Mobility driven thermoelectric and optical properties of two-dimensional halide-based hybrid perovskites: impact of organic cation rotation.

The pivotal impact of organic cation rotation may result in structural complexity in two-dimensional (2D) halide-based hybrid perovskites. The crucial role of the orientation of the organic cation (MA = CH3NH3+) in the 2D Ruddlesden-Popper phase (2DRP) is explored using density functional theory (DFT) calculations. Our results propose that the MA cation rotation imposes the structural distortion in the PbI6 network, which is further responsible for the changes in nature and value of the electronic bandgap, charge density and optical absorption. The spin-orbit coupling effect results in a wide range of Rashba splitting parameters being obtained from 0.04 to 0.278 eV Å. The simulated optical absorption spectra suggest that absorption edge for the alignment of the MA molecule along the X-axis (having unidirectional hydrogen bonds) is higher than that of the alignment of the MA cation in the z-direction. Furthermore, the unidirectional hydrogen bonds between the MA cation and Pb-I framework significantly help to achieve the highest mobility of charge carriers up to ∼1437 cm2 V-1 s-1. Such high mobility leads to supremacy in the thermoelectric transport properties, which are investigated for the first time with the rotation of the MA cation. The calculated thermoelectric power factor at room temperature shows exceptionally high values (up to 2.04 mW m-1 K-2), leading to desired applications in thermoelectric devices. The rotation of the MA cation might be utilized as a useful tool for variation in optical absorption and transport coefficients. Therefore, our results spark the idea to develop 2D perovskites for real-time perspective in solar and heat energy utilization.

Thermal conductivity of free-standing silicon nanowire using Raman spectroscopy.

Low dimensional systems, nanowires (NWs), in particular, have exhibited excellent optical and electronic properties. Understanding the thermal properties in semiconductor NWs is very important for their applications in electronic devices. In the present study, the thermal conductivity of a freestanding silicon NW is estimated by employing Raman spectroscopy. The advantage of this technique is that the excitation source (laser) acts as both the heater and probe. The variations of the first-order Raman peak position of the freestanding silicon NW with respect to temperature and laser power are recorded. From the analysis of effective laser power absorbed by exposed silicon NW and a detailed Raman study along with the concept of longitudinal heat distribution in silicon NW, the thermal conductivity of the freestanding silicon NW of ∼112 nm diameter is estimated to be ∼53 W m-1 K- 1.

Modulating the electronic and optical properties of monolayer arsenene phases by organic molecular doping.

Recently, arsenene monolayer structure of the arsenic with two phases has displayed semiconducting behavior. We have systematically investigated the electronic and optical properties of single-layer arsenene with two types of functionalized organic molecules; an electrophilic molecule [tetracyanoquinodimethane (TCNQ)] and a nucleophilic molecule [tetrathiafulvalene (TTF)], as an electron acceptor and electron donor, respectively. The interfacial charge transfer between the arsenene monolayer and TCNQ/TTF molecules extensively reduces the band gap of arsenene and accordingly resulted in a p- or n-type semiconducting behavior, respectively. We have also performed the interfacial charge transfer from organic molecules to monolayer arsenene and vice versa. The interfacial surface molecular modification has established an efficient way to develop the light harvesting of arsenene in different polarization directions. Our theoretical investigation suggests that such n- and p-type arsenene semiconductors would broaden the applications in the field of nanoelectronic and optoelectronic devices such as photodiodes and it is also useful for constructing functional electronic systems.

Surface energy engineering for tunable wettability through controlled synthesis of MoS2.

MoS2 is an important member of the transition metal dichalcogenides that is emerging as a potential 2D atomically thin layered material for low power electronic and optoelectronic applications. However, for MoS2 a critical fundamental question of significant importance is how the surface energy and hence the wettability is altered at the nanoscale in particular, the role of crystallinity and orientation. This work reports on the synthesis of large area MoS2 thin films on insulating substrates (SiO2/Si and Al2O3) with different surface morphology via vapor phase deposition by varying the growth temperatures. The samples were examined using transmission electron microscopy and Raman spectroscopy. From contact angle measurements, it is possible to correlate the wettability with crystallinity at the nanoscale. The specific surface energy for few layers MoS2 is estimated to be about 46.5 mJ/m(2). Moreover a layer thickness-dependent wettability study suggests that the lower the thickness is, the higher the contact angle will be. Our results shed light on the MoS2-water interaction that is important for the development of devices based on MoS2 coated surfaces for microfluidic applications.

Thermally Driven Multilevel Non-Volatile Memory with Monolayer MoS2 for Brain-Inspired Artificial Learning.

The demands of modern electronic components require advanced computing platforms for efficient information processing to realize in-memory operations with a high density of data storage capabilities toward developing alternatives to von Neumann architectures. Herein, we demonstrate the multifunctionality of monolayer MoS2 memtransistors, which can be used as a high-geared intrinsic transistor at room temperature; however, at a high temperature (>350 K), they exhibit synaptic multilevel memory operations. The temperature-dependent memory mechanism is governed by interfacial physics, which solely depends on the gate field modulated ion dynamics and charge transfer at the MoS2/dielectric interface. We have proposed a non-volatile memory application using a single Field Effect Transistor (FET) device where thermal energy can be ventured to aid the memory functions with multilevel (3-bit) storage capabilities. Furthermore, our devices exhibit linear and symmetry in conductance weight updates when subjected to electrical potentiation and depression. This feature has enabled us to attain a high classification accuracy while training and testing the Modified National Institute of Standards and Technology datasets through artificial neural network simulation. This work paves the way toward reliable data processing and storage using 2D semiconductors with high-packing density arrays for brain-inspired artificial learning.

Bipolar Resistive Switching in TiO2 Artificial Synapse Mimicking Pavlov's Associative Learning.

Memristive devices are among the most emerging electronic elements to realize artificial synapses for neuromorphic computing (NC) applications and have potential to replace the traditional von-Neumann computing architecture in recent times. In this work, pulsed laser deposition-manufactured Ag/TiO2/Pt memristor devices exhibiting digital and analog switching behavior are considered for NC. The TiO2 memristor shows excellent performance of digital resistive switching with a memory window of order ∼103. Furthermore, the analog resistive switching offers multiple conductance levels supporting the development of the bioinspired synapse. A possible mechanism for digital and analog switching behavior in our device is proposed. Remarkably, essential synaptic functions such as pair-pulse facilitation, long-term potentiation (LTP), and long-term depression (LTD) are successfully realized based on the change in conductance through analog memory characteristics. Based on the LTP-LTD, a neural network simulation for the pattern recognition task using the MNIST data set is investigated, which shows a high recognition accuracy of 95.98%. Furthermore, more complex synaptic behavior such as spike-time-dependent plasticity and Pavlovian classical conditioning is successfully emulated for associative learning of the biological brain. This work enriches the TiO2-based resistive random-access memory, which provides information about the simultaneous existence of digital and analog behavior, thereby facilitating the further implementation of memristors in low-power NC.

Reconfigurable Low-Power TiO2 Memristor for Integration of Artificial Synapse and Nociceptor.

Bio-mimetic advanced electronic systems are emerging rapidly, engrossing their applications in neuromorphic computing, humanoid robotics, tactile sensors, and so forth. The biological synaptic and nociceptive functions are governed by intricate neurotransmitter dynamics that involve both short-term and long-term plasticity. To emulate the neuronal dynamics in an electronic device, an Ag/TiO2/Pt/SiO2/Si memristor is fabricated, exhibiting compliance current controlled reversible transition of volatile switching (VS) and non-volatile switching (NVS). The origin of the VS and NVS depends on the diameter of the conducting filament, which is explained using a field-induced nucleation theory and validated by temporal current response measurements. The switching delay of the device is used to determine the characteristic nociceptive behaviors such as threshold, relaxation, inadaptation, allodynia, and hyperalgesia. The short-term and long-term retention loss attributed to the VS and NVS, respectively, is used to emulate short-term memory and long-term memory of the biological brain in a single device. More importantly, synergistically modulating the VS-NVS transition, the complex spike rate-dependent (SRDP) and spike time-dependent plasticity (STDP) with a weight change of up to 600% is demonstrated in the same device, which is the highest reported so far for TiO2 memristors. Furthermore, the device exhibits very low power consumption, ∼3.76 pJ/spike, and can imitate synaptic and nociceptive functions. The consolidation of complex nociceptive and synaptic behavior in a single memristor facilitates low-power integration of scalable intelligent sensors and neuromorphic devices.

Strain-mediated ferromagnetism and low-field magnetic reversal in Co doped monolayer [Formula: see text].

Strain-mediated magnetism in 2D materials and dilute magnetic semiconductors hold multi-functional applications for future nano-electronics. Herein, First principles calculations are employed to study the influence of biaxial strain on the magnetic properties of Co-doped monolayer [Formula: see text]. The non-magnetic [Formula: see text] shows ferromagnetic signature upon Co doping due to spin polarization, which is further improved at low compressive (-2 %) and tensile (+2 %) strains. From the PDOS and spin density analysis, the opposite magnetic ordering is found to be favourable under the application of compressive and tensile strains. The double exchange interaction and p-d hybridization mechanisms make Co-doped [Formula: see text] a potential host for magnetism. More importantly, the competition between exchange and crystal field splittings, i.e. ([Formula: see text]), of the Co-atom play pivotal roles in deciding the values of the magnetic moments under applied strain. Micromagnetic simulation reveals, the ferromagnetic behavior calculated from DFT exhibits low-field magnetic reversal (190 Oe). Moreover, the spins of Co-doped [Formula: see text] are slightly tilted from the easy axis orientations showing slanted ferromagnetic hysteresis loop. The ferromagnetic nature of Co-doped [Formula: see text] suppresses beyond [Formula: see text] strain, which is reflected in terms of decrease in the coercivity in the micromagnetic simulation. The understanding of low-field magnetic reversal and spin orientations in Co-doped [Formula: see text] may pave the way for next-generation spintronics and straintronics applications.

Effect of Charge Injection on the Conducting Filament of Valence Change Anatase TiO2 Resistive Random Access Memory Device.

The recent observation of stable quantized conductance in anatase TiO2 resistive random access memory (ReRAM) devices opens up a new pathway toward the realization of brain-inspired neuromorphic computing devices. Herein, for the first time, ab initio calculations are implemented to understand the resistive switching phenomena in anatase TiO2. Oxygen vacancy configurations with different charge states are studied to gain insight into the ON and OFF states of ReRAM devices. Among the trivacancy configurations, the Vo+ state is observed to induce highly dispersed defect states within the bandgap forming a charge density channel where the carriers behave as free electrons leading to the formation of a conducting filament (CF). On the contrary, the breakdown of the CF is noticed by the removal of an oxygen vacancy from the trivacancy configuration. In this OFF state, the defect state carriers are found to be highly localized. In addition, we have also investigated the effect of charge injection on the crystal field symmetry of the CF. The reduction of symmetry due to the trivacancy configuration lowers the eg manifold energy, whereas the divacancy configuration lowers the t2g manifold energy.

Rashba Splitting in Two Dimensional Hybrid Perovskite Materials for High Efficient Solar and Heat Energy Harvesting.

The physical properties of two-dimensional (2D) lead halide based hybrid perovskites are quite exciting and challenging. Further, the role of organic cations in 2D perovskites is still in a debate. We investigated layered (CH3(CH2)3NH3)2(CH3NH3)Pb2I7 2D Ruddlesden-Popper (2DRP) phase (M1) and 2D derivative of CH3NH3PbI3 (M2) using density functional theory. The spin orbit coupling mediates the significantly large Rashba splitting energy of 328.5 meV for M2, which is higher than earlier 2D hybrid perovskites. At the picosecond time scale, the dynamical Rashba effect was observed due to organic and inorganic cation dynamics. Two step absorption suggests an indirect optical gap of 2.38 and 2.15 eV for M1 and M2, respectively and solar performance depicts excellent power conversion efficiency of 14.92% and 19.75% for M1 and M2, respectively. For the first time, we explored the thermoelectric properties of 2D hybrid perovskites and perceived high power factor for p-type doping in M2. Our findings suggest that these novel 2D perovskites have the potential to be used in solar and heat energy harvesting.

Phonon confinement in stressed silicon nanocluster.

Confined acoustic and optical phonons in Si nanoclusters embedded in sapphire, synthesized using ion-beam implantation are investigated using Raman spectroscopy. The l=0 and l=2 confined acoustic phonons, found at low Raman shift, are analyzed using complex frequency model and the size of the nanoparticles are estimated as 4 and 6 nm. For the confined optical phonon, in contrast to expected red shift, the Raman line shape shows a substantial blue shift, which is attributed to size dependent compressive stress in the nanoparticles. The calculated Raman line shape for the stressed nanoparticles fits well to data. The sizes of Si nanoparticles obtained using complex frequency model are consistent with the size estimated from the fitting of confined optical phonon line shapes and those found from X-ray diffraction and TEM.

Confined acoustic phonon in CdSC(1-x)Se(x) nanoparticles in borosilicate glass.

We calculate low-frequency Raman scattering from the confined acoustic phonon modes of CdS(1-x)Se(x) nanoparticles embedded in borosilicate glass. The calculation of the Raman scattering by acoustic phonons in nanoparticles has been performed by using third-order perturbation theory. The deformation potential approximation is used to describe the electron-phonon interaction. The Raman-Brillouin electronic density and the electron-phonon interaction are found to increases with decreasing size of nanoparticle. A good agreement between the calculated and reported low-frequency Raman spectra is found.

Spin-Polarized Tunneling through Chemical Vapor Deposited Multilayer Molybdenum Disulfide.

The two-dimensional (2D) semiconductor molybdenum disulfide (MoS2) has attracted widespread attention for its extraordinary electrical-, optical-, spin-, and valley-related properties. Here, we report on spin-polarized tunneling through chemical vapor deposited multilayer MoS2 (∼7 nm) at room temperature in a vertically fabricated spin-valve device. A tunnel magnetoresistance (TMR) of 0.5-2% has been observed, corresponding to spin polarization of 5-10% in the measured temperature range of 300-75 K. First-principles calculations for ideal junctions result in a TMR up to 8% and a spin polarization of 26%. The detailed measurements at different temperature, bias voltages, and density functional theory calculations provide information about spin transport mechanisms in vertical multilayer MoS2 spin-valve devices. These findings form a platform for exploring spin functionalities in 2D semiconductors and understanding the basic phenomena that control their performance.

Thermal conductivity of freestanding single wall carbon nanotube sheet by Raman spectroscopy.

Thermal properties of single wall carbon nanotube sheets (SWCNT-sheets) are of significant importance in the area of thermal management, as an isolated SWCNT possesses high thermal conductivity of the value about 3000 W m(-1) K(-1). Here we report an indirect method of estimating the thermal conductivity of a nanometer thick suspended SWCNT-sheet by employing the Raman scattering technique. Tube diameter size is examined by the transmissions electron microscopy study. The Raman analysis of the radial breathing modes predicts narrow diameter size distribution with achiral (armchair) symmetry of the constituent SWCNTs. From the first order temperature coefficient of the A1g mode of the G band along with the laser power dependent frequency shifting of this mode, the thermal conductivity of the suspended SWCNT-sheet is estimated to be about ∼18.3 W m(-1) K(-1). Our theoretical study shows that the thermal conductivity of the SWCNT-sheet has contributions simultaneously from the intratube and intertube thermal transport. The intertube thermal conductivity (with contributions from the van der Waals interaction) is merely around 0.7 W m(-1) K(-1), which is three orders smaller than the intratube thermal conductivity, leading to an abrupt decrease in the thermal conductivity of the SWCNT-sheet as compared to the reported value for isolated SWCNT.

Laser-power-induced multiphonon resonant raman scattering in laser-heated CdS nanocrystal.

The size stability of nanoparticles is crucial from an application point of view. We probe, using Raman spectroscopy, particle size evolution of CdS nanoparticles by varying laser power. Multiphonon resonant Raman scattering has also been demonstrated. With increase in laser power, the intensity ratio of 2-longitudinal optical (LO) to 1-LO is found to increase dramatically, and LO phonon overtones up to fourth order are observed. Resonant Raman scattering has been achieved by suitably matching the band gap with the excitation photon energy, by varying the local temperature. The effect of increase in local temperature on the band gap is also discussed.