Boosting the Output Performance of the MoS2 Monolayer-Based Piezoelectric Nanogenerator by Artificial Dual Strain Concentration.

Piezoelectric nanogenerators (PENGs) with molybdenum disulfide (MoS2) monolayers have been intensively studied owing to their superior mechanical durability and stability. However, the limited output performance resulting from a small active area and low strain levels continues to pose a significant challenge that should be overcome. Herein, we report a novel strategy for the epoch-making output performance of a PENG with a MoS2 monolayer by adopting the additive strain concentration concept. The simulation study indicates that strain in the MoS2 monolayer can be initially augmented by the wavy structure resulting from the prestretched poly(dimethylsiloxane) (PDMS) and is further increased through flexural deformation (i.e., bending). Based on these studies, we have developed concentrated strain-applied PENGs with MoS2 monolayers. The wavy structures effectively applied strain to the MoS2 monolayer and generated a piezoelectric output voltage and current of around 580 mV and 47.5 nA, respectively. Our innovative approach to enhancing the performance of PENGs with MoS2 monolayers through the artificial dual strain concept has led to groundbreaking results, achieving the highest recorded output voltage and current for PENGs based on two-dimensional (2D) materials, which provides unique opportunities for the 2D-based energy harvesting field and structural insight into how to improve the net strain on 2D materials.

Sustainable power generation via hydro-electrochemical effects.

Recent efforts towards energy scavenging with eco-friendly methods and abundant water look very promising for powering wearables and distributed electronics. However, the time duration of electricity generation is typically too short, and the current level is not sufficient to meet the required threshold for the proper operation of electronics despite the relatively large voltage. This work newly introduced an electrochemical method in combination with hydro-effects in order to extend the energy scavenging time and boost the current. Our device consists of corroded porous steel electrodes whose corrosion overpotential was lowered when the water concentration was increased and vice versa. Then a potential difference was created between two electrodes, generating electricity via the hydro-electrochemical method up to an open-circuit voltage of 750 mV and a short-circuit current of 90 µA cm-2. Furthermore, electricity was continuously generated for more than 1500 minutes by slow water diffusion against gravity from the bottom electrode. Lastly, we demonstrated that our hydro-electrochemical power generators successfully operated electronics, showing the feasibility of offering electrical power for sufficiently long time periods in practice.

Precise Layer Control and Electronic State Modulation of a Transition Metal Dichalcogenide via Phase-Transition-Induced Growth.

Wafer-scale growth of transition metal dichalcogenides with precise control over the number of layers, and hence the electronic state is an essential technology for expanding the practical application of 2D materials. Herein, a new growth method, phase-transition-induced growth (PTG), is proposed for the precisely controlled growth of molybdenum disulfide (MoS2 ) films consisting of one to eleven layers with spatial uniformity on a 2 in. wafer. In this method, an energetically unstable amorphous MoSx Oy (a-MoSx Oy ) phase is effectively converted to a thermodynamically stable crystalline MoS2 film. The number of MoS2 layers is readily controlled layer-by-layer by controlling the amount of Mo atoms in a-MoSx Oy , which is also applicable for the growth of heteroatom-inserted MoS2 . The electronic states of intrinsic and Nb-inserted MoS2 with one and four layers grown by PTGare are analyzed based on their work functions. The work function of monolayer MoS2 effectively increases with the substitution of Nb for Mo. As the number of layers increases to four, charge screening becomes weaker, dopant ionization becomes easier, and ultimately the work function increases further. Thus, better electronic state modulation is achieved in a thicker layer, and in this respect, PTG has the advantage of enabling precise control over the film thickness.

Colossal thermo-hydro-electrochemical voltage generation for self-sustainable operation of electronics.

Thermoelectrics are suited to converting dissipated heat into electricity for operating electronics, but the small voltage (~0.1 mV K-1) from the Seebeck effect has been one of the major hurdles in practical implementation. Here an approach with thermo-hydro-electrochemical effects can generate a large thermal-to-electrical energy conversion factor (TtoE factor), -87 mV K-1 with low-cost carbon steel electrodes and a solid-state polyelectrolyte made of polyaniline and polystyrene sulfonate (PANI:PSS). We discovered that the thermo-diffusion of water in PANI:PSS under a temperature gradient induced less (or more) water on the hotter (or colder) side, raising (or lowering) the corrosion overpotential in the hotter (or colder) side and thereby generating output power between the electrodes. Our findings are expected to facilitate subsequent research for further increasing the TtoE factor and utilizing dissipated thermal energy.

Mixed Triboelectric and Flexoelectric Charge Transfer at the Nanoscale.

The triboelectric effect is a ubiquitous phenomenon in which the surfaces of two materials are easily charged during the contact-separation process. Despite the widespread consequences and applications, the charging mechanisms are not sufficiently understood. Here, the authors report that, in the presence of a strain gradient, the charge transfer is a result of competition between flexoelectricity and triboelectricity, which could enhance charge transfer during triboelectric measurements when the charge transfers of both effects are in the same direction. When they are in the opposite directions, the direction and amount of charge transfer could be modulated by the competition between flexoelectric and triboelectric effects, which leads to a distinctive phenomenon, that is, the charge transfer is reversed with varying forces. The subsequent results on the electrical power output signals from the triboelectrification support the proposed mechanism. Therefore, the present study emphasizes the key role of the flexoelectric effect through experimental approaches, and suggests that both the amount and direction of charge transfer can be modulated by manipulating the mixed triboelectric and flexoelectric effects. This finding may provide important information on the triboelectric effect and can be further extended to serve as a guideline for material selection during a nanopatterned device design.

Antiphase Boundaries as Faceted Metallic Wires in 2D Transition Metal Dichalcogenides.

Antiphase boundaries (APBs) in 2D transition metal dichalcogenides have attracted wide interest as 1D metallic wires embedded in a semiconducting matrix, which could be exploited in fully 2D-integrated circuits. Here, the anisotropic morphologies of APBs (i.e., linear and saw-toothed APBs) in the nanoscale are investigated. The experimental and computational results show that despite their anisotropic nanoscale morphologies, all APBs adopt a predominantly chalcogen-oriented dense structure to maintain the energetically most stable atomic configuration. Moreover, the effect of the nanoscale morphology of an APB on electron transport from two-probe field effect transistor measurements is investigated. A saw-toothed APB has a considerably lower electron mobility than a linear APB, indicating that kinks between facets are the main factors of scattering. The observations contribute to the systematical understanding of the faceted APBs and its impact on electrical transport behavior and it could potentially extend the applications of 2D materials through defect engineering to achieve the desired properties.

Investigation on energy bandgap states of amorphous SiZnSnO thin films.

The variation in energy bandgaps of amorphous oxide semiconducting SiZnSnO (a-SZTO) has been investigated by controlling the oxygen partial pressure (Op). The systematic change in Op during deposition has been used to control the electrical characteristics and energy bandgap of a-SZTO. As Op increased, the electrical properties degraded, while the energy bandgap increased systematically. This is mainly due to the change in the oxygen vacancy inside the a-SZTO thin film by controlling Op. Changes in oxygen vacancies have been observed by using X-ray photoelectron spectroscopy (XPS) and investigated by analyzing the variation in density of states (DOS) inside the energy bandgaps. In addition, energy bandgap parameters, such as valence band level, Fermi level, and energy bandgap, were extracted by using ultraviolet photoelectron spectroscopy, Kelvin probe force microscopy, and high-resolution electron energy loss spectroscopy. As a result, it was confirmed that the difference between the conduction band minimum and the Fermi level in the energy bandgap increased systematically as Op increases. This shows good agreement with the measured results of XPS and DOS analyses.

Mechanism of carrier controllability with metal capping layer on amorphous oxide SiZnSnO semiconductor.

The change of electrical performance of amorphous SiZnSnO thin film transistors (a-SZTO TFTs) has been investigated depending on various metal capping layers on the channel layer by causing different contact property. It was confirmed that the change of electrical characteristics was sensitively dependent on the change of the capping layer materials on the same channel layer between the source/drain electrodes. This sensitive change in the electrical characteristics is mainly due to different work function of metal capping layer on the channel layer. The work function of each capping layer material has been analyzed and derived by using Kelvin probe force microscopy and compared with the energy bandgap of the SZTO layer. When the work function of the capping layer is larger than that of the channel layer, electrons are depleted from the channel layer to the capping layer. On the contrary, in the case of using a material having a work function smaller than that of the channel layer, the electrical characteristics were improved because electrons were injected into the channel layer. Based on depletion and injection mechanism caused by different contact barrier between metal capping layer and channel layer, NOT, NAND, and NOR logic circuits have been implemented simply by changing metal capping layer on the channel layer.

A Surface-Functionalized Ionovoltaic Device for Probing Ion-Specific Adsorption at the Solid-Liquid Interface.

Aqueous ion-solid interfacial interactions at an electric double layer (EDL) are studied in various research fields. However, details of the interactions at the EDL are still not fully understood due to complexity induced from the specific conditions of the solid and liquid parts. Several technical tools for ion-solid interfacial probing are experimentally and practically proposed, but they still show limitations in applicability due to the complicated measurements. Recently, an energy conversion device based on ion dynamics (called ionovoltaic device) was also introduced as another monitoring tool for the EDL, showing applicability as a novel probing method for interfacial interactions. Herein, a monitoring technique for specific ion adsorption (Cu2+ and Pb2+ in the range of 5 × 10-6 -1000 × 10-6 m) in the solid-liquid interface based on the ionovoltaic device is newly demonstrated. The specific ion adsorption and the corresponding interfacial potentials profiles are also investigated to elucidate a working mechanism of the device. The results give the insight of molecular-level ion adsorption through macroscopic water-motion-induced electricity generation. The simple and cost-effective detection of the device provides an innovative route for monitoring specific adsorption and expandability as a monitoring tool for various solid-liquid interfacial phenomena that are unrevealed.

Influence of Gas Adsorption and Gold Nanoparticles on the Electrical Properties of CVD-Grown MoS2 Thin Films.

Molybdenum disulfide (MoS2) has increasingly attracted attention from researchers and is now one of the most intensively explored atomic-layered two-dimensional semiconductors. Control of the carrier concentration and doping type of MoS2 is crucial for its application in electronic and optoelectronic devices. Because the MoS2 layers are atomically thin, their transport characteristics may be very sensitive to ambient gas adsorption and the resulting charge transfer. We investigated the influence of the ambient gas (N2, H2/N2, and O2) choice on the resistance (R) and surface work function (WF) of trilayer MoS2 thin films grown via chemical vapor deposition. We also studied the electrical properties of gold (Au)-nanoparticle (NP)-coated MoS2 thin films; their R value was found to be 2 orders of magnitude smaller than that for bare samples. While the WF largely varied for each gas, R was almost invariant for both the bare and Au-NP-coated samples regardless of which gas was used. Temperature-dependent transport suggests that variable range hopping is the dominant mechanism for electrical conduction for bare and Au-NP-coated MoS2 thin films. The charges transferred from the gas adsorbates might be insufficient to induce measurable R change and/or be trapped in the defect states. The smaller WF and larger localization length of the Au-NP-coated sample, compared with the bare sample, suggest that more carriers and less defects enhanced conduction in MoS2.

Mie Resonance-Modulated Spatial Distributions of Photogenerated Carriers in Poly(3-hexylthiophene-2,5-diyl)/Silicon Nanopillars.

Organic/silicon hybrid solar cells have great potential as low-cost, high-efficiency photovoltaic devices. The superior light trapping capability, mediated by the optical resonances, of the organic/silicon hybrid nanostructure-based cells enhances their optical performance. In this work, we fabricated Si nanopillar (NP) arrays coated with organic semiconductor, poly(3-hexylthiophene-2,5-diyl), layers. Experimental and calculated optical properties of the samples showed that Mie-resonance strongly concentrated incoming light in the NPs. Spatial mapping of surface photovoltage, i.e., changes in the surface potential under illumination, using Kelvin probe force microscopy enabled us to visualize the local behavior of the photogenerated carriers in our samples. Under red light, surface photovoltage was much larger (63 meV) on the top surface of a NP than on a planar sample (13 meV), which demonstrated that the confined light in the NPs produced numerous carriers within the NPs. Since the silicon NPs provide pathways for efficient carrier transportation, high collection probability of the photogenerated carriers near the NPs can be expected. This suggests that the optical resonance in organic/silicon hybrid nanostructures benefits not only broad-band light trapping but also efficient carrier collection.

Photoheat-induced Schottky nanojunction and indirect Mott transition in VO2: photocurrent analysis.

In order to elucidate a mechanism of the insulator-to-metal transition (IMT) for a Mott insulator VO2 (3d(1)), we present Schottky nanojunctions and the structural phase transition (SPT) by simultaneous nanolevel measurements of photocurrent and Raman scattering in microlevel devices. The Schottky nanojunction with the monoclinic metallic phase between the monoclinic insulating phases is formed by the photoheat-induced IMT not accompanied with the SPT. The temperature dependence of the Schottky junction reveals that the Mott insulator has an electronic structure of an indirect subband between the main Hubbard d bands. The IMT as reverse process of the Mott transition occurs by temperature-induced excitation of bound charges in the indirect semiconductor band, most likely formed by impurities such as oxygen deficiency. The metal band (3d(1)) for the Mott insulator is screened (trapped) by the indirect band (impurities).

Plasmon-Enhanced Surface Photovoltage of ZnO/Ag Nanogratings.

We investigated the surface photovoltage (SPV) behaviors of ZnO/Ag one-dimensional (1D) nanogratings using Kelvin probe force microscopy (KPFM). The grating structure could couple surface plasmon polaritons (SPPs) with photons, giving rise to strong light confinement at the ZnO/Ag interface. The larger field produced more photo-excited carriers and increased the SPV. SPP excitation influenced the spatial distribution of the photo-excited carriers and their recombination processes. As a result, the SPV relaxation time clearly depended on the wavelength and polarization of the incident light. All of these results suggested that SPV measurement using KPFM should be very useful for studying the plasmonic effects in nanoscale metal/semiconductor hybrid structures.

Selective photochemical synthesis of Ag nanoparticles on position-controlled ZnO nanorods for the enhancement of yellow-green light emission.

A novel technique for the selective photochemical synthesis of silver (Ag) nanoparticles (NPs) on ZnO nanorod arrays is established by combining ultraviolet-assisted nanoimprint lithography (UV-NIL) for the definition of growth sites, hydrothermal reaction for the position-controlled growth of ZnO nanorods, and photochemical reduction for the decoration of Ag NPs on the ZnO nanorods. During photochemical reduction, the size distribution and loading of Ag NPs on ZnO nanorods can be tuned by varying the UV-irradiation time. The photochemical reduction is hypothesized to facilitate the adsorbed citrate ions on the surface of ZnO, allowing Ag ions to preferentially form Ag NPs on ZnO nanorods. The ratio of visible emission to ultraviolet (UV) emission for the Ag NP-decorated ZnO nanorod arrays, synthesized for 30 min, is 20.5 times that for the ZnO nanorod arrays without Ag NPs. The enhancement of the visible emission is believed to associate with the surface plasmon (SP) effect of Ag NPs. The Ag NP-decorated ZnO nanorod arrays show significant SP-induced enhancement of yellow-green light emission, which could be useful in optoelectronic applications. The technique developed here requires low processing temperatures (120 °C and lower) and no high-vacuum deposition tools, suitable for applications such as flexible electronics.

Fractal Nature of Metallic and Insulating Domain Configurations in a VO2 Thin Film Revealed by Kelvin Probe Force Microscopy.

We investigated the surface work function (WS) and its spatial distribution for epitaxial VO2/TiO2 thin films using Kelvin probe force microscopy (KPFM). Nearly grain-boundary-free samples allowed observation of metallic and insulating domains with distinct WS values, throughout the metal-insulator transition. The metallic fraction, estimated from WS maps, describes the evolution of the resistance based on a two-dimensional percolation model. The KPFM measurements also revealed the fractal nature of the domain configuration.

Novel architecture of plasmon excitation based on self-assembled nanoparticle arrays for photovoltaics.

An efficient approach to producing hexagonally self-assembled and well-dispersed gold (Au) nanoparticles (NPs) in the pores of porous anodic aluminum oxide (AAO) is reported. This approach is particularly useful for tuning the surface plasmon resonance frequency of Au NPs by varying the effective dielectric constant of AAO. A strongly enhanced Raman spectrum of dye molecule rhodamine 6G using these well-dispersed Au NPs revealed that such a self-assembled Au NP array can induce a strong plasmonic field. Furthermore, we demonstrated a new architecture of plasmon excitation in a bulk heterojunction (BHJ) inverted organic solar cell (IOSC) using the Au NP array with AAO. The optical response of an active layer poly(3-hexylthiophene):(6,6)-phenyl-C61-butyric acid methyl ester was enhanced by this strong plasmonic field associated a well-dispersed Au NP array. A comparative study of AAO with and without Au NPs confirmed plasmonic improvement of the BHJ IOSC. Simulation results showed that Au NPs concentrate the incoming light into a strongly localized field and enhance light absorption in a wide wavelength range.