Soonmin Yim

Controlled Doping of Vacancy-Containing Few-Layer MoS2 via Highly Stable Thiol-Based Molecular Chemisorption

MoS2 is considered a promising two-dimensional active channel material for future nanoelectronics. However, the development of a facile, reliable, and controllable doping methodology is still critical for extending the applicability of MoS2. Here, we report surface charge transfer doping via thiol-based binding chemistry for modulating the electrical properties of vacancy-containing MoS2 (v-MoS2). Although vacancies present in 2D materials are generally regarded as undesirable components, we show that the electrical properties of MoS2 can be systematically engineered by exploiting the tight binding between the thiol group and sulfur vacancies and by choosing different functional groups. For example, we demonstrate that NH2-containing thiol molecules with lone electron pairs can serve as an n-dopant and achieve a substantial increase of electron density (Δn = 3.7 × 10(12) cm(-2)). On the other hand, fluorine-rich molecules can provide a p-doping effect (Δn = -7.0 × 10(11) cm(-2)) due to its high electronegativity. Moreover, the n- and p-doping effects were systematically evaluated by photoluminescence (PL), X-ray photoelectron spectroscopy (XPS), and electrical measurement results. The excellent binding stability of thiol molecules and recovery properties by thermal annealing will enable broader applicability of ultrathin MoS2 to various devices.

High-resolution nanotransfer printing applicable to diverse surfaces via interface-targeted adhesion switching.

Nanotransfer printing technology offers outstanding simplicity and throughput in the fabrication of transistors, metamaterials, epidermal sensors and other emerging devices. Nevertheless, the development of a large-area sub-50 nm nanotransfer printing process has been hindered by fundamental reliability issues in the replication of high-resolution templates and in the release of generated nanostructures. Here we present a solvent-assisted nanotransfer printing technique based on high-fidelity replication of sub-20 nm patterns using a dual-functional bilayer polymer thin film. For uniform and fast release of nanostructures on diverse receiver surfaces, interface-specific adhesion control is realized by employing a polydimethylsiloxane gel pad as a solvent-emitting transfer medium, providing unusual printing capability even on biological surfaces such as human skin and fruit peels. Based on this principle, we also demonstrate reliable printing of high-density metallic nanostructures for non-destructive and rapid surface-enhanced Raman spectroscopy analyses and for hydrogen detection sensors with excellent responsiveness.

In Situ Nanolithography with Sub-10 nm Resolution Realized by Thermally Assisted Spin-Casting of a Self-Assembling Polymer.

In situ nanolithography is realized based on warm spin-casting of block copolymer solutions. This advancement is based on Si-containing block copolymers with an appropriate thermodynamic driving force for spontaneous phase-separation combined with the thermal assistance provided by slight temperature elevations during the spin-casting. Sub-10 nm half-pitch nanoscale patterns are produced within 30 s without a separate annealing process.

Atomic Layer Etching Mechanism of MoS2 for Nanodevices

Among the layered transition metal dichalcogenides (TMDs) that can form stable two-dimensional crystal structures, molybdenum disulfide (MoS2) has been intensively investigated because of its unique properties in various electronic and optoelectronic applications with different band gap energies from 1.29 to 1.9 eV as the number of layers decreases. To control the MoS2 layers, atomic layer etching (ALE) (which is a cyclic etching consisting of a radical-adsorption step such as Cl adsorption and a reacted-compound-desorption step via a low-energy Ar+-ion exposure) can be a highly effective technique to avoid inducing damage and contamination that occur during the reactive steps. Whereas graphene is composed of one-atom-thick layers, MoS2 is composed of three-atom-thick S(top)-Mo(mid)-S(bottom) layers; therefore, the ALE mechanisms of the two structures are significantly different. In this study, for MoS2 ALE, the Cl radical is used as the adsorption species and a low-energy Ar+ ion is used as the desorption species. A MoS2 ALE mechanism (by which the S(top), Mo(mid), and S(bottom) atoms are sequentially removed from the MoS2 crystal structure due to the trapped Cl atoms between the S(top) layer and the Mo(mid) layer) is reported according to the results of an experiment and a simulation. In addition, the ALE technique shows that a monolayer MoS2 field effect transistor (FET) fabricated after one cycle of ALE is undamaged and exhibits electrical characteristics similar to those of a pristine monolayer MoS2 FET. This technique is also applicable to all layered TMD materials, such as tungsten disulfide (WS2), molybdenum diselenide (MoSe2), and tungsten diselenide (WSe2).

Highly Asymmetric n+–p Heterojunction Quantum‐Dot Solar Cells with Significantly Improved Charge‐Collection Efficiencies

The depletion region width of metal-oxide/quantum-dot (QD) heterojunction solar cells is increased by a new method in which heavily boron-doped n(+)-ZnO is employed. It is effectively increased in the QD layer by 30% compared to the counterpart with conventional n-ZnO, and provides 41% and 37% improvement of J(sc) (16.7 mA cm(-2) to 23.5 mA cm(-2) ) and power conversion efficiency (5.52% to 7.55%), respectively.

Interfacial band-edge engineered TiO2 protection layer on Cu2O photocathodes for efficient water reduction reaction

Photoelectrochemical (PEC) water splitting has emerged as a potential pathway to produce sustainable and renewable chemical fuels. Here, we present a highly active Cu2O/TiO2 photocathode for H2 production by enhancing the interfacial band-edge energetics of the TiO2 layer, which is realized by controlling the fixed charge density of the TiO2 protection layer. The band-edge engineered Cu2O/TiO2 (where TiO2 was grown at 80 °C via atomic layer deposition) enhances the photocurrent density up to −2.04 mA/cm2 at 0 V vs. RHE under 1 sun illumination, corresponding to about a 1,200% enhancement compared to the photocurrent density of the photocathode protected with TiO2 grown at 150 °C. Moreover, band-edge engineering of the TiO2 protection layer prevents electron accumulation at the TiO2 layer and enhances both the Faraday efficiency and the stability for hydrogen production during the PEC water reduction reaction. This facile control over the TiO2/electrolyte interface will also provide new insight for designing highly efficient and stable protection layers for various other photoelectrodes such as Si, InP, and GaAs.

Area-Selective Lift-Off Mechanism Based on Dual-Triggered Interfacial Adhesion Switching: Highly Facile Fabrication of Flexible Nanomesh Electrode

With the recent emergence of flexible and wearable optoelectronic devices, the achievement of sufficient bendability and stretchability of transparent and conducting electrodes (TCEs) has become an important requirement. Although metal-mesh-based structures have been investigated for TCEs because of their excellent performances, the fabrication of mesh or grid structures with a submicron line width is still complex due to the requirements of laborious lithography and pattern transfer steps. Here, we introduce an extremely facile fabrication technique for metal patterns embedded in a flexible substrate based on submicron replication and an area-selective delamination (ASD) pattern. The high-yield, area-specific lift-off process is based on the principle of solvent-assisted delamination of deposited metal thin films and a mechanical triggering effect by soft wiping or ultrasonication. Our fabrication process is very simple, convenient, and cost-effective in that it does not require any lithography/etching steps or sophisticated facilities. Moreover, their outstanding optical and electrical properties (e.g., sheet resistances of 0.43 Ω sq-1 at 94% transmittance), which are markedly superior to those of other flexible TCEs, are demonstrated. Furthermore, there is no significant change of resistance over 1000 repeated bending cycles, with a bending radius of 5 mm, and immersion in various solvents such as salt water and organic solvents. Finally, we demonstrate high-performance transparent heaters and flexible touch panels fabricated using the nanomesh electrode, confirming the long-range electrical conduction and reliability of the electrode.

Extremely Small Pyrrhotite Fe7S8 Nanocrystals with Simultaneous Carbon‐Encapsulation for High‐Performance Na–Ion Batteries

Na/FeSx batteries have remarkable potential applicability due to their high theoretical capacity and cost-effectiveness. However, realization of high power-capability and long-term cyclability remains a major challenge. Herein, ultrafine Fe7 S8 @C nanocrystals (NCs) as a promising anode material for a Na-ion battery that addresses the above two issues simultaneously is reported. An Fe7 S8 core with quantum size (≈10 nm) overcomes the kinetic and thermodynamic constraints of the Na-S conversion reaction. In addition, the high degree of interconnection through carbon shells improves the electronic transport along the structure. As a result, the Fe7 S8 @C NCs electrode achieves excellent power capability of 550 mA h g-1 (≈79% retention of its theoretical capacity) at a current rate of 2700 mA g-1 . Furthermore, a conformal carbon shell acts as a buffer layer to prevent severe volume change, which provides outstanding cyclability of ≈447 mA h g-1 after 1000 cycles (≈71% retention of the initial charge capacity).

Long-Term Stable 2H-MoS2 Dispersion: Critical Role of Solvent for Simultaneous Phase Restoration and Surface Functionalization of Liquid-Exfoliated MoS2

Chemical exfoliation approaches such as Li-intercalation for the production of two-dimensional MoS2 are highly attractive due to their high yield of monolayer forms, cost-effectiveness, and mass-scalability. However, the loss of the semiconducting property and poor dispersion stability in solvent have limited the extent of their potential applications. Here, we report simultaneous phase recovery and surface functionalization for the preparation of a highly stable 2H-MoS2 dispersion in water. This study shows that high-yield restoration of the semiconducting 2H phase from a chemically exfoliated MoS2 (ce-MoS2) can be induced by a mild-temperature (180 °C) solvent thermal treatment in N-methyl-2-pyrrolidone (NMP). In addition to a phase transition, this solvent thermal treatment in NMP realizes concurrent surface functionalization of the 2H-MoS2 surface, which provides an outstanding dispersion stability to 2H-MoS2 in water for more than 10 months. Finally, we report the humidity sensor based on the functionalized 2H-MoS2, which shows a substantial response enhancement compared with a nonfunctionalized 2H-MoS2 or ce-MoS2.

Nanopatterned High-Frequency Supporting Structures Stably Eliminate Substrate Effects Imposed on Two-Dimensional Semiconductors

Despite the outstanding physical and chemical properties of two-dimensional (2D) materials, due to their extremely thin nature, eliminating detrimental substrate effects such as serious degradation of charge-carrier mobility or light-emission yield remains a major challenge. However, previous approaches have suffered from limitations such as structural instability or the need of costly and high-temperature deposition processes. Herein, we propose a new strategy based on the insertion of high-density topographic nanopatterns as a nanogap-containing supporter between 2D materials and substrate to minimize their contact and to block the substrate-induced undesirable effects. We show that well-controlled high-frequency SiO x nanopillar structures derived from the self-assembly of Si-containing block copolymer securely prevent the collapse or deformation of transferred MoS2 and guarantee excellent mechanical stability. The nanogap supporters formed below monolayer MoS2 lead to dramatic enhancement of the photoluminescence emission intensity (8.7-fold), field-effect mobility (2.0-fold, with a maximum of 4.3-fold), and photoresponsivity (12.1-fold) compared to the sample on flat SiO2. Similar favorable effects observed for graphene strongly suggest that this simple but powerful nanogap-supporting method can be extensively applicable to a variety of low-dimensional materials and contribute to improved device performance.