Hoseok Heo

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.

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.

Tunable Catalytic Alloying Eliminates Stacking Faults in Compound Semiconductor Nanowires

Planar defects in compound (III-V and II-VI) semiconductor nanowires (NWs), such as twin and stacking faults, are universally formed during the catalytic NW growth, and they detrimentally act as static disorders against coherent electron transport and light emissions. Here we report a simple synthetic route for planar-defect free II-VI NWs by tunable alloying, i.e. Cd(1-x)Zn(x)Te NWs (0 ≤ x ≤ 1). It is discovered that the eutectic alloying of Cd and Zn in Au catalysts immediately alleviates interfacial instability during the catalytic growth by the surface energy minimization and forms homogeneous zinc blende crystals as opposed to unwanted zinc blende/wurtzite mixtures. As a direct consequence of the tunable alloying, we demonstrated that intrinsic energy band gap modulation in Cd(1-x)Zn(x)Te NWs can exploit the tunable spectral and temporal responses in light detection and emission in the full visible range.

Growth of straight one-dimensional Ge/ZnSe heterojunctions with atomically sharp interfaces by catalytic residue controls.

One-dimensional (1D) heteroepitaxy with an abrupt interface is essential to construct the 1D heterojunctions required for photonic and electronic devices. During catalytic 1D heteroepitaxial growth, however, the heterojunctions are generically kinked and composition-diffused across the interfaces. Here, we report a simple synthetic route for straight 1D heteroepitaxy with atomically sharp interfaces of group IV(Ge)/group II-VI(ZnSe) nanowires (NWs) during Au-catalytic growth. Specifically, it is discovered that eliminating residues in Au catalysts by Se vapour treatments lowers the energy barrier for the Ge NW axial heteroepitaxy on ZnSe NWs, and forms atomically abrupt heterointerfaces. We verified such 1D variation in the local electronic band structure of the grown Ge/ZnSe NW heterojunctions with spatially resolved photocurrent measurements.

Kinetics-driven high power Li-ion battery with a-Si/NiSi x core-shell nanowire anodes

Anode architectures are closely related with Li-ion battery performance, particularly when the anodes are three-dimensional at the nanometer scale. Therein, the achievable electrochemical capacity and the power characteristics are inherently determined by a series of phase transitions involved in the anode during lithiation/delithiation. Here, we report an amorphous-silicon (a-Si) supported by metallic NiSi x nanowire (NW) core grown by simple two-step SiH4 CVD on Ni films for a Li-ion battery anode structure, where the metallic core act as a mechanical supporter and supplies kinetically unlimited electron transport. We achieved the highly reversible capacity over 3000 mAh/g even at 2C rate with its stable cyclic retention. We argue that a-Si/NiSi x NW follow a potentially ideal route for reversible and fast phase transitions, compared to bare Si NWs, and thus can provide implication for the high power and high capacity energy storage devices.