Paribesh Acharyya

Bio: Paribesh Acharyya is an academic researcher from Jawaharlal Nehru Centre for Advanced Scientific Research. The author has contributed to research in topics: Materials science & Photoluminescence. The author has an hindex of 8, co-authored 13 publications receiving 183 citations. Previous affiliations of Paribesh Acharyya include Indian Institute of Technology Kharagpur.

Intrinsically Ultralow Thermal Conductivity in Ruddlesden–Popper 2D Perovskite Cs2PbI2Cl2: Localized Anharmonic Vibrations and Dynamic Octahedral Distortions

Abstract: Fundamental understanding of the correlation between chemical bonding and lattice dynamics in intrinsically low thermal conductive crystalline solids is important to thermoelectrics, thermal barrier coating, and more recently to photovoltaics. Two-dimensional (2D) layered halide perovskites have recently attracted widespread attention in optoelectronics and solar cells. Here, we discover intrinsically ultralow lattice thermal conductivity (κL) in the single crystal of all-inorganic layered Ruddlesden-Popper (RP) perovskite, Cs2PbI2Cl2, synthesized by the Bridgman method. We have measured the anisotropic κL value of the Cs2PbI2Cl2 single crystal and observed an ultralow κL value of ∼0.37-0.28 W/mK in the temperature range of 295-523 K when measured along the crystallographic c-axis. First-principles density functional theory (DFT) analysis of the phonon spectrum uncovers the presence of soft (frequency ∼18-55 cm-1) optical phonon modes that constitute relatively flat bands due to localized vibrations of Cs and I atoms. A further low energy optical mode exists at ∼12 cm-1 that originates from dynamic octahedral rotation around Pb caused by anharmonic vibration of Cl atoms induced by a 3s2 lone pair. We provide experimental evidence for such low energy optical phonon modes with low-temperature heat capacity and temperature-dependent Raman spectroscopic measurements. The strong anharmonic coupling of the low energy optical modes with acoustic modes causes damping of heat carrying acoustic phonons to ultrasoft frequency (maximum ∼37 cm-1). The combined effect of soft elastic layered structure, abundance of low energy optical phonons, and strong acoustic-optical phonon coupling results in an intrinsically ultralow κL value in the all-inorganic layered RP perovskite Cs2PbI2Cl2.

Single pot synthesis of indirect band gap 2D CsPb2Br5 nanosheets from direct band gap 3D CsPbBr3 nanocrystals and the origin of their luminescence properties

Abstract: Two-dimensional (2D) perovskites recently attracted significant interest due to their unique and novel optoelectronic properties. CsPb2Br5, a 2D inorganic perovskite halide, is an indirect band gap semiconductor, and hence it is not supposed to be luminescent. However, a fundamental understanding of the origin of its luminescence properties is still lacking as there are contradictory literature reports present concerning its luminescence properties. Here, we demonstrate a single pot solution based transformation of 2D CsPb2Br5 nanosheets from the nanocrystals of 3D CsPbBr3 and investigate the origin of its luminescence properties by detailed experiments and density functional theory (DFT) calculations. The photoluminescence of CsPb2Br5 originates from the different amorphous lead bromide ammonium complexes which are present at the surface of the nanosheets. We have also highlighted the formation mechanism of 2D nanosheets from 3D CsPbBr3 nanocrystals. These combined theoretical and experimental studies offer significant insights into the optical properties and formation mechanism of 2D CsPb2Br5 perovskites.

Ultralow Thermal Conductivity, Enhanced Mechanical Stability, and High Thermoelectric Performance in (GeTe)1–2x(SnSe)x(SnS)x

Abstract: Thermoelectric (TE) energy conversion demands high performance crystalline inorganic solids that exhibit ultralow thermal conductivity, high mechanical stability, and good TE device properties. Pb-free germanium telluride (GeTe)-based material has recently attracted significant attention in TE power generation in mid temperatures, but pristine GeTe possesses significantly higher lattice thermal conductivity (κlatt) compared to that of its theoretical minimum (κmin) of ∼0.3 W/mK. Herein, we have demonstrated the reduction of κlatt of (GeTe)1-2x(SnSe)x(SnS)x very near to its κmin. The (GeTe)1-2x(SnSe)x(SnS)x system behaves as a coexistence of point-defect rich solid solution and phase separation. Initially, the addition of equimolar SnSe and SnS in the GeTe reduces the κlatt by effective phonon scattering because of the excess point defects and rich microstructures. In the second step, introduction of Sb-doping leads to additional phonon scattering centers and optimizes the p-type carrier concentration. Notably, 10 mol % Sb-doped (GeTe)0.95(SnSe)0.025(SnS)0.025 exhibits ultralow κlatt of ∼0.30 W/mK at 300 K. Subsequently, 10 mol % Sb-doped (GeTe)0.95(SnSe)0.025(SnS)0.025 exhibits a high TE figure of merit (zT) of ∼1.9 at 710 K. The high-performance sample exhibits a Vickers microhardness (mechanical stability) value of ∼194 HV that is significantly higher compared to the pristine GeTe and other state-of-the-art thermoelectric materials. Further, we have achieved a high output power, ∼150 mW for the temperature difference of 462 K, in single leg TE device based on 10 mol % Sb-doped (GeTe)0.95(SnSe)0.025(SnS)0.025.

Synthesis of Ultrathin Few-Layer 2D Nanoplates of Halide Perovskite Cs3Bi2I9 and Single-Nanoplate Super-Resolved Fluorescence Microscopy.

Abstract: The discovery of new two-dimensional (2D) perovskite halides has created sensation recently because of their structural diversity and intriguing optical properties. The toxicity of Pb-based perovskite halides led to the development of Pb-free halides. Herein, we have demonstrated a one-pot solution-based synthesis of 2D ultrathin (∼1.78 nm) few-layer (2–4 layers) nanoplates (300–600 nm lateral dimension), nanosheets (0.6–1.5 μm), and nanocrystals of layered Cs3Bi2I9 by varying the reaction temperature from 110 to 180 °C. We have established a mechanistic pathway for the variation of morphology of Cs3Bi2I9 with temperature in the presence of organic capping ligands. Further, we have synthesized the bulk powder of Cs3Bi2I9 by mechanochemical synthesis and liquid-assisted grinding and crystalline ingot by vacuum-sealed tube melting. 2D nanoplates and bulk Cs3Bi2I9 demonstrate optical absorption edge along with excitonic transition. Photoluminescence properties of individual nanoplates were studied by super-r...

2D layered all-inorganic halide perovskites: recent trends in their structure, synthesis and properties

Abstract: Recently, halide perovskites have appeared as a superior class of materials for diverse applications, mainly in optoelectronics and photovoltaics. Perovskite halides are broadly classified as hybrid organic-inorganic and all-inorganic analogues depending on the chemical nature of the A cation in the ABX3-type structure. Immense progress has already been achieved in halide perovskites focusing mainly on the hybrid equivalents and all-inorganic three-dimensional (3D) structures, however all-inorganic two-dimensional (2D) layered halide perovskites are relatively new and their nanostructures have gained significant attention in the last few years. In this minireview, we presented a discussion on the recently developed all-inorganic 2D layered halide perovskites highlighting their crystal structure, synthetic methodologies, chemical transformations, and optical properties. We have demonstrated a significant number of examples of Pb-free 2D halide perovskite nanostructures. Strategies for the shape-controlled synthesis of nanostructures and their excitonic properties are discussed in detail. Thermal conductivity and thermoelectric properties are emphasized along with the magnetic properties of layered transition-metal based perovskites. We have also mentioned the recent examples of all-inorganic 2D halide perovskites as photocatalysts for solar-driven CO2 reduction. Finally, we have concluded the article with an outlook for the further progress in 2D all-inorganic halide perovskites toward the structural diversity and prospective new applications.

Nanostructured Transition Metal Oxides for Aqueous Hybrid Electrochemical Supercapacitors

Abstract: In this paper, we wish to present an overview of the research carried out in our laboratories with low-cost transition metal oxides (manganese dioxide, iron oxide and vanadium oxide) as active electrode materials for aqueous electrochemical supercapacitors. More specifically, the paper focuses on the approaches that have been used to increase the capacitance of the metal oxides and the cell voltage of the supercapacitor. It is shown that the cell voltage of an electrochemical supercapacitor can be increased significantly with the use of hybrid systems. The most relevant associations are Fe3O4 or activated carbon as the negative electrode and MnO2 as the positive. The cell voltage of the Fe3O4/MnO2 device is 1.8 V and this value was increased to 2.2 V by using activated carbon instead of Fe3O4. These two systems have shown superior behavior compared to a symmetric MnO2/MnO2 device which only works within a 1 V potential window in aqueous K2SO4. Furthermore, the activated carbon/MnO2 hybrid device exhibits a real power density of 605 W/kg (maximum power density =19.0 kW/kg) with an energy density of 17.3 Wh/kg. These values compete well with those of standard electrochemical double layer capacitors working in organic electrolytes.

Stacking-dependent magnetism in bilayer CrI3

Abstract: We report the connection between the stacking order and magnetic properties of bilayer CrI3 using first-principles calculations. We show that the stacking order defines the magnetic ground state. By changing the interlayer stacking order, one can tune the interlayer exchange interaction between antiferromagnetic and ferromagnetic. To measure the predicted stacking-dependent magnetism, we propose using linear magnetoelectric effect. Our results not only gives a possible explanation for the observed antiferromagnetism in bilayer CrI3 but also have direct implications in heterostructures made of two-dimensional magnets.

Hydrochromic CsPbBr 3 Nanocrystals for Anti‑Counterfeiting

Abstract: Hydrochromic materials that can reversibly change color upon water treatment have attracted much attention owing to their potential applications in diverse fields. Herein, for the first time, we report that space-confined CsPbBr3 nanocrystals (NCs) are hydrochromic. When CsPbBr3 NCs are loaded into a porous matrix, reversible transition between luminescent CsPbBr3 and non-luminescent CsPb2 Br5 can be achieved upon the exposure/removal of water. The potential applications of hydrochromic CsPbBr3 NCs in anti-counterfeiting are demonstrated by using CsPbBr3 NCs@mesoporous silica nanospheres (around 100 nm) as the starting material. Owing to the small particle size and negatively charged surface, the as-prepared particles can be laser-jet printed with high precision and high speed. We demonstrate the excellent stability over repeated transformation cycles without color fade. This new discovery may not only deepen the understanding of CsPbX3 , but also open a new way to design CsPbX3 materials for new applications.