Structure Low Dimensionality and Lone-Pair Stereochemical Activity: the Key to Low Thermal Conductivity in the Pb-Sn-S System.

Recently, metal sulfides have begun to receive attention as potential cost-effective materials for thermoelectric applications beyond optoelectronic and photovoltaic devices. Herein, based on a comparative analysis of the structural and transport properties of 2D PbSnS2 and 1D PbSnS3, we demonstrate that the intrinsic effects that govern the low lattice thermal conductivity (κL) of these sulfides originate from the combination of the low dimensionality of their crystal structures with the stereochemical activity of the lone-pair electrons of cations. The presence of weak bonds in these materials, responsible for phonon scattering, results in inherently low κL of 1.0 W/m K in 1D PbSnS3 and 0.6 W/m K in 2D PbSnS2 at room temperature. However, the nature of the thermal transport is quite distinct. 1D PbSnS3 exhibits a higher thermal conductivity with a crystalline-like peak at low temperatures, while 2D PbSnS2 demonstrates glassy thermal conductivity in the entire temperature range investigated. First-principles density functional theory calculations reveal that the presence of antibonding states below the Fermi level, especially in PbSnS2, contributes to the very low κL. In addition, the calculated phonon dispersions exhibit very soft acoustic phonon branches that give rise to soft lattices and very low speeds of sounds.

Three-Fold Coordination of Copper in Sulfides: A Blockade for Hole Carrier Delocalization but a Driving Force for Ultralow Thermal Conductivity.

Copper-rich sulfides are very promising for energy conversion applications due to their environmental compatibility, cost effectiveness, and earth abundance. Based on a comparative analysis of the structural and transport properties of Cu3BiS3 with those of tetrahedrite (Cu12Sb4S13) and other Cu-rich sulfides, we highlight the role of the cationic coordination types and networks on the electrical and thermal properties. By precession-assisted 3D electron diffraction analysis, we find very high anisotropic thermal vibration of copper attributed to its 3-fold coordination, with an anisotropic atomic displacement parameter up to 0.09 Å2. Density functional theory calculations reveal that these Cu atoms are weakly bonded and give rise to low-energy Einstein-like vibrational modes that strongly scatter heat-carrying acoustic phonons, leading to ultralow thermal conductivity. Importantly, we demonstrate that the 3-fold coordination of copper in Cu3BiS3 and in other copper-rich sulfides constituted of interconnected CuS3 networks causes a hole blockade. This phenomenon hinders the possibility of optimizing the carrier concentration and electronic properties through mixed valency Cu+/Cu2+, differently from tetrahedrite and most other copper-rich chalcogenides, where the main interconnected Cu-S network is built of CuS4 tetrahedra. The comparison with various copper-rich sulfides demonstrates that seeking for frameworks characterized by the coexistence of tetrahedral and 3-fold coordinated copper is very attractive for the discovery of efficient thermoelectric copper-rich sulfides. Considering that lattice vibrations and carrier concentration are key factors for engineering transport phenomena (electronic, phonon, ionic, etc.) in copper-rich chalcogenides for various types of applications, our findings improve the guidelines for the design of materials enabling sustainable energy solutions with wide-ranging applications.

2D nanosheets of layered double perovskites: synthesis, photostable bright orange emission and photoluminescence blinking.

Lead (Pb)-free layered double perovskites (LDPs) with exciting optical properties and environmental stability have sparked attention in optoelectronics, but their high photoluminescence (PL) quantum yield and understanding of the PL blinking phenomenon at the single particle level are still elusive. Herein, we not only demonstrate a hot-injection route for the synthesis of two-dimensional (2D) ∼2-3 layer thick nanosheets (NSs) of LDP, Cs4CdBi2Cl12 (pristine), and its partially Mn-substituted analogue [i.e., Cs4Cd0.6Mn0.4Bi2Cl12 (Mn-substituted)], but also present a solvent-free mechanochemical synthesis of these samples as bulk powders. Bright and intense orange emission has been perceived for partially Mn-substituted 2D NSs with a relatively high PL quantum yield (PLQY) of ∼21%. The PL and lifetime measurements both at cryogenic (77 K) and room temperatures were employed to understand the de-excitation pathways of charge carriers. With the implementation of super-resolved fluorescence microscopy and time-resolved single particle tracking, we identified the occurrence of metastable non-radiative recombination channels in a single NS. In contrast to the rapid photo-bleaching that resulted in a PL blinking-like nature of the controlled pristine NS, the 2D NS of the Mn-substituted sample displayed negligible photo-bleaching with suppression of PL fluctuation under continuous illumination. The blinking-like nature in pristine NSs appeared due to a dynamic equilibrium flanked by the active and in-active states of metastable non-radiative channels. However, the partial substitution of Mn2+ stabilized the in-active state of the non-radiative channels, which increased the PLQY and suppressed PL fluctuation and photo-bleaching events in Mn-substituted NSs.

Strong Antibonding I (p)-Cu (d) States Lead to Intrinsically Low Thermal Conductivity in CuBiI4.

Chemical bonding present in crystalline solids has a significant impact on how heat moves through a lattice, and with the right chemical tuning, one can achieve extremely low thermal conductivity. The desire for intrinsically low lattice thermal conductivity (κlat) has gained widespread attention in thermoelectrics, in refractories, and nowadays in photovoltaics and optoelectronics. Here we have synthesized a high-quality crystalline ingot of cubic metal halide CuBiI4 and explored its chemical bonding and thermal transport properties. It exhibits an intrinsically ultralow κlat of ∼0.34-0.28 W m-1 K-1 in the temperature range 4-423 K with an Umklapp crystalline peak of 1.82 W m-1 K-1 at 20 K, which is surprisingly lower than other copper-based halide or chalcogenide materials. The crystal orbital Hamilton population analysis shows that antibonding states generated just below the Fermi level (Ef), which arise from robust copper 3d and iodine 5p interactions, cause copper-iodide bond weakening, which leads to reduction of the elastic moduli and softens the lattice, finally to produce extremely low κlat in CuBiI4. The chemical bonding hierarchy with mixed covalent and ionic interactions present in the complex crystal structure generates significant lattice anharmonicity and a low participation ratio in low-lying optical phonon modes originating mostly from localized copper-iodide bond vibrations. We have obtained experimental evidence of these low-lying modes by low-temperature specific heat capacity measurement as well as Raman spectroscopy. The presence of strong p-d antibonding interactions between copper and iodine leads to anharmonic soft crystal lattice which gives rise to low-energy localized optical phonon bands, suppressing the heat-carrying acoustic phonons to steer intrinsically ultralow κlat in CuBiI4.

Glassy thermal conductivity in Cs3Bi2I6Cl3 single crystal.

As the periodic atomic arrangement of a crystal is made to a disorder or glassy-amorphous system by destroying the long-range order, lattice thermal conductivity, κL, decreases, and its fundamental characteristics changes. The realization of ultralow and unusual glass-like κL in a crystalline material is challenging but crucial to many applications like thermoelectrics and thermal barrier coatings. Herein, we demonstrate an ultralow (~0.20 W/m·K at room temperature) and glass-like temperature dependence (2-400 K) of κL in a single crystal of layered halide perovskite, Cs3Bi2I6Cl3. Acoustic phonons with low cut-off frequency (20 cm-1) are responsible for the low sound velocity in Cs3Bi2I6Cl3 and make the structure elastically soft. While a strong anharmonicity originates from the low energy and localized rattling-like vibration of Cs atoms, synchrotron X-ray pair-distribution function evidence a local structural distortion in the Bi-halide octahedra and Cl vacancy. The hierarchical chemical bonding and soft vibrations from selective sublattice leading to low κL is intriguing from lattice dynamical perspective as well as have potential applications.

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

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.

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

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.

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

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.

Synthesis and Localized Photoluminescence Blinking of Lead-Free 2D Nanostructures of Cs3 Bi2 I6 Cl3 Perovskite.

Two-dimensional (2D) lead-free halide perovskites have generated enormous perception in the field of optoelectronics due to their fascinating optical properties. However, an in-depth understanding on their shape-controlled charge-carrier recombination dynamics is still lacking, which could be resolved by exploring the photoluminescence (PL) blinking behaviour at the single-particle level. Herein, we demonstrate, for the first time, the synthesis of nanocrystals (NCs) and 2D nanosheets (NSs) of layered mixed halide, Cs3 Bi2 I6 Cl3 , by solution-based method. We applied fluorescence microscopy and super-resolution optical imaging at single-particle level to investigate their morphology-dependent PL properties. Narrow emission line widths and passivation of non-radiative defects were evidenced for 2D layered nanostructures, whereas the activation of shallow trap states was recognized at 77 K. Interestingly, individual NCs were found to display temporal intermittency (blinking) in PL emission. On the other hand, NS showed temporal PL intensity fluctuations within localized domains of the crystal. In addition, super-resolution optical image of the NS from localization-based method showed spatial inhomogeneity of the PL intensity within perovskite crystal.

Mechanochemical Synthesis and Temperature-Dependent Optical Properties of Thermochromic (Ag1-x Cux )2 HgI4.

Thermochromic materials are generally synthesized via high-temperature melting reaction or solution-based synthesis. Herein, all-inorganic thermochromic compounds of (Ag1-x Cux )2 HgI4 were synthesized by solvent-free simple and scalable mechanochemical grinding at room temperature. Temperature-dependent electronic absorption spectroscopy along with DSC analysis confirmed the thermochromic events within these materials, and the phase transition temperature varied with solid solution compositions. The photoluminescence (PL) spectra is red-shifted with the increase in the Cu content in (Ag1-x Cux )2 HgI4 (x=0-1).

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

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.

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

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-resolution fluorescence imaging, which indicated the blinking behavior down to the level of an individual Cs3Bi2I9 nanoplate along with its emission at the far-red region and high photostability.

Evolution of Silver-Mediated, Enhanced Fluorescent Au-Ag Nanoclusters under UV Activation: A Platform for Sensing.

Here, we report the synthesis of dopamine (DA)-mediated Au-Ag bimetallic nanoclusters in aqueous solution under UV activation. The success story emerges from monometallic fluorescent nanocluster evolution from photoactivation of gold as well as silver precursor compounds along with DA. The intriguing fluorescence property of the nanocluster relates to facile incorporation of Ag in Au, showing a 6-fold enhancement of the emission profile than simply DA-mediated Au nanoclusters. Silver effect, which is classified under the synergism, is the main reason behind such enhancement of fluorescence. The as-synthesized nanoclusters are robust and can be vacuum-dried and redispersed for repetitive application. The intriguing fluorescence of bimetallic nanoclusters is found to be quenched selectively in the presence of sulfide ion in an aqueous medium, paving the way for nanomolar detection of sulfide in water. The utility of the sensing platform has been verified employing different environmental water effluents.

Advance Aqueous Asymmetric Supercapacitor Based on Large 2D NiCo2O4 Nanostructures and the rGO@Fe3O4 Composite.

NiCo2O4 nanostructure is a widely studied pseudocapacitor material because of its high specific capacitance value. Most of the time, the thickness of the nanostructure inhibits the electrode material from whole-body participation and causes sluggish charge transportation. These phenomena directly interfere with the electrochemical performance of the electrode, such as specific capacitance value, stability, energy density, and so forth. Here, two different thin two-dimensional morphologies (nanosheet and nanoplate) of the NiCo2O4 nanocomposite with a large lateral size are reported using ammonia as a hydrolyzing agent. The large size and flat surface of the as-synthesized materials offer enormous active sites during the electrochemical reaction, and the thin wall makes the ion penetration and transportation very effective and facile. Therefore, the NiCo2O4 nanosheet and nanoplate structures exhibited high specific capacitance values of 1540 and 1333 F/g, respectively, with excellent rate and good cycling stability. Here also, two different advance aqueous asymmetric supercapacitors have been reported utilizing two NiCo2O4 nanostructure materials as positive electrodes and the rGO@Fe3O4 composite as a negative electrode, which exhibited excellent rate and high specific energy without sacrificing the specific power. We also studied the electrochemical activity of the rGO@Fe3O4 composite at different compositions.