Ravishankar Sundararaman

Rensselaer Polytechnic Institute | RPI · Department of Materials Science and Engineering

Fully harnessing electrochemical interfaces for reactions requires a detailed understanding of solvent effects in the electrochemical double layer. Predicting the significant impact of solvent on entropic and electronic properties of electrochemical interfaces has remained an open challenge of computational electrochemistry. Using molecular dynamic...

The increasing resistance of Cu interconnects for decreasing dimensions is a major challenge in continued downscaling of integrated circuits beyond the 7-nm technology node as it leads to unacceptable signal delays and power consumption in computing. The resistivity of Cu increases due to electron scattering at surfaces and grain boundaries of the...

The increasing resistance of Cu interconnects for decreasing dimensions is a major challenge in continued downscaling of integrated circuits beyond the 7-nm technology node as it leads to unacceptable signal delays and power consumption in computing. The resistivity of Cu increases due to electron scattering at surfaces and grain boundaries of the...

Carrier transport in materials is often diffusive due to momentum-relaxing scattering with phonons and defects. Suppression of momentum-relaxing scattering can lead to the ballistic and hydrodynamic transport regimes, wherein complex non-Ohmic current flow patterns, including current vortices, can emerge. In the ballistic regime addressed here, tra...

The resistivity size effect in the ordered intermetallic CuTi compound is quantified using in situ and ex situ thin film resistivity ρ measurements at 295 and 77 K, and density functional theory Fermi surface and electron–phonon scattering calculations. Epitaxial CuTi(001) layers with thickness d = 5.8–149 nm are deposited on MgO(001) at 350 °C and...

Knowing the dielectric properties of the interfacial region in polymer nanocomposites is critical to predicting and controlling dielectric properties. They are, however, difficult to characterize due to their nanoscale dimensions. Electrostatic force microscopy (EFM) provides a pathway to local dielectric property measurements, but extracting local...

Realizing the potential of plasmonic hot carrier harvesting for energy conversion and photodetection requires new materials that resolve the bottleneck of extracting carriers prior to energy relaxation within the metal. Using first-principles calculations of optical response and carrier transport properties, we show that directional conductors with...

Protected surface states arising from non-trivial bandstructure topology in semimetals can potentially enable new device functionalities in compute, memory, interconnect, sensing, and communication. This necessitates a fundamental understanding of surface-state transport in nanoscale topological semimetals. Here, we investigate quantum transport in...

Spintronics in halide perovskites has drawn significant attention in recent years, due to highly tunable spin-orbit fields and intriguing interplay with lattice symmetry. Spin lifetime - a key parameter that determines the applicability of materials for spintronics and spin-based quantum information applications - has been extensively measured in h...

Increasing resistivity of metal wires with reducing nanoscale dimensions is a major performance bottleneck of semiconductor computing technologies. We show that metals with suitably anisotropic Fermi velocity distributions can strongly suppress electron scattering by surfaces and outperform isotropic conductors such as copper in nanoscale wires. We...

Interactions of charge carriers with lattice vibrations, or phonons, play a critical role in unconventional electronic transport of metals and semimetals. Recent observations of phonon-mediated collective electron flow in bulk semimetals, termed electron hydrodynamics, present new opportunities in the search for strong electron-electron interaction...

The increasing resistance of Cu interconnects for decreasing dimensions is a major challenge in continued downscaling of integrated circuits beyond the 7-nm technology node as it leads to unacceptable signal delays and power consumption in computing. The resistivity of Cu increases due to electron scattering at surfaces and grain boundaries of the...

Polymer Nanodielectrics are class of materials with intriguing combinations of properties. Predicting and designing the properties, however, is complex due to the number of parameters controlling the properties. This makes it difficult to compare results across groups, validate models, and develop a design methodology. This presentation will share...

Spintronic devices, by harnessing the spin degree of freedom, are expected to outperform charge-based devices in terms of energy efficiency and speed of operation. The use of an electric field to control spin at room temperature has been pursued for decades. A major hurdle that has contributed to the slow progress in this regard is the dilemma betw...

Predicting and designing the properties of polymer nanodielectrics is challenging due to the number of parameters controlling properties and the breadth of scale (from electronic to mm). This paper summarizes a preliminary study using elongated semiconducting nanoparticles with an extrinsic interface that enhanced carrier trapping to attempt to fin...

Realizing the potential of plasmonic hot carrier harvesting for energy conversion and photodetection requires new materials that resolve the bottleneck of extracting carriers prior to energy relaxation within the metal. Using first-principles calculations of optical response and carrier transport properties, we show that directional conductors with...

Atomistic simulation of the electrochemical double layer is an ambitious undertaking, requiring quantum mechanical description of electrons, phase space sampling of liquid electrolytes, and equilibration of electrolytes over nanosecond time scales. All models of electrochemistry make different trade-offs in the approximation of electrons and atomic...

We have calculated the time constants of the electron dynamics in traps in a metal-insulator-metal (MIM) plasmonic structure. Because of electron relaxation in metal, the surface plasmon polaritons decays into hot electrons near the surface of the metal, which facilitates the trap of electrons in the interfacial layer of the dielectric. We have cal...

Electrons in graphene are theoretically expected to retain spin states much longer than most materials, making graphene a promising platform for spintronics and quantum information technologies. Here, we use first-principles density-matrix (FPDM) dynamics simulations to show that interaction with electric fields and substrates strongly enhances spi...

Controlling electrochemical reactivity requires a detailed understanding of the charging behavior and thermodynamics of the electrochemical interface.Experiments can independently probe the overall charge response of the electrochemical double layer by capacitance measurements, and the thermodynamics of the inner layer with potential of maximum ent...

Spin relaxation and decoherence is at the heart of spintronics and spin-based quantum information science. Currently, theoretical approaches that can accurately predict spin relaxation of general solids including necessary scattering pathways and are capable of nanosecond to millisecond simulation time are urgently needed. We present a first-princi...

The electrical resistance of interconnect wires increases with decreasing size, causing signal delay and energy consumption that limits further downscaling of integrated circuits. Electron scattering at surfaces and grain-boundaries of current-technology Cu and Co conductors causes the resistivity of narrow lines to be an order of magnitude above b...

This chapter introduces a novel approach to first principles computational electrochemistry that occupies a unique intermediate niche among available approaches, offering the advantages of the alternate approaches without the consequent disadvantages. It presents a new, complementary approach which maintains both computational efficiency and quanti...

Through First-Principles real-time Density-Matrix (FPDM) dynamics simulations, we investigate spin relaxation due to electron-phonon and electron-impurity scatterings with spin-orbit coupling in two-dimensional Dirac materials - silicene and germanene, at finite temperatures and under external fields. We discussed the applicability of conventional...

Identifying collective variables for chemical reactions is essential to reduce the 3$N$ dimensional energy landscape into lower dimensional basins and barriers of interest. However in condensed phase processes, the non-meaningful motions of bulk solvent often overpower the ability of dimensionality reduction methods to identify correlated motions t...

Identifying collective variables for chemical reactions is essential to reduce the 3$N$ dimensional energy landscape into lower dimensional basins and barriers of interest. However in condensed phase processes, the non-meaningful motions of bulk solvent often overpower the ability of dimensionality reduction methods to identify correlated motions t...

This paper presents a fully ab initio many-body photoemission framework that includes coherent three-body electron-photon-phonon scattering to predict the transverse momentum distributions and the mean transverse energies (MTEs) of bulk photoelectrons from single-crystal photocathodes. The need to develop such a theory stems from the lack of studie...

Metal nanostructures capture light efficiently due to plasmonic enhancement and generate energetic electrons and holes that can be used to drive chemical reactions or transferred across metal–semiconductor interfaces for solar cells and photodetectors. The overall efficiency of plasmonic hot-carrier devices depends on the generated energy distribut...

In situ transport measurements on 5.8–92.1 nm thick epitaxial Ti4SiC3(0001) layers are used to experimentally verify the previously predicted low resistivity scaling. Magnetron co-sputtering from three elemental sources at 1000 °C onto 12-nm-thick TiC(111) nucleation layers on Al2O3(0001) substrates yields epitaxial growth with Ti4SiC3(0001) || Al2...

The detailed understanding of energy transfer between hot electrons and lattice vibrations at non-cryogenic temperatures relies primarily upon the interpretation of ultrafast pump–probe experiments, where thermo-optical models provide insight into the relationship between optical response and temperature of the respective sub-systems; in one of the...

Interphase regions in polymer nanocomposite materials are difficult to characterize due to their nano-scale dimensions. Electrostatic force microscopy (EFM) provides a pathway to local dielectric property measurements, but extracting local dielectric permittivity in complex interphase geometries from EFM measurements remains a challenge. We demonst...

Intermetallic compounds have been proposed as potential interconnect materials for advanced semiconductor devices. This study reports the interdiffusion reliability and resistivity scaling of three low-resistivity intermetallic compounds (Cu2Mg, CuAl2, and NiAl) formed on thermally grown SiO2. Experimental observations and thermodynamic calculation...

Computational quantum chemistry provides fundamental chemical and physical insights into solvated reaction mechanisms across many areas of chemistry, especially in homogeneous and heterogeneous renewable energy catalysis. Such reactions may depend on explicit interactions with ions and solvent molecules that are nontrivial to characterize. Rigorous...

Potential-induced changes in charge and surface structure are significant drivers of the reactivity of electrochemical interfaces but are frequently difficult to decouple from the effects of surface solvation. Here, we consider the Cu(100) surface with a c(2 × 2)-Cl adlayer, a model surface with multiple geometry measurements under both ultrahigh v...

Experimental spin relaxation times in graphene, critical for spintronics and quantum information technologies, are two orders of magnitude below previous theoretical predictions for spin-phonon relaxation. Here, ab initio density-matrix dynamics simulations reveal that electric fields and substrates strongly reduce spin-phonon relaxation time to th...

A fundamental understanding of hot-carrier dynamics in photo-excited metal nanostructures is needed to unlock their potential for photodetection and photocatalysis. Despite numerous studies on the ultrafast dynamics of hot electrons, so far, the temporal evolution of hot holes in metal–semiconductor heterostructures remains unknown. Here, we report...

div>Computational quantum chemistry modeling provides fundamental chemical and physical insights into solvated reaction mechanisms across many areas of chemistry, especially in homogeneous and heterogeneous renewable energy catalysis. Such reactions may depend on explicit interactions with ions and solvent molecules that are non-trivial to characte...

Inspired by the ability of super-resolved fluorescence microscopy to circumvent the diffraction barrier, two-color super-resolution interference lithography exploits non-equilibrium kinetics in materials to achieve large area nanopatterning while using visible light. Periodic patterns with super-resolved features down to tens of nanometers have bee...

Merging concepts from the fields of ab initio materials science and nanophotonics, there is now an opportunity to engineer new photonic materials whose optical, transport, and scattering properties are tailored to attain thermodynamic and quantum limits. Here we present first-principles calculations predicting that Argentene, a single-crystalline h...

This manuscript presents, to our knowledge, the first fully ab initio many-body photoemission framework to predict the transverse momentum distributions and the mean transverse energies (MTEs) of photoelectrons from single-crystal photocathodes. The need to develop such a theory stems from the lack of studies that provide complete understanding of...

Designing new quantum materials with long-lived electron spin states urgently requires a general theoretical formalism and computational technique to reliably predict intrinsic spin relaxation times. We present a new, accurate and universal first-principles methodology based on Lindbladian dynamics of density matrices to calculate spin-phonon relax...

Among plasmonic metals, copper (Cu) has great potential for realizing optoelectronic and photoelectrochemical hot carrier devices, owing to its CMOS compatibility and catalytic ability for electrochemical carbon dioxide reduction. Yet, copper hot carrier dynamics have received little attention and the fundamental properties of photoexcited carriers...

First-principles predictions play an important role in understanding chemistry at the electrochemical interface. Electronic structure calculations are straightforward for vacuum interfaces, but do not easily account for the interfacial fields and solvation that fundamentally change the nature of electrochemical reactions. Prevalent techniques for f...

Point defects in two-dimensional (2D) materials hold great promise for optoelectronic and quantum technologies. Their properties depend sensitively on the dielectric environment and number of 2D layers, but this has remained a challenge to include in first-principles calculations on account of the high computational cost. Recent first-principles te...

First-principles identification of localized trap states in polymer nanocomposite interfaces - Abhishek Shandilya, Linda S. Schadler, Ravishankar Sundararaman

Spin and valley degrees of freedom in materials without inversion symmetry promise previously unknown device functionalities, such as spin-valleytronics. Control of material symmetry with electric fields (ferroelectricity), while breaking additional symmetries, including mirror symmetry, could yield phenomena where chirality, spin, valley, and crys...

The design of new quantum materials with long-lived electron spin states requires a general theoretical formalism and computational technique to predict intrinsic spin relaxation times, but current methods require specialized approaches for each class of material and electronic structure. We present a new, universal first-principles methodology bas...

Super resolution microscopy (SRM) brings the advantages of optical microscopy to the imaging of nanostructured soft matter, and in colloidal microgels, promises to quantify variations of crosslink densities at unprecedented length scales. However, the distribution of all crosslinks does not coincide with that of dye-tagged crosslinks, and density q...

Two-dimensional (2D) materials are strongly affected by the dielectric environment, including substrates, making it an important factor in designing materials for quantum and electronic technologies. Yet, first-principles evaluations of charged defect energetics in 2D materials typically do not include substrates due to the high computational cost....

CMOS-compatible, refractory conductors are emerging as the materials that will advance novel concepts into real, practical plasmonic technologies. From the available pallet of materials, those with negative real permittivity at very short wavelengths are extremely rare; importantly they are vulnerable to oxidation – upon exposure to far UV radiatio...

Transport of charged carriers in regimes of strong non-equilibrium is critical in a wide array of applications ranging from solar energy conversion and semiconductor devices to quantum information. Plasmonic hot-carrier science brings this regime of transport physics to the forefront since photo-excited carriers must be extracted far from equilibri...

Electron transport in clean 2D systems with weak electron-phonon (e-ph) coupling can transition from an Ohmic to a ballistic or a hydrodynamic regime. The ballistic regime occurs when electron-electron (e-e) scattering is weak whereas the hydrodynamic regime arises when this scattering is strong. Despite this difference, we find that vortices and a...

The Dirac point and linear band structure in graphene bestow it with remarkable electronic and optical properties, a subject of intense ongoing research. Explanations of high electronic mobility in graphene often invoke the masslessness of electrons based on the effective relativistic Dirac-equation behavior, which are inaccessible to most undergra...

Plasmonic-metal nanostructures offer unique opportunities for solar photocatalysis via photo-excitation of highly energetic "hot" carriers at both metal-semiconductor and metal-electrolyte interfaces that can drive photochem. reactions. While examples of hot-electron-driven processes have been widely reported, little is known about the nature of pl...

We report on quantum emission from Pb-related color centers in diamond following ion implantation and high-temperature vacuum annealing. First-principles calculations predict a negatively charged Pb-vacancy (PbV) center in a split-vacancy configuration, with a zero-phonon transition around 2.4 eV. Cryogenic photoluminescence measurements performed...

Harvesting non-equilibrium hot carriers from photo-excited metal nanoparticles has enabled plasmon-driven photochemical transformations and tunable photodetection with resonant nanoantennas. Despite numerous studies on the ultrafast dynamics of hot electrons, to date, the temporal evolution of hot holes in metal-semiconductor heterostructures remai...

Harvesting non-equilibrium hot carriers from photo-excited metal nanoparticles has enabled plasmon-driven photochemical transformations and tunable photodetection with resonant nanoantennas. Despite numerous studies on the ultrafast dynamics of hot electrons, to date, the temporal evolution of hot holes in metal-semiconductor heterostructures remai...

Harnessing photoexcited "hot" carriers in metallic nanostructures could define a new phase of non-equilibrium optoelectronics for photodetection and photocatalysis. Surface plasmons are considered pivotal for enabling efficient operation of hot carrier devices. Clarifying the fundamental role of plasmon excitation is therefore critical for exploiti...

Transition metal dichalcogenides have been the primary materials of interest in the field of valleytronics for their potential in information storage, yet the limiting factor has been achieving long valley decoherence times. We explore the dynamics of four monolayer TMDCs (MoS2, MoSe2, WS2, WSe2) using ab initio calculations to describe electron-el...

Transition metal dichalcogenides have been the primary materials of interest in the field of valleytronics for their potential in information storage, yet the limiting factor has been achieving long valley decoherence times. We explore the dynamics of four monolayer TMDCs (MoS$_2$, MoSe$_2$, WS$_2$, WSe$_2$) using ab initio calculations to describe...

Two-dimensional materials exhibit a fascinating range of electronic and photonic properties vital for nanophotonics, quantum optics and emerging quantum information technologies. Merging concepts from the fields of ab initio materials science and nanophotonics, there is now an opportunity to engineer new photonic materials whose optical, transport,...

We report on quantum emission from Pb-related color centers in diamond following ion implantation and high temperature vacuum annealing. First-principles calculations predict a negatively-charged Pb-vacancy center in a split-vacancy configuration, with a zero-phonon transition around 2.3 eV. Cryogenic photoluminescence measurements performed on emi...

In this work we investigate the effects of the diffuse double layer thickness on the electrochemical Stark tuning and oxidation of carbon monoxide at Pt(111) surfaces in perchloric acid solution. The diffuse double layer thickness was modified by changing the concentration (ionic strength) of the supporting electrolyte. The Stark tuning slope of th...

The origins of hydrodynamic transport in strongly interacting Dirac and Weyl semimetals have remained elusive in theoretical descriptions and experimental measurements. We investigate the structure and microscopic properties of transport in WP$_2$, a type-II Weyl semimetal, to probe the emergence of hydrodynamic phenomena. We characterize the quant...

Reliable first-principles calculations of electrochemical processes require simultaneously capturing interfacial capacitance and energetics of adsorbed species accurately, a challenge for current computationally-efficient continuum solvation methodologies. We develop a model for the double layer of a metallic electrode that reproduces the features...

Decay of plasmons to hot carriers has recently attracted considerable interest for fundamental studies and applications in quantum plasmonics. Although plasmon-assisted hot carriers in metals have already enabled remarkable physical and chemical phenomena, much remains to be understood to engineer devices. Here, we present an analysis of the spatio...

Nanoparticles attached just above a flat metallic surface can trap optical fields in the nanoscale gap. This enables local spectroscopy of a few molecules within each coupled plasmonic hotspot, with near thousand-fold enhancement of the incident fields. As a result of non-radiative relaxation pathways, the plasmons in such sub-nanometre cavities ge...