Photoluminescence Excitation Spectroscopy Research Articles

Effect of Post-Implantation Heat Treatment Conditions on Photoluminescent Properties of Ion-Synthesized Gallium Oxide Nanocrystals.

A novel and promising way for creating nanomaterials based on gallium oxide is the ion synthesis of Ga2O3 nanocrystals in a SiO2/Si dielectric matrix. The properties of nanocrystals are determined by the conditions of ion synthesis-the parameters of ion irradiation and post-implantation heat treatment. In this work, the light-emitting properties of Ga2O3 nanocrystals were studied depending on the temperature and annealing atmosphere. It was found that annealing at a temperature of 900 °C leads to the appearance of intense luminescence with a maximum at ~480 nm caused by the recombination of donor-acceptor pairs. An increase in luminescence intensity upon annealing in an oxidizing atmosphere is shown. Based on data from photoluminescence excitation spectroscopy and high-resolution transmission electron microscopy, a hypothesis about the possibility of the participation of a quantum-size effect during radiative recombination is proposed. A mechanism for the formation of Ga2O3 nanocrystals during ion synthesis is suggested, which makes it possible to describe the change in the luminescent properties of the synthesized samples with varying conditions of post-implantation heat treatment.

Engineering shallow and deep level defects in κ-Ga2O3 thin films: comparing metal-organic vapour phase epitaxy to molecular beam epitaxy and the effect of annealing treatments

Orthorhombic gallium oxide (κ-Ga2O3) is an ultra-wide bandgap semiconductor with great potential in new generation electronics. Its application is hindered at present by the limited physical understanding of the relationship between synthesis and functional properties. This work discusses the effects of growth method (metal-organic vapour phase epitaxy and molecular beam epitaxy) as well as annealing treatments in different atmospheres (O2, H2) on point defects in κ-Ga2O3 layers epitaxially grown on c-plane sapphire. Comprehensive experimental characterization by X-ray diffraction, photo current-as well as photoluminescence excitation spectroscopy, and X-ray photo electron spectroscopy is combined with first principles calculations of the point defects’ formation and complex-dissociation energies. We demonstrate that for κ-Ga2O3 the concentration of shallow and deep level defects can be sensitively controlled through annealing treatments at temperatures (T = 500 °C) well below the thermal stability threshold of this polymorph. In particular, our results suggest that hydrogen-related defects (e.g., H-interstitials, Ga-vacancies—H complexes) play a key role in this process. While we provide direct exemplary implications of our results for the performances of κ-Ga2O3 based photodetectors, these findings are predicted to impact further application fields of κ-Ga2O3, such as high electron mobility transistors or memory devices.

Fluctuations in the Photoluminescence Excitation Spectra of Individual Semiconductor Nanocrystals.

Most single quantum emitters display non-steady emission properties. Models that explain this effect have primarily relied on photoluminescence measurements that reveal variations in intensity, wavelength, and excited-state lifetime. While photoluminescence excitation spectroscopy could provide complementary information, existing experimental methods cannot collect spectra before individual emitters change in intensity (blink) or wavelength (spectrally diffuse). Here, we present an experimental approach that circumvents such issues, allowing the collection of excitation spectra from individual emitters. Using rapid modulation of the excitation wavelength, we collect and classify excitation spectra from individual CdSe/CdS/ZnS core/shell/shell quantum dots. The spectra, along with simultaneous time-correlated single-photon counting, reveal two separate emission-reduction mechanisms caused by charging and trapping, respectively. During bright emission periods, we also observe a correlation between emission red-shifts and the increased oscillator strength of higher excited states. Quantum-mechanical modeling indicates that diffusion of charges in the vicinity of an emitter polarizes the exciton and transfers the oscillator strength to higher-energy transitions.

Role of arsenic vapor pressure in transformation of InAs quantum dots during overgrowth by a GaAs capping layer

The results of a study of the optical properties of self-assembled InAs/GaAs (001) quantum dots (QDs) overgrown under different arsenic pressures, obtained using photoluminescence (PL) and PL excitation spectroscopy, are presented. If the arsenic pressure during overgrowth is low (2.5·10−6 Pa), a series of pronounced QD-related peaks is observed in the 77-K PL spectrum over a 200-meV broad spectral interval with the brightest one located at 1.37 eV. With increasing arsenic pressure, the PL spectrum becomes smoother and is red-shifted to 1.16 eV at 1·10−5 Pa and to 1.26 eV at 3·10−5 Pa. We explain this behavior in terms of enhanced QD decomposition, the mechanism of which is strongly dependent on the arsenic deficiency or excess during the overgrowth process, determined by the arsenic pressure. Supported by the analysis of the wetting layer luminescence, we also conclude that the total indium content in the QD layer decreases with decreasing arsenic pressure during the overgrowth. This study reveals an essential role of the arsenic pressure in the overgrowth of InAs QDs.

Anisotropy of optical transitions in β-Ga2O3 investigated by polarized photoluminescence excitation spectroscopy

The monoclinic beta-phase of gallium oxide possesses an ultra-wide bandgap that surpasses other wide bandgap materials such as SiC and GaN, making it a promising candidate for power electronic device technologies. We investigate the first fundamental optical transitions in this material, which exhibit a strong directional dependence. To determine the energies and orientations of these transitions, temperature-dependent and angular resolved photoluminescence excitation spectroscopy is applied. We observe a distinct excitation channel located energetically between those of the first two optical transitions Γ1−1 and Γ1−2. While previous absorption edge and reflectance spectroscopy studies have assigned a transition in this spectral range to either the Γ1−1 or the Γ1−2 transition, our findings demonstrate no pronounced polarization dependence of this excitation channel within the (010) plane, an observation not reflected in calculations of the band-to-band transitions in β-Ga2O3.

Photoluminescence Excitation Spectroscopy of Stimulated Emission from AlGaN‐Based Multiple Quantum Wells with an Emission Wavelength Around 280 nm

Photoluminescence Excitation Spectroscopy of Stimulated Emission from AlGaN‐Based Multiple Quantum Wells with an Emission Wavelength Around 280 nm

Anomalous redshift in interlayer exciton emission with increasing twist angle in WSe2/MoSe2 heterostructures

Van der Waals heterostructures utilizing semiconducting transition metal dichalcogenide (TMDC) monolayers have surfaced as compelling candidates due to their intriguing optical characteristics, which can be effectively controlled by the manipulation of the stacking twist angle. This study investigates the intricate correlation between twist angle, band offset, and interlayer exciton emission within twisted WSe2/MoSe2 heterostructures. Our findings suggest a crucial influence of monolayer stacking order on the band offset and the dipole orientation in twisted heterostructures that leads to either blueshift or redshift in emission energy. Herein, we fabricate heterobilayers with twist angles varying from 1 ∘ to 56 ∘ and observe an anomalous redshift energy of 100 meV in the interlayer exciton emission. Additionally, photoluminescence excitation spectroscopy measurements highlight the systematic twist angle dependence of intralayer exciton resonances, indicating significant angle dependent effects on individual monolayer bandgaps and on the interlayer coupling strength. Our fundamental study of exciton resonances provides comprehensive insights into the nuanced interplay between twist angle, dipole orientation, and dielectric asymmetry, providing a deeper understanding of the factors governing the optical properties of layered TMDC heterostructures.

Carbon-Related Quantum Emitter in Hexagonal Boron Nitride with Homogeneous Energy and 3-Fold Polarization.

Most hexagonal boron nitride (hBN) single-photon emitters (SPEs) studied to date suffer from variable emission energy and unpredictable polarization, two crucial obstacles to their application in quantum technologies. Here, we report an SPE in hBN with an energy of 2.2444 ± 0.0013 eV created via carbon implantation that exhibits a small inhomogeneity of the emission energy. Polarization-resolved measurements reveal aligned absorption and emission dipole orientations with a 3-fold distribution, which follows the crystal symmetry. Photoluminescence excitation (PLE) spectroscopy results show the predictability of polarization is associated with a reproducible PLE band, in contrast with the non-reproducible bands found in previous hBN SPE species. Photon correlation measurements are consistent with a three-level model with weak coupling to a shelving state. Our ab initio excited-state calculations shed light on the atomic origin of this SPE defect, which consists of a pair of substitutional carbon atoms located at boron and nitrogen sites separated by a hexagonal unit cell.

Charge carrier recombination processes, intragap defect states, and photoluminescence mechanisms in stoichiometric and reduced TiO2 brookite nanorods: an interpretation scheme through in situ photoluminescence excitation spectroscopy in controlled environment.

The study of titanium dioxide (TiO2) in the brookite phase is gaining popularity as evidence has shown the efficient photocatalytic performance of this less investigated polymorph. It has been recently reported that defective anisotropic brookite TiO2 nanorods display remarkable substrate-specific reactivity towards alcohol photoreforming, with rates of hydrogen production significantly (18-fold) higher than those exhibited by anatase TiO2 nanoparticles. To elucidate the basic photo-physical mechanisms and peculiarities leading to such an improvement in the photoactive efficiency, we investigated the recombination processes of photoexcited charge carriers in both stoichiometric and reduced brookite nanorods via photoluminescence excitation spectroscopy in controlled environment. Through an investigation procedure employing both supragap and subgap excitation during successive exposure to oxidizing and reducing gaseous agents, we firstly obtained an interpretation scheme describing the main photoluminescence and charge recombination pathways in stoichiometric and reduced brookite, which includes information about the spatial and energetic position of the intragap states involved in photoluminescence mechanisms, and secondly identified a specific photoluminescence enhancement process occurring in only reduced brookite nanorods, which indicates the injection of a conduction band electron during ethanol photo-oxidation. The latter finding may shed light on the empirical evidence about the exceptional reactivity of reduced brookite nanorods toward the photo-oxidation of alcohols and the concomitant efficiency of photocatalytic hydrogen generation.

(Poster Award - 2nd Place) Layer-Number Engineered Momentum-Indirect Interlayer Excitons with Large Spectral Tunability

The diversity of two-dimensional (2D) materials provides van der Waals heterostructures with abundant degrees of freedom and makes the family a promising candidate to realize novel optoelectronic devices and an attractive platform for exploring physical phenomena. Interlayer excitons in type-II van der Waals heterostructures are equipped with an oriented permanent dipole moment and long lifetime and thus would allow promising applications in excitonic and optoelectronic devices. However, in the widely studied van der Waals heterostructures constructed by transition metal dichalcogenides, the formation of interlayer excitons is limited by the lattice mismatch, rotational and translational alignment between the constituent layers, increasing the complexity of the device fabrication. Here, I will report on the robust momentum-indirect interlayer exciton emission with widely tunable emission energy via layer engineering in transition metal dichalcogenide/2D perovskite heterostructures. The transition metal dichalcogenides with different thicknesses and 2D perovskites with different layer numbers of the inorganic octahedral slabs are stacked to form type-II van der Waals heterostructures without considering special orientation arrangement and momentum mismatch. The presence of interlayer excitons is supported by the excitation-power- and temperature-dependent photoluminescence studies, photoluminescence excitation spectroscopy, time-resolved photoluminescence decay studies and electric field-dependent photoluminescence studies. Taking advantage of the thickness- or layer-number-dependence of the electronic band structure of the constituent materials, the emission energy of the interlayer excitons in our heterostructures can be tuned from 1.3 eV to 1.6 eV, providing strong evidence for the applications of van der Waals interface engineering to broad-spectrum optoelectronics. In addition, the diffusion coefficient of interlayer excitons in our heterostructures can be estimated to be ~10 cm2 s−1, which is at least one order of magnitude larger than that in the van der Waals heterostructures with Moiré superlattice, suggesting a non-localized nature that would be beneficial to the excitonic devices. Our study would offer new insights into the nature of interlayer excitons and provoke further research into their dynamics.

Energy transfer from SnO2 host to Eu3+ ions and photoluminescence quenching of SnO2:Eu3+ nanocrystals

SnO2:Eu3+ nanoparticles were prepared by hydrothermal method. The crystal structure, size, phase composition, and morphology of the materials were investigated by X-ray diffraction measurements, scanning electron microscopy, Raman scattering spectroscopy. The absorption and optical properties of the materials were studied by UV–vis absorption spectroscopy, photoluminescence excitation spectroscopy, and photoluminescence spectroscopy. Results showed that the SnO2:Eu3+ nanoparticles had a tetragonal rutile crystal structure and were about 5–15 nm in size. They were also smaller than pure SnO2. When doping Eu3+ into SnO2, the crystal size of SnO2:Eu3+ nanoparticles decreased, the defects increased, and the crystallinity decreased. The SnO2:Eu3+ samples emitted in the emission region related to the SnO2 host and the emission peaks of the Eu3+ ion impurity. Moreover, energy transfer occurred from the SnO2 host to Eu3+ ions. The photoluminescence spectra of SnO2:Eu3+ nanoparticles with indirect and direct excitation were further studied. The influences of Eu3+ concentration on the structure, morphology, and optical properties of SnO2:Eu3+ nanoparticles were investigated in detail.

Shallow Silicon Vacancy Centers with Lifetime-Limited Optical Linewidths in Diamond Nanostructures.

The negatively charged silicon vacancy center (SiV-) in diamond is a promising, yet underexplored candidate for single-spin quantum sensing at sub-kelvin temperatures and tesla-range magnetic fields. A key ingredient for such applications is the ability to perform all-optical, coherent addressing of the electronic spin of near-surface SiV- centers. We present a robust and scalable approach for creating individual, ∼50 nm deep SiV- with lifetime-limited optical linewidths in diamond nanopillars through an easy-to-realize and persistent optical charge-stabilization scheme. The latter is based on single, prolonged 445 nm laser illumination that enables continuous photoluminescence excitation spectroscopy without the need for any further charge stabilization or repumping. Our results constitute a key step toward the use of near-surface, optically coherent SiV- for sensing under extreme conditions, and offer a powerful approach for stabilizing the charge-environment of diamond color centers for quantum technology applications.

Exciton energy transfer under low temperature in a lateral heteromonolayer of WSe2–MoSe2

We examined the exciton energy transfer process in a lateral heteromonolayer of WSe2–MoSe2 at low temperature. Position-dependent photoluminescence (PL) and PL excitation spectroscopy measurements revealed the occurrence of exciton energy transport from WSe2 to MoSe2 both at RT and 15 K. The effective energy transport distance in WSe2 was longer at 15 K than at RT, suggesting that the dark excitons with longer diffusion length than bright excitons preferentially contributed to the exciton energy transport across the heterojunction interface at 15 K. Additionally, we observed that no valley information was transported from WSe2 to MoSe2 via the energy transfer process. This study provides useful insights for the development of excitonic devices based on exciton transport in transition metal dichalcogenides.

Improving near-infrared luminescence in Er3+ doped CsPbBr3 quantum dots glasses through a certain energy transfer process

Er3+ has received extensive attention due to its excellent optical properties, especially its emission at 1535 nm in atmospheric propagation window. Enhancement and regulation of 1535 nm emission of Er3+ is of great significance to optical communication. In this work, growing of CsPbBr3 QDs has been controlled through adjusting annealing time which would precisely regulate conduction band of CsPbBr3 QDs to match energy levels of Er3+ enabling energy transfer between Er3+ and CsPbBr3 QDs. By steady-state and transient PL emission and excitation spectroscopy, we reveal multiple energy transfer processes between Er3+ and CsPbBr3 QDs under different excitation wavelengths in Er3+ doped CsPbBr3 QDs glass: under higher energy excitation (∼378 nm), energy transfer from Er3+ to CsPbBr3 QDs and this extra energy within CsPbBr3 QDs decay via a non-radiative pathway; under lower energy excitation (∼524 nm), energy transfer from conduction band of CsPbBr3 QDs to 4S3/2 energy level of Er3+ which significantly enhances PL emission of Er3+ in near infrared region (∼1535 nm, 4I13/2 → 4I15/2). These results provide a facile approach to enhance and regulate PL emission of Er3+ in near infrared region.

Dual-emitting from Bi[formula omitted], Ln[formula omitted] (Ln [formula omitted] Eu, Sm) co-activated Ca[formula omitted]Sb[formula omitted]O[formula omitted] phosphor for optical temperature measurement

In this paper, a series of Ca(2−x−y) Sb2O7: xBi3+, yLn3+ (Ln = Eu, Sm) fluorescent powder samples were successfully obtained, which used the traditional high-temperature solid-phase synthesis method in the preparation process. Samples of Ca2Sb2O7: Bi3+, Ln3+ (Ln = Eu, Sm) fluorescent powder samples were structurally and optically characterized​ using X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM), photoluminescence excitation spectroscopy and emission spectroscopy, and fluorescence decay measurements. The results show that the prepared Ca(2−x−y) Sb2O7: xBi3+, yLn3+ (Ln = Eu, Sm) samples have an orthogonal spider web structure, which remains unchanged whether Bi3+ is single doped or Bi3+ is co-doped with Ln3+ (Ln = Eu, Sm). Under ultraviolet lamp (λex=340nm) irradiation, Bi3+ doped Ca2Sb2O7 powder shows a wide emission band centered at 435 nm, which is owing to the 3P1→1S0 transition of Bi3+ ion. Therefore, the effect of Bi3+ and Ln3+ (Ln = Eu, Sm) co-doped Ca2Sb2O7 samples on the luminescence intensity of the samples at different concentrations was studied. When the temperature was varied from 293 K to 483 K, the absolute temperature sensitivity (Sa) of doped Bi3+/Eu3+ and Bi3+/Sm3+ phosphors is 0.001K−1 (at 483 K) and 0.02K−1 (at 293 K), respectively, and the relative temperature sensitivity (Sr) is 1.03% K−1 (at 343 K) and 1.19% K−1 (at 293 K), respectively. These results demonstrate that Ca(2−x−y) Sb2O7: xBi3+, yLn3+(Ln = Eu, Sm) phosphors are prospective double emission thermal thermometers.

Biexciton binding energy in CH3NH3PbBr3 as determined by multiphoton photoluminescence excitation spectroscopy

Biexciton binding energy in CH3NH3PbBr3 as determined by multiphoton photoluminescence excitation spectroscopy

The influence of Eu3+ doping on the optical and structural properties of the Ge2Y2O7 crystalline phase through a soft chemical process

The present work reports on the synthesis, structural and optical properties of Ge2Y2-xEuxO7 composition powders, with x ranging from 0.0 to 0.16 (from 0.0 to 4.0 mol% Eu3+). We synthesized stable and transparent sols, homogeneous gels, and powders treated at 1100 °C by a soft chemical route, and the effect of Eu3+ concentrations was evaluated. X-ray diffraction (XRD), infrared vibrational spectroscopy (FTIR), Raman spectroscopy, diffuse reflectance spectroscopy (DRS), emission and excitation photoluminescence spectroscopy (PL, PLE), decay curves of emission intensity as a function of time and quantum yield were obtained. An annealing temperature of 1100 °C was enough to obtain a single Ge2Y2O7 crystalline phase and the decrease of Χ2 value (from 2.32 to 1.74) with the increase of Eu3+ doping in the matrix, observed with the Rietveld refinement of the XRD patterns of the samples, is due to the crystallization process. Diffuse reflectance spectra and optical bandgap of 4.7 eV for Ge2Y0.88Eu0.12O7 (3.0 mol% Eu3+) – determined by Kubelka- Munk model – showed the good optical quality of the samples, which were considered non-conducting. All doped samples possessed visible photoluminescence emission from Eu3+ ions under excitation at 394 nm, with higher emissions occurring in the red region from 5D0 → 7F2 transition, with R/O relation equal to 2.6 and purity of red color higher than 85 % for the sample with x = 0.012. Analyzing photoluminescence emission spectra, the lifetime values and Judd-Ofelt parameters, we determined that Eu3+ occupied two different sites of the Ge2Y2O7 host matrix, replacing Y3+ ions, with the quenching concentration occurring between x = 0.12 and x = 0.16. The average decay lifetime of 5D0 level from Eu3+ was around 1.66 ms, with average quantum efficiency around of 48 % and an internal quantum yield equal to 7.17 %. Moreover, we evaluated their emission luminescence properties upon 394 nm excitation to explore for the first time the possibility of using this material in thermal sensing applications.

Electron paramagnetic resonance

We have studied literature from investigation of the impact of Mechanothermal effects in the creation of defect structures in dispersed systems after prolonged mechanical treatment of ZnO powders. This work illustrates some potential applications of electron paramagnetic resonance. EPR application beginning of a variety of paramagnetic processes is based on the knowledge that this centre happens when some materials are mechanically treated. These facilities can act as EPR sondes of various thermal processes that appear when systems are being mechanically treated consisting of ZnO.Zn was evaporated in air, dry and humid argon flow, and dry and humid nitrogen flow to create Zno tetrapod nanostructures. SEM, X-ray diffraction, photoluminescence, photoluminescence excitation (PLE) spectroscopy (at various temperatures), and electron paramagnetic resonance (EPR) spectroscopy at −160 ℃ and room temperature have all been used to explore the characteristics. It is discovered that the fabrication conditions have a considerable impact on the acquired EPR and PL spectra. while some of the samples exhibit a g = 1.96 EPR signal. We used microwave processing to create and mix ZnO nanoparticles (ZnO-NPs) with various amounts of graphene oxide (GO) (10 %, 20 %, and 30 %).The process delivered evenly distributed ZnO-NPs onto and between the rGO layers.(GZCs). The UV–vis absorption, PL emission, defect states of the ZnO, EPR signals, photo-electrochemical reaction, and charge transfer properties were all influenced by the annealing temperature and graphene oxide content. The GZCs' HRTEM microscopy pictures revealed interpenetrating structures and vacancy flaws that were easily seen. The findings showed that following hybridization with GO, the defect sites (Zn interstitials, oxygen vacancy, ionised oxygen vacancy, and oxygen interstitials) greatly decreased. The GZC-10photo-conversion 10 %'s efficiency(ŋ= 13.1 × 10-3%) We have studied literature from Ref.[1]which show that.

How Pendant Groups Dictate Energy and Electron Transfer in Perovskite–Rhodamine Light Harvesting Assemblies

Energy and electron transfer processes allow for efficient manipulation of excited states within light harvesting assemblies for photocatalytic and optoelectronic applications. We have now successfully probed the influence of acceptor pendant group functionalization on the energy and electron transfer between CsPbBr3 perovskite nanocrystals and three rhodamine-based acceptor molecules. The three acceptors─rhodamine B (RhB), rhodamine isothiocyanate (RhB-NCS), and rose Bengal (RoseB)─contain an increasing degree of pendant group functionalization that affects their native excited state properties. When interacting with CsPbBr3 as an energy donor, photoluminescence excitation spectroscopy reveals that singlet energy transfer occurs with all three acceptors. However, the acceptor functionalization directly influences several key parameters that dictate the excited state interactions. For example, RoseB binds to the nanocrystal surface with an apparent association constant (Kapp = 9.4 × 106 M-1) 200 times greater than RhB (Kapp = 0.05 × 106 M-1), thus influencing the rate of energy transfer. Femtosecond transient absorption reveals the observed rate constant of singlet energy transfer (kEnT) is an order-of-magnitude greater for RoseB (kEnT = 1 × 1011 s-1) than for RhB and RhB-NCS. In addition to energy transfer, each acceptor had a subpopulation of molecules (∼30%) that underwent electron transfer as a competing pathway. Thus, the structural influence of acceptor moieties must be considered for both excited state energy and electron transfer in nanocrystal-molecular hybrids. The competition between electron and energy transfer further highlights the complexity of excited state interactions in nanocrystal-molecular complexes and the need for careful spectroscopic analysis to elucidate competitive pathways.

Effect of surface gallium termination on the formation and emission energy of an InGaAs wetting layer during the growth of InGaAs quantum dots by droplet epitaxy

Self-assembled quantum dots (QDs) based on III–V semiconductors have excellent properties for applications in quantum optics. However, the presence of a 2D wetting layer (WL) which forms during the Stranski–Krastanov growth of QDs can limit their performance. Here, we investigate WL formation during QD growth by the droplet epitaxy technique. We use a combination of photoluminescence excitation spectroscopy, lifetime measurements, and transmission electron microscopy to identify the presence of an InGaAs WL in these droplet epitaxy QDs, even in the absence of distinguishable WL luminescence. We observe that increasing the amount of Ga deposited on a GaAs (100) surface prior to the growth of InGaAs QDs leads to a significant reduction in the emission wavelength of the WL to the point where it can no longer be distinguished from the GaAs acceptor peak emission in photoluminescence measurements. However increasing the amount of Ga deposited does not suppress the formation of a WL under the growth conditions used here.