Sampath Gamage

Nanoscopy reveals surface-metallic black phosphorus

Black phosphorus (BP) is an emerging two-dimensional material with intriguing physical properties. It is highly anisotropic and highly tunable by means of both the number of monolayers and surface doping. Here, we experimentally investigate and theoretically interpret the near-field properties of a-few-atomic-monolayer nanoflakes of BP. We discover near-field patterns of bright outside fringes and a high surface polarizability of nanofilm BP consistent with its surface-metallic, plasmonic behavior at mid-infrared frequencies <1176 cm−1. We conclude that these fringes are caused by the formation of a highly polarizable layer at the BP surface. This layer has a thickness of ~1 nm and exhibits plasmonic behavior. We estimate that it contains free carriers in a concentration of n≈1.1 × 1020 cm−3. Surface plasmonic behavior is observed for 10–40 nm BP thicknesses but absent for a 4-nm BP thickness. This discovery opens up a new field of research and potential applications in nanoelectronics, plasmonics and optoelectronics.

Control of Plasmonic Nanoantennas by Reversible Metal-insulator Transition

We demonstrate dynamic reversible switching of VO2 insulator-to-metal transition (IMT) locally on the scale of 15 nm or less and control of nanoantennas, observed for the first time in the near-field. Using polarization-selective near-field imaging techniques, we simultaneously monitor the IMT in VO2 and the change of plasmons on gold infrared nanoantennas. Structured nanodomains of the metallic VO2 locally and reversibly transform infrared plasmonic dipole nanoantennas to monopole nanoantennas. Fundamentally, the IMT in VO2 can be triggered on femtosecond timescale to allow ultrafast nanoscale control of optical phenomena. These unique features open up promising novel applications in active nanophotonics.

Near-field edge fringes at sharp material boundaries

We have studied the formation of near-field fringes when sharp edges of materials are imaged using scattering-type scanning near-field optical microscope (s-SNOM). The materials we have investigated include dielectrics, metals, a near-perfect conductor, and those that possess anisotropic permittivity and hyperbolic dispersion. For our theoretical analysis, we use a technique that combines full-wave numerical simulations of tip-sample near-field interaction and signal demodulation at higher orders akin to what is done in typical s-SNOM experiments. Unlike previous tip-sample interaction near-field models, our advanced technique allows simulation of the realistic tip and sample structure. Our analysis clarifies edge imaging of recently emerged layered materials such as hexagonal boron nitride and transition metal dichalcogenides (in particular, molybdenum disulfide), as well as traditional plasmonic materials such as gold. Hexagonal boron nitride is studied at several wavelengths, including the wavelength where it possesses excitation of phonon-polaritons and hyperbolic dispersion. Based on our results of s-SNOM imaging in different demodulation orders, we specify resonant and non-resonant types of edges and describe the edge fringes for each case. We clarify near-field edge-fringe formation at material sharp boundaries, both outside bright fringes and the low-contrast region at the edge, and elaborate on the necessity of separating them from propagating waves on the surface of polaritonic materials.

Growth temperature - phase stability relation in In 1-x Ga x N epilayers grown by high-pressure CVD

The influence of the growth temperature on the phase stability and composition of singlephase In 1-x Ga x N epilayers has been studied. The In 1-x Ga x N epilayers were grown by high-pressure Chemical Vapor Deposition with nominally composition of x = 0.6 at a reactor pressure of 15 bar at various growth temperatures. The layers were analyzed by x-ray diffraction, optical transmission spectroscopy, atomic force microscopy, and Raman spectroscopy. The results showed that a growth temperature of 925 °C led to the best single phase InGaN layers with the smoothest surface and smallest grain areas.

Geometric constraints on phase coexistence in vanadium dioxide single crystals

The appearance of stripe phases is a characteristic signature of strongly correlated quantum materials, and its origin in phase-changing materials has only recently been recognized as the result of the delicate balance between atomic and mesoscopic materials properties. A vanadium dioxide (VO2) single crystal is one such strongly correlated material with stripe phases. Infrared nano-imaging on low-aspect-ratio, single-crystal VO2 microbeams decorated with resonant plasmonic nanoantennas reveals a novel herringbone pattern of coexisting metallic and insulating domains intercepted and altered by ferroelastic domains, unlike previous reports on high-aspect-ratio VO2 crystals where the coexisting metal/insulator domains appear as alternating stripe phases perpendicular to the growth axis. The metallic domains nucleate below the crystal surface and grow towards the surface with increasing temperature as suggested by the near-field plasmonic response of the gold nanorod antennas.

Effect of reactor pressure on the electrical and structural properties of InN epilayers grown by high-pressure chemical vapor deposition

The influence of super-atmospheric reactor pressures (2.5‐18.5bar) on the electrical and structural properties of InN epilayers deposited on GaN/sapphire (0001) templates by high-pressure chemical vapor deposition has been studied. The epilayers were analyzed by Raman, x-ray diffraction (XRD), and Fourier transform infrared reflectance spectrometry to determine the structural properties as well as the phonon frequencies, dielectric function, plasma frequency, layer thickness and damping parameters of the epilayers. For the studied process parameter space, best material properties were achieved at a reactor pressure of 12.5bar and a group-V/III ratio of 2500 with a free carrier concentration of 1.5 � 10 18 cm � 3 , a mobility of the bulk InN layer of 270 cm 2 V � 1 s � 1 , and a Raman (E2 high) FWHM value of 10.3cm � 1 . This study shows that the crystalline layer properties—probed by XRD 2h‐x scans—improve with increasing reactor pressure. V C 2012

Reactor pressure - growth temperature relation for InN epilayers grown by high-pressure CVD

Results on the achievable growth temperature as a function of the reactor pressure for the growth of InN by high-pressure CVD are presented. As the reactor pressure was increased from 1 bar to 19 bar, the optimal growth temperature raised from 759°C to 876°C, an increase of 6.6 °C/bar. The InN layers were grown in a horizontal flow channel reactor, using a pulsed precursor injection scheme. The structural and optical properties of the epilayers have been investigated by Raman spectroscopy, X-ray diffraction, and IR reflectance spectroscopy.

Recent Progress on Stability and Passivation of Black Phosphorus

From a fundamental science perspective, black phosphorus (BP) is a canonical example of a material that possesses fascinating surface and electronic properties. It has extraordinary in-plane anisotropic electrical, optical, and vibrational states, as well as a tunable band gap. However, instability of the surface due to chemical degradation in ambient conditions remains a major impediment to its prospective applications. Early studies were limited by the degradation of black phosphorous surfaces in air. Recently, several robust strategies have been developed to mitigate these issues, and these novel developments can potentially allow researchers to exploit the extraordinary properties of this material and devices made out of it. Here, the fundamental chemistry of BP degradation and the tremendous progress made to address this issue are extensively reviewed. Device performances of encapsulated BP are also compared with nonencapsulated BP. In addition, BP possesses sensitive anisotropic photophysical surface properties such as excitons, surface plasmons/phonons, and topologically protected and Dirac semi-metallic surface states. Ambient degradation as well as any passivation method used to protect the surface could affect the intrinsic surface properties of BP. These properties and the extent of their modifications by both the degradation and passivation are reviewed.

Nanoscopy of Phase Separation in InxGa1-xN Alloys.

Phase separations in ternary/multinary semiconductor alloys is a major challenge that limits optical and electronic internal device efficiency. We have found ubiquitous local phase separation in In1-xGaxN alloys that persists to nanoscale spatial extent by employing high-resolution nanoimaging technique. We lithographically patterned InN/sapphire substrates with nanolayers of In1-xGaxN down to few atomic layers thick that enabled us to calibrate the near-field infrared response of the semiconductor nanolayers as a function of composition and thickness. We also developed an advanced theoretical approach that considers the full geometry of the probe tip and all the sample and substrate layers. Combining experiment and theory, we identified and quantified phase separation in epitaxially grown individual nanoalloys. We found that the scale of the phase separation varies widely from particle to particle ranging from all Ga- to all In-rich regions and covering everything in between. We have found that between 20 and 25% of particles show some level of Ga-rich phase separation over the entire sample region, which is in qualitative agreement with the known phase diagram of In1-xGaxN system.

Strongly correlated perovskite lithium ion shuttles

Significance Designing solid-state ion conductors is of broad interest to energy conversion, bioengineering, and information processing. Here, we demonstrate a new class of Li-ion conducting quantum materials in the perovskite family. Rare-earth perovskite nickelate films of the chemical formula SmNiO3 are shown to exhibit high Li-ion conductivity while minimizing their electronic conductivity. This process occurs by electron injection into Ni orbitals when the Li ions are inserted from a reservoir. The mechanism of doping is studied by high-resolution experimental and first-principles theoretical methods to provide evidence for ion shuttling in the lattice and the atomistic pathways. The experiments are then extended to other small ions such as Na+, demonstrating the generality of the approach. Solid-state ion shuttles are of broad interest in electrochemical devices, nonvolatile memory, neuromorphic computing, and biomimicry utilizing synthetic membranes. Traditional design approaches are primarily based on substitutional doping of dissimilar valent cations in a solid lattice, which has inherent limits on dopant concentration and thereby ionic conductivity. Here, we demonstrate perovskite nickelates as Li-ion shuttles with simultaneous suppression of electronic transport via Mott transition. Electrochemically lithiated SmNiO3 (Li-SNO) contains a large amount of mobile Li+ located in interstitial sites of the perovskite approaching one dopant ion per unit cell. A significant lattice expansion associated with interstitial doping allows for fast Li+ conduction with reduced activation energy. We further present a generalization of this approach with results on other rare-earth perovskite nickelates as well as dopants such as Na+. The results highlight the potential of quantum materials and emergent physics in design of ion conductors.