Manifestation of anharmonicities in terms of Fano scattering and phonon lifetime of scissors modes in α-MoO3.

α-MoO3 exhibits promising potential in the field of infrared detection and thermoelectricity owing to its exceptional characteristics of ultra-low-loss phonon polaritons (PhPs). It is of utmost importance to comprehend the phonon interaction exhibited by α-MoO3 in order to facilitate the advancement of phonon-centric devices. The intriguing applications of α-MoO3 for phonon-centric technology are found to be strongly dependent on scissors Raman modes. In this study, we have investigated the temperature-dependent asymmetric Raman line-shape characteristics of two scissors modes, Ag(1) and B1g(1), in the orthorhombic phase of bulk α-MoO3 within a temperature range spanning from 138 K to 498 K at 633 nm excitation wavelength. The Fano-Raman line-shape function was employed to analyze the asymmetry in terms of electron-phonon coupling strength, which varies from 0.050 to 0.313 and -0.017 to -0.192 for Ag(1) and B1g(1) modes, respectively, with temperature. This asymmetric behavior of Ag(1) and B1g(1) scissors modes are attributed to interference between the electronic energy continuum and discrete TO and LO phonon states, respectively. Therefore, the line-shape asymmetry in two scissors modes with increasing temperature stemming from the Fano resonance is also consistent with a 488 nm excitation wavelength. Additionally, anharmonicity caused by temperature results in redshift, and linewidth broadening of these two scissors modes through cubic-phonon decay has been observed. Moreover, the ultrashort lifetime of these optical phonons diminishes from ∼1.37 ps to ∼0.53 ps with increasing temperature due to the dominance of cubic-phonon decay over quartic-phonon decay. Our findings strongly emphasize the significance of investigating anharmonic interactions with Fano resonance to acquire an extensive comprehension of the vibrational characteristics of α-MoO3 for novel functionalities.

Elucidating the Role of Electron Transfer in the Photoluminescence of MoS2 Quantum Dots Synthesized by fs-Pulse Ablation.

Herein, MoS2 quantum dots (QDs) with controlled optical, structural, and electronic properties are synthesized using the femtosecond pulsed laser ablation in liquid (fs-PLAL) technique by varying the pulse width, ablation power, and ablation time to harness the potential for next-generation optoelectronics and quantum technology. Furthermore, this work elucidates key aspects of the mechanisms underlying the near-UV and blue emissions the accompanying large Stokes shift, and the consequent change in sample color with laser exposure parameters pertaining to MoS2 QDs. Through spectroscopic analysis, including UV-visible absorption, photoluminescence, and Raman spectroscopy, we successfully unraveled the mechanisms for the change in optoelectronic properties of MoS2 QDs with laser parameters. We realize that the occurrence of a secondary phase, specifically MoO3-x, is responsible for the significant Stokes shift and blue emission observed in this QD system. The primary factor influencing these activities is the electron transfer observed between these two phases, as validated by excitation-dependent photoluminescence and XPS and Raman spectroscopies.

Observation of positive trions in α-MoO3/MoS2 van der Waals heterostructures.

Mono-layer transition metal dichalcogenides (TMDCs) have emerged as an ideal platform for the study of many-body physics. As a result of their low dimensionality, these materials show a strong Coulomb interaction primarily due to reduced dielectric screening that leads to the formation of stable excitons (bound electron-hole pairs) and higher order excitons, including trions, and bi-excitons even at room temperature. van der Waals (vdW) heterostructures (HSs) of TMDCs provide an additional degree of freedom for altering the properties of 2D materials because charge carriers (electrons) in the different atomically thin layers are exposed to interlayer coupling and charge transfer takes place between the layers of vdW HSs. Astoundingly, it leads to the formation of different types of quasi-particles. In the present work, we report the synthesis of vdW HSs, i.e., α-MoO3/MoS2, on a 300 nm SiO2/Si substrate and investigate their temperature-dependent photoluminescence (PL) spectra. Interestingly, an additional PL peak is observed in the case of the HS, along with A and B excitonic peaks. The emergence of a new PL peak in the low-energy regime has been assigned to the formation of a positive trion. The formation of positive trions in the HS is due to the high work function of α-MoO3, which enables the spontaneous transit of electrons from MoS2 to α-MoO3 and injection of holes into the MoS2 layer. In order to confirm charge transfer in the α-MoO3/MoS2 HS, systematic power and wavelength-dependent Raman and PL studies, as well as first-principle calculations using Bader charge analysis, have been carried out, which clearly validate our mechanism. We believe that this study will provide a platform towards the integration of vdW HSs for next-generation excitonic devices.

Femtosecond Pulse Ablation Assisted Mg-ZnO Nanoparticles for UV-Only Emission.

The need for improved UV emitting luminescent materials underscored by applications in optical communications, sterilization and medical technologies is often addressed by wide bandgap semiconducting oxides. Among these, the Mg-doped ZnO system is of particular interest as it offers the opportunity to tune the UV emission by engineering its bandgap via doping control. However, both the doped system and its pristine congener, ZnO, suffer from being highly prone to parasitic defect level emissions, compromising their efficiency as light emitters in the ultraviolet region. Here, employing the process of femtosecond pulsed laser ablation in a liquid (fs-PLAL), we demonstrate the systematic control of enhanced UV-only emission in Mg-doped ZnO nanoparticles using both photoluminescence and cathodoluminescence spectroscopies. The ratio of luminescence intensities corresponding to near band edge emission to defect level emission was found to be six-times higher in Mg-doped ZnO nanoparticles as compared to pristine ZnO. Insights from UV-visible absorption and Raman analysis also reaffirm this defect suppression. This work provides a simple and effective single-step methodology to achieve UV-emission and mitigation of defect emissions in the Mg-doped ZnO system. This is a significant step forward in its deployment for UV emitting optoelectronic devices.

Insights into non-noble metal based nanophotonics: exploration of Cr-coated ZnO nanorods for optoelectronic applications.

Herein, the room temperature photoluminescence and Raman spectra of hydrothermally grown ZnO nanorods coated with Cr are investigated for optoelectronic applications. A thorough examination of the photoluminescence spectra of Cr coated ZnO nanorods showed the suppression of deep level emissions by more than twenty five times with Cr coating compared to that of pristine ZnO nanorods. Moreover, the underlying mechanism was proposed and can be attributed to the formation of Schottky contacts between Cr and ZnO resulting in defect passivation, weak exciton-plasmon coupling, enhanced electric field effect and formation of hot carriers due to interband transitions. Interestingly, with the increase in sputtering time, the ratio of the intensities corresponding to the band gap emission and deep level emission was observed to increase from 6.2 to 42.7, suggesting its application for UV only emission. Further, a planar photodetector was fabricated (Ag-ZnO-Ag planar configuration) and it was observed that the dark current value got reduced by more than ten times with Cr coating, thereby opening up its potential for transistor applications. Finally, Cr coated ZnO nanorods were employed for green light sensing. Our results demonstrated that ZnO nanorods decorated with Cr shed light on developing stable and high-efficiency non-noble metal based nanoplasmonic devices such as photodetectors, phototransistors and solar cells.

Near Infrared Random Lasing in Multilayer MoS2.

We demonstrated room temperature near infrared (NIR) region random lasing (RL) (800-950 nm), with a threshold of nearly 500 µW, in ∼200 nm thick MoS2/Au nanoparticles (NPs)/ZnO heterostructures using photoluminescence spectroscopy. The RL in the above system arises mainly due to the following three reasons: (1) enhanced multiple scattering because of Au/ZnO disordered structure, (2) exciton-plasmon coupling because of Au NPs, and (3) enhanced charge transfer from ZnO to thick MoS2 flakes. RL has recently attracted tremendous interest because of its wide applications in the field of telecommunication, spectroscopy, and specifically in biomedical tissue imaging. This work provides new dimensions toward realization of low power on-chip NIR random lasers made up of biocompatible materials.

Influence of Parametric Variations on Hydrothermal Growth of ZnO Nanostructures for Hybrid Polymer/ZnO Based Photodetector.

Dumbbell and flower like ZnO nano-crystals were grown via hydrothermal process. The as-prepared dumbbells, with length of 0.8-10 µm and edge length of 0.3-0.8 µm possess a hexagonal structure, while flowers with lengths ranging from 1-6 µm with hexagonal structure have been synthesized. The effect of temperature, solution concentration and growth time on the size and shapes of the ZnO nanostructures has been studied using Field emission scanning electron microscope (FESEM) and X-ray diffractometer (XRD). Further the optical properties of nanostructures were investigated by Photoluminescence (PL) spectroscopy, which shows emission in UV and visible regions. From Diffused reflectance spectroscopic analysis (DRA) it was observed that ZnO nanodumbbells and nanoflowers have a direct band gap of 3.27 eV and 3.25 eV respectively. The I-V plot showed dependence of current values under dark and illumination over the annealing temperature during the growth stage. Thus we report a control over the shape and dimension of nanostructures by varying various parameters having implications for (opto)electronic devices.

Effect of Addition of KI on the Hydrothermal Growth of ZnO Nanostructures Towards Hybrid Optoelectronic Device Applications.

We report the structural and optoelectronic properties of Zinc oxide (ZnO) nanostructures prepared by hydrothermal method. The morphological, structural and optical properties of the grown ZnO nanostructures were investigated using X-ray diffraction (XRD), scanning electron microscope (SEM) and photoluminescence spectroscopy (PL) respectively. Upon addition of relatively small amount of KI during the in-situ hydrothermal growth the nanorods were formed, further increasing the concentration led to increased diameter of these nanorods and finally at relatively higher concentration of KI, ZnO nanosheets were formed. Later these structures were used to fabricate bi-layer ZnO/P3HT based hybrid photodiode. Subsequent hybrid photodiode measurement with ZnO nanorods and ZnO nanosheets indicated that the nanosheets exhibited improved photodiode response. Compared to the ZnO nanorod/P3HT devices, the optimized photodiode with the dense ZnO nanosheets/P3HT have shown significant increase in the rectification ratio and the photosenstivity from 3.21 to 1420 and from 5.85 to 1330 respectively. The enhanced photodiode response of bi-layered devices consisting of ZnO nanosheets indicated that optimizing the shape and size of ZnO nanostructures had a significant influence on the overall photocurrent and the observed results have been explained on the basis of reduction in the defect density with pronounced absorption in the UV region, thus leading to improved transmission of light in the visible range through these layers.