Bivas Saha

Epitaxial superlattices with titanium nitride as a plasmonic component for optical hyperbolic metamaterials

Significance Plasmonic and metamaterial devices require high-performance material building blocks, both plasmonic and dielectric, to be useful in any real-world application. Here, we develop both plasmonic and dielectric materials that can be grown epitaxially into ultrathin and ultrasmooth layers with sharp interfaces. We show that a superlattice consisting of titanium nitride as a plasmonic component behaves as an optical hyperbolic metamaterial and exhibits extremely high photonic density of states. Titanium nitride (TiN) is a plasmonic material having optical properties resembling gold. Unlike gold, however, TiN is complementary metal oxide semiconductor-compatible, mechanically strong, and thermally stable at higher temperatures. Additionally, TiN exhibits low-index surfaces with surface energies that are lower than those of the noble metals which facilitates the growth of smooth, ultrathin crystalline films. Such films are crucial in constructing low-loss, high-performance plasmonic and metamaterial devices including hyperbolic metamaterials (HMMs). HMMs have been shown to exhibit exotic optical properties, including extremely high broadband photonic densities of states (PDOS), which are useful in quantum plasmonic applications. However, the extent to which the exotic properties of HMMs can be realized has been seriously limited by fabrication constraints and material properties. Here, we address these issues by realizing an epitaxial superlattice as an HMM. The superlattice consists of ultrasmooth layers as thin as 5 nm and exhibits sharp interfaces which are essential for high-quality HMM devices. Our study reveals that such a TiN-based superlattice HMM provides a higher PDOS enhancement than gold- or silver-based HMMs.

Thermoelectric properties of epitaxial ScN films deposited by reactive magnetron sputtering onto MgO(001) substrates

Epitaxial ScN(001) thin films were grown on MgO(001) substrates by dc reactive magnetron sputtering. The deposition was performed in an Ar/N2 atmosphere at 2 × 10−3 Torr at a substrate temperature of 850 °C in a high vacuum chamber with a base pressure of 10−8 Torr. In spite of oxygen contamination of 1.6 ± 1 at. %, the electrical resistivity, electron mobility, and carrier concentration obtained from a typical film grown under these conditions by room temperature Hall measurements are 0.22 mΩ cm, 106 cm2 V−1 s−1, and 2.5 × 1020 cm−3, respectively. These films exhibit remarkable thermoelectric power factors of 3.3–3.5 × 10−3 W/mK2 in the temperature range of 600 K to 840 K. The cross-plane thermal conductivity is 8.3 W/mK at 800 K yielding an estimated ZT of 0.3. Theoretical modeling of the thermoelectric properties of ScN calculated using a mean-free-path of 23 nm at 300 K is in very good agreement with the experiment. These results also demonstrate that further optimization of the power factor of ScN is...

Electronic structure, vibrational spectrum, and thermal properties of yttrium nitride: A first-principles study

Yttrium nitride (YN) is a promising semiconductor for use in metal/semiconductor superlattices for thermoelectric applications. We determine its electronic structure, vibrational spectrum, and thermal properties using first-principles density functional theory (DFT) based simulations with a generalized gradient approximation (GGA) of the exchange correlation energy. We employ GGA+U and GW approximations in our calculations to (a) improve the accuracy of the calculation of bandgaps and (b) determine specific features of its electronic structure relevant to transport properties, such as transverse (mt*) and longitudinal (m1*) conduction band effective mass. To evaluate consequences of forming alloys of YN with other materials to its electronic properties, we have determined the volume deformation potentials. Our results for phonons show a large longitudinal optical (LO) and transverse optical (TO) splitting at the Γ point in the vibrational spectrum with a gap of 325 cm−1 arising from long- range dipole-dip...

Electronic and optical properties of ScN and (Sc,Mn)N thin films deposited by reactive DC-magnetron sputtering

Scandium nitride (ScN) is a rocksalt semiconductor that has attracted significant attention from various researchers for a diverse range of applications. Motivated by the prospect of using its interesting electronic structure for optoelectronic and dilute magnetic semiconductor applications, we present detailed studies of the electronic transport and optical properties of ScN and its alloys with manganese nitride (MnN). Our results suggest (a) dilute manganese doping in ScN compensates for the high n-type carrier concentrations arising due to oxygen impurities and (b) an n-type to p-type carrier type transition occurs at a composition between 5.8% and 11% Mn on Sc sites. In terms of its optical properties, our analysis clearly indicates direct and indirect bandgap absorption edges of ScN located at 2.04 eV and 1.18 eV, respectively. In addition to the direct gap absorption edge, (Sc,Mn)N samples also show Mn-defect induced electronic absorption. Photoluminescence measurements at room temperature from ScN films exhibit a yellowish-green emission corresponding to direct gap radiative recombination. Direct gap recombination is not expected given the smaller indirect gap. A possible role of high excitation intensities in suppressing relaxation and recombination across the indirect bandgap is suspected. Raman spectroscopic and ellipsometric characterization of the dielectric permittivities of ScN and (Sc,Mn)N are also presented to assist in understanding the potential of ScN for optoelectronic applications.

Thermoelectric properties of HfN/ScN metal/semiconductor superlattices: a first-principles study.

Nitride-based metal/semiconductor superlattices are promising candidates for high-temperature thermoelectric applications. Motivated by recent experimental studies, we perform first-principles density functional theory based analysis of electronic structure, vibrational spectra and transport properties of HfN/ScN metal/semiconductor superlattices for their potential applications in thermoelectric and thermionic energy conversion devices. Our results suggest (a) an asymmetric linearly increasing density of states and (b) flattening of conduction bands along the cross-plane Γ-Z direction near the Fermi energy of these superlattices, as is desirable for a large power factor. The n-type Schottky barrier height of 0.13 eV at the metal/semiconductor interface is estimated by the microscopic averaging technique of the electrostatic potential. Vibrational spectra of these superlattices show softening of transverse acoustic phonon modes and localization of ScN phonons in the vibrational energy gap between the HfN (metal) and ScN (semiconductor) states. Our estimates of lattice thermal conductivity within the Boltzmann transport theory suggests up to two orders of magnitude reduction in the cross-plane lattice thermal conductivity of these superlattices compared to their individual bulk components.

First-principles analysis of ZrN/ScN metal/semiconductor superlattices for thermoelectric energy conversion

We present a first-principles density functional theory-based analysis of the electronic structure, vibrational spectra, and transport properties of ZrN/ScN metal/semiconductor superlattices aiming to understand its potential and suitability for thermoelectric applications. We demonstrate (a) the presence of Schottky barriers of 0.34 eV at the metal/semiconductor interface and (b) a large asymmetry in the electronic densities of states and flattening of electronic bands along the cross-plane directions near the Fermi energy of these superlattices, desirable for high Seebeck coefficient. The vibrational spectra of these superlattices show softening of transverse acoustic phonon modes along the growth direction and localization of ScN phonons in the vibrational energy gap between metal and semiconductor layers. Boltzmann transport theory-based analysis suggests a reduction of lattice thermal conductivity by an order of magnitude compared to its individual bulk components, which makes these materials suitable for thermoelectric applications.

Enhanced hardness in epitaxial TiAlScN alloy thin films and rocksalt TiN/(Al,Sc)N superlattices

High hardness TiAlN alloys for wear-resistant coatings exhibit limited lifetimes at elevated temperatures due to a cubic-AlN to hexagonal-AlN phase transformation that leads to decreasing hardness. We enhance the hardness (up to 46 GPa) and maximum operating temperature (up to 1050 °C) of TiAlN-based coatings by alloying with scandium nitride to form both an epitaxial TiAlScN alloy film and epitaxial rocksalt TiN/(Al,Sc)N superlattices on MgO substrates. The superlattice hardness increases with decreasing period thickness, which is understood by the Orowan bowing mechanism of the confined layer slip model. These results make them worthy of additional research for industrial coating applications.

Dislocation-pipe diffusion in nitride superlattices observed in direct atomic resolution

Device failure from diffusion short circuits in microelectronic components occurs via thermally induced migration of atoms along high-diffusivity paths: dislocations, grain boundaries, and free surfaces. Even well-annealed single-grain metallic films contain dislocation densities of about 1014 m−2; hence dislocation-pipe diffusion (DPD) becomes a major contribution at working temperatures. While its theoretical concept was established already in the 1950s and its contribution is commonly measured using indirect tracer, spectroscopy, or electrical methods, no direct observation of DPD at the atomic level has been reported. We present atomically-resolved electron microscopy images of the onset and progression of diffusion along threading dislocations in sequentially annealed nitride metal/semiconductor superlattices, and show that this type of diffusion can be independent of concentration gradients in the system but governed by the reduction of strain fields in the lattice.

Compensation of native donor doping in ScN: Carrier concentration control and p-type ScN

Scandium nitride (ScN) is an emerging indirect bandgap rocksalt semiconductor that has attracted significant attention in recent years for its potential applications in thermoelectric energy conversion devices, as a semiconducting component in epitaxial metal/semiconductor superlattices and as a substrate material for high quality GaN growth. Due to the presence of oxygen impurities and native defects such as nitrogen vacancies, sputter-deposited ScN thin-films are highly degenerate n-type semiconductors with carrier concentrations in the (1–6)  × 1020 cm−3 range. In this letter, we show that magnesium nitride (MgxNy) acts as an efficient hole dopant in ScN and reduces the n-type carrier concentration, turning ScN into a p-type semiconductor at high doping levels. Employing a combination of high-resolution X-ray diffraction, transmission electron microscopy, and room temperature optical and temperature dependent electrical measurements, we demonstrate that p-type Sc1-xMgxN thin-film alloys (a) are substit...

Phonon wave effects in the thermal transport of epitaxial TiN/(Al,Sc)N metal/semiconductor superlattices

Epitaxial single crystalline TiN/(Al,Sc)N metal/semiconductor superlattice metamaterials have generated significant interest in recent years for their potential applications in high temperature thermoelectric devices, optical hyperbolic metamaterials in the visible and near infrared-spectral range, and as candidates for solar-thermophotovoltaics and high temperature electronic materials. While significant progress in their structural, mechanical, and optical properties has been made, in-depth analysis and detailed understanding of their thermal transport mechanism remain to be addressed. In this article, we show that in short-period epitaxial, lattice-matched TiN/(Al,Sc)N metal/semiconductor superlattices, thermal transport is dominated by phonon wave effects as the wavelengths of phonons that carry significant amounts of heat become comparable to the superlattice period thickness. Due to the increasing contribution of such phonon wave-modes, the cross-plane thermal conductivity at short-periods increases...