gain values up to 200 cm −1. Furthermore cubic GaN samples with different cavity lengths from 250 to 600 µm were cleaved to investigate the influence of the sample geometry on the gain mechanisms. In these samples increased gain values up to 150 cm −1 as well as lower threshold excitation densities were observed, indicating the potential of cubic GaN for device applications. The results of GaN will be compared with intensity-dependent gain measurements on InGaN samples, grown on GaAs with varying In-content. The observed gain mechanisms in cubic InGaN will be discussed in detail.

Mechanisms of Optical Gain in Cubic GaN and Ingan

AbstractThe epitaxial growth of zinc-blende (cubic) GaN and InGaN on GaAs with a common cleavage plane and readily high-quality, low-cost wafers may be considered as an alternative approach for the future realization of cleaved laser cavities. To obtain detailed information about the potential of cubic GaN and InGaN for device applications we performed optical gain spectroscopy accompanied by time-integrated and time-dependent photoluminescence measurements at 2 K and 300 K. From intensity-dependent gain measurements, the identification of the gain processes was possible. For moderate excitation levels, the biexciton decay is likely to be responsible for a gain structure at 3.265 eV in cubic GaN [10]. For the highest pump intensities, the electron- hole-plasma is the dominant gain process, providing gain values up to 200 cm-1. Furthermore cubic GaN samples with different cavity lengths from 250 to 600 mim were cleaved to investigate the influence of the sample geometry on the gain mechanisms. In these samples increased gain values up to 150 cm-1 as well as lower threshold excitation densities were observed, indicating the potential of cubic GaN for device applications. The results of GaN will be compared with intensity-dependent gain measurements on InGaN samples, grown on GaAs with varying In-content. The observed gain mechanisms in cubic InGaN will be discussed in detail.

Capture of carriers excited by interband and intersubband absorption in GaAs/AlAs/AlGaAs double-barrier quantum wells

We report on the carrier dynamics in n-type double-barrier quantum well structures in an electric field. Both the intersubband and interband photocurrents, excited by long-wavelength (4μm) and short-wavelength (0.5μm) radiation, respectively, show a photovoltaic asymmetry with respect to the applied field. This asymmetry arises from an internal field due to an asymmetric dopant distribution with respect to the well centers. Time-dependent photoluminescence measurements allow us to determine the field dependence of the electron and hole capture times.

Hole localization and charge transfer excitation of Fe 2+ in GaP:Fe by time-dependent photoluminescence measurements

The time dependence of the radiative 0.41 eV 5T 2 → 5E transition of Fe 2+ in GaP: Fe has been measured for the case of below-gap excitation, and the results have been compared to dynamical calculations of the excitation-recombinaion process. The data were found to compare well with a model assuming an optically-induced charge transfer (Fe 3+ → Fe 2+) excitation mechanism. The observed exponential decay of the Fe 2+ luminescence intensity is interpreted as evidence for localization of the photo-induced hole at the Fe 2+ site.