Ji Ho Sung

Deterministic Two-Dimensional Polymorphism Growth of Hexagonal n-Type SnS2 and Orthorhombic p-Type SnS Crystals

van der Waals layered materials have large crystal anisotropy and crystallize spontaneously into two-dimensional (2D) morphologies. Two-dimensional materials with hexagonal lattices are emerging 2D confined electronic systems at the limit of one or three atom thickness. Often these 2D lattices also form orthorhombic symmetries, but these materials have not been extensively investigated, mainly due to thermodynamic instability during crystal growth. Here, we show controlled polymorphic growth of 2D tin-sulfide crystals of either hexagonal SnS2 or orthorhombic SnS. Addition of H2 during the growth reaction enables selective determination of either n-type SnS2 or p-type SnS 2D crystal of dissimilar energy band gap of 2.77 eV (SnS2) or 1.26 eV (SnS) as a final product. Based on this synthetic 2D polymorphism of p-n crystals, we also demonstrate p-n heterojunctions for rectifiers and photovoltaic cells, and complementary inverters.

Rotation‐Misfit‐Free Heteroepitaxial Stacking and Stitching Growth of Hexagonal Transition‐Metal Dichalcogenide Monolayers by Nucleation Kinetics Controls

2D vertical stacking and lateral stitching growth of monolayer (ML) hexagonal transition-metal dichalcogenides are reported. The 2D heteroepitaxial manipulation of MoS2 and WS2 MLs is achieved by control of the 2D nucleation kinetics during the sequential vapor-phase growth. It enables the creation of hexagon-on-hexagon unit-cell stacking and hexagon-by-hexagon stitching without interlayer rotation misfits.

Interlayer orientation-dependent light absorption and emission in monolayer semiconductor stacks

Two-dimensional stacks of dissimilar hexagonal monolayers exhibit unusual electronic, photonic and photovoltaic responses that arise from substantial interlayer excitations. Interband excitation phenomena in individual hexagonal monolayer occur in states at band edges (valleys) in the hexagonal momentum space; therefore, low-energy interlayer excitation in the hexagonal monolayer stacks can be directed by the two-dimensional rotational degree of each monolayer crystal. However, this rotation-dependent excitation is largely unknown, due to lack in control over the relative monolayer rotations, thereby leading to momentum-mismatched interlayer excitations. Here, we report that light absorption and emission in MoS2/WS2 monolayer stacks can be tunable from indirect- to direct-gap transitions in both spectral and dynamic characteristics, when the constituent monolayer crystals are coherently stacked without in-plane rotation misfit. Our study suggests that the interlayer rotational attributes determine tunable interlayer excitation as a new set of basis for investigating optical phenomena in a two-dimensional hexagonal monolayer system.

Enhancement of the anisotropic photocurrent in ferroelectric oxides by strain gradients

The phase separation of multiple competing structural/ferroelectric phases has attracted particular attention owing to its excellent electromechanical properties. Little is known, however, about the strain-gradient-induced electronic phenomena at the interface of competing structural phases. Here, we investigate the polymorphic phase interface of bismuth ferrites using spatially resolved photocurrent measurements, present the observation of a large enhancement of the anisotropic interfacial photocurrent by two orders of magnitude, and discuss the possible mechanism on the basis of the flexoelectric effect. Nanoscale characterizations of the photosensitive area through position-sensitive angle-resolved piezoresponse force microscopy and electron holography techniques, in conjunction with phase field simulation, reveal that regularly ordered dipole-charged domain walls emerge. These findings offer practical implications for complex oxide optoelectronics.

Thermoelectric materials by using two-dimensional materials with negative correlation between electrical and thermal conductivity

In general, in thermoelectric materials the electrical conductivity σ and thermal conductivity κ are related and thus cannot be controlled independently. Previously, to maximize the thermoelectric figure of merit in state-of-the-art materials, differences in relative scaling between σ and κ as dimensions are reduced to approach the nanoscale were utilized. Here we present an approach to thermoelectric materials using tin disulfide, SnS2, nanosheets that demonstrated a negative correlation between σ and κ. In other words, as the thickness of SnS2 decreased, σ increased whereas κ decreased. This approach leads to a thermoelectric figure of merit increase to 0.13 at 300 K, a factor ∼1,000 times greater than previously reported bulk single-crystal SnS2. The Seebeck coefficient obtained for our two-dimensional SnS2 nanosheets was 34.7 mV K−1 for 16-nm-thick samples at 300 K.

Atomic Layer-by-Layer Thermoelectric Conversion in Topological Insulator Bismuth/Antimony Tellurides

Material design for direct heat-to-electricity conversion with substantial efficiency essentially requires cooperative control of electrical and thermal transport. Bismuth telluride (Bi2Te3) and antimony telluride (Sb2Te3), displaying the highest thermoelectric power at room temperature, are also known as topological insulators (TIs) whose electronic structures are modified by electronic confinements and strong spin-orbit interaction in a-few-monolayers thickness regime, thus possibly providing another degree of freedom for electron and phonon transport at surfaces. Here, we explore novel thermoelectric conversion in the atomic monolayer steps of a-few-layer topological insulating Bi2Te3 (n-type) and Sb2Te3 (p-type). Specifically, by scanning photoinduced thermoelectric current imaging at the monolayer steps, we show that efficient thermoelectric conversion is accomplished by optothermal motion of hot electrons (Bi2Te3) and holes (Sb2Te3) through 2D subbands and topologically protected surface states in a geometrically deterministic manner. Our discovery suggests that the thermoelectric conversion can be interiorly achieved at the atomic steps of a homogeneous medium by direct exploiting of quantum nature of TIs, thus providing a new design rule for the compact thermoelectric circuitry at the ultimate size limit.

Ultra-high modulation depth exceeding 2,400% in optically controlled topological surface plasmons.

Modulating light via coherent charge oscillations in solids is the subject of intense research topics in opto-plasmonics. Although a variety of methods are proposed to increase such modulation efficiency, one central challenge is to achieve a high modulation depth (defined by a ratio of extinction with/without light) under small photon-flux injection, which becomes a fundamental trade-off issue both in metals and semiconductors. Here, by fabricating simple micro-ribbon arrays of topological insulator Bi2Se3, we report an unprecedentedly large modulation depth of 2,400% at 1.5 THz with very low optical fluence of 45 μJ cm−2. This was possible, first because the extinction spectrum is nearly zero due to the Fano-like plasmon–phonon-destructive interference, thereby contributing an extremely small denominator to the extinction ratio. Second, the numerator of the extinction ratio is markedly increased due to the photoinduced formation of massive two-dimensional electron gas below the topological surface states, which is another contributor to the ultra-high modulation depth.

Detection of electrically formed photosensitive area in Ca-doped BiFeO3 thin films

We report on the visualization of n-p junctions formed by oxygen vacancy movement under the application of an electric field in a Ca-doped BiFeO3 thin film through spatially resolved scanning photocurrent mapping. The photocurrent mapping, in conjunction with the spectroscopic approach, provides clues to local electronic structures and defect levels associated with oxygen vacancies. These observations provide insights into the spatial redistribution of oxygen vacancies in an electric field.

Selectively tunable optical Stark effect of anisotropic excitons in atomically thin ReS2.

The optical Stark effect is a coherent light–matter interaction describing the modification of quantum states by non-resonant light illumination in atoms, solids and nanostructures. Researchers have strived to utilize this effect to control exciton states, aiming to realize ultra-high-speed optical switches and modulators. However, most studies have focused on the optical Stark effect of only the lowest exciton state due to lack of energy selectivity, resulting in low degree-of-freedom devices. Here, by applying a linearly polarized laser pulse to few-layer ReS2, where reduced symmetry leads to strong in-plane anisotropy of excitons, we control the optical Stark shift of two energetically separated exciton states. Especially, we selectively tune the Stark effect of an individual state with varying light polarization. This is possible because each state has a completely distinct dependence on light polarization due to different excitonic transition dipole moments. Our finding provides a methodology for energy-selective control of exciton states.

Spatially Resolved Photodetection in Leaky Ferroelectric BiFeO3

Potential gradients due to the spontaneous polarization of BiFeO(3) yield asymmetric and nonlinear photocarrier dynamics. Photocurrent direction is determined by local ferroelectric domain orientation, whereas magnitude is spectrally centered around charged domain walls that are associated with oxygen vacancy migration. Photodetection can be electrically controlled by manipulating ferroelectric domain configurations.