Jian Shi

Three-dimensional high-density hierarchical nanowire architecture for high-performance photoelectrochemical electrodes.

Three-dimensional (3D) nanowire (NW) networks are promising for designing high-performance photoelectrochemical (PEC) electrodes owing to their long optical path for efficient light absorption, high-quality one-dimensional conducting channels for rapid electron-hole separation and charge transportation, as well as high surface areas for fast interfacial charge transfer and electrochemical reactions. By growing titanium dioxide (TiO(2)) nanorods (NRs) uniformly on dense Si NW array backbones, we demonstrated a novel three-dimensional high-density heterogeneous NW architecture that could enhance photoelectrochemical efficiency. A 3D NW architecture consisting of 20 μm long wet-etched Si NWs and dense TiO(2) NRs yielded a photoelectrochemical efficiency of 2.1%, which is three times higher than that of TiO(2) film-Si NWs having a core-shell structure. This result suggests that the 3D NW architecture is superior to straight NW arrays for PEC electrode design. The efficiency could be further improved by optimizing the number of overcoating cycles and the length/density of NW backbones. By implementing these 3D NW networks into electrode design, one may be able to advantageously impact PEC and photovoltaic device performance.

PVDF microbelts for harvesting energy from respiration

In this paper, we report a technique that uses piezoelectric polyvinylidene fluoride (PVDF) microbelts to convert the energy from low-speed air flow to electricity via their resonant oscillation. The micrometre thick PVDF thin films were fabricated by a top-down reactive ion etching process, where the thickness was controlled by etching time and the piezoelectric phase was well preserved. The thickness, air flow speed and electrical output relationship was predicted theoretically and characterized experimentally. The PVDF microbelts were able to generate sufficient electrical energy from low speed air flow for the sustained operation of small electronic devices. Their capability for harvesting energy from simulated respiration was also demonstrated.

A correlated nickelate synaptic transistor

Inspired by biological neural systems, neuromorphic devices may open up new computing paradigms to explore cognition, learning and limits of parallel computation. Here we report the demonstration of a synaptic transistor with SmNiO₃, a correlated electron system with insulator-metal transition temperature at 130°C in bulk form. Non-volatile resistance and synaptic multilevel analogue states are demonstrated by control over composition in ionic liquid-gated devices on silicon platforms. The extent of the resistance modulation can be dramatically controlled by the film microstructure. By simulating the time difference between postneuron and preneuron spikes as the input parameter of a gate bias voltage pulse, synaptic spike-timing-dependent plasticity learning behaviour is realized. The extreme sensitivity of electrical properties to defects in correlated oxides may make them a particularly suitable class of materials to realize artificial biological circuits that can be operated at and above room temperature and seamlessly integrated into conventional electronic circuits.

Cancer-targeted optical imaging with fluorescent zinc oxide nanowires.

Herein we demonstrate that intrinsically fluorescent zinc oxide (ZnO) nanowires (NWs) can be adopted for molecularly targeted imaging of cancer cells, after they are functionalized to render water solubility, biocompatibility, and low cellular toxicity. Optical imaging of integrin α(v)β(3) on U87MG human glioblastoma cells was achieved with RGD peptide-conjugated green fluorescent ZnO NWs, which opened up new avenues of research for investigating ZnO NW-based agents in tumor vasculature-targeted molecular imaging and drug delivery.

Fundamental study of mechanical energy harvesting using piezoelectric nanostructures

This paper numerically estimates the potential, the output power and the energy conversion efficiency of piezoelectric nanostructures, including rectangular nanowires (NWs), hexagonal NWs, and two-dimensional vertical thin films (the nanofins). Static analysis studies the maximum piezoelectric potential that can be produced by a BaTiO3 NW, a ZnO NW, and a ZnO nanofin when they are subjected to a constant external force. Dynamic analysis is performed to study the power generation ability via the vibration of these nanostructures agitated by ambient vibration energy. ZnO NW and nanofin are selected as two representative nanogenerator elements. Their dynamic responses are modeled using a single-degree of freedom system with a series of damping ratios. Combining the transfer functions of mechanical vibration and piezoelectric charge generation, we define the output power and efficiencies as functions of the vibration frequency and the sizes. The optimal size for constructing a high efficiency and high-power n...

Interface Engineering by Piezoelectric Potential in ZnO-Based Photoelectrochemical Anode

Through a process of photoelectrochemical (PEC) water splitting, we demonstrated an effective strategy for engineering the barrier height of a heterogeneous semiconductor interface by piezoelectric polarization, known as the piezotronic effect. A consistent enhancement or reduction of photocurrent was observed when tensile or compressive strains were applied to the ZnO anode, respectively. The photocurrent variation is attributed to a changed barrier height at the ZnO/ITO interface, which is a result of the remnant piezoelectric potential across the interface due to a nonideal free charge distribution in the ITO electrode. In our system, ∼1.5 mV barrier height change per 0.1% applied strain was identified, and 0.21% tensile strain yielded a ∼10% improvement of the maximum PEC efficiency. The remnant piezopotential is dictated by the screening length of the materials in contact with piezoelectric component. The difference between this time-independent remnant piezopotential effect and time-dependent piezoelectric effect is also studied in details.

Growth of Titanium Dioxide Nanorods in 3D-Confined Spaces

Three-dimensional (3D) nanowire (NW) networks are promising architectures for effectively translating the extraordinary properties of one-dimensional objects into a 3D space. However, to uniformly grow NWs in a 3D confined space is a serious challenge due to the coupling between crystal growth and precursor concentration that is often dictated by the mass flow characteristic of vapor or liquid phase reactants within the high-aspect ratio submicrometer channels in current strategies. We report a pulsed chemical vapor deposition (CVD) process that successfully addressed this issue and grew TiO(2) nanorods uniformly covering the entire inner surface of highly confined nanochannels. We propose a mechanism for the anisotropic growth of anatase TiO(2) based on the surface-reaction-limited CVD process. This strategy would lead to the realization of NW-based 3D nanoarchitectures from various functional materials for the applications of sensors, solar cells, catalysts, energy storage systems, and so forth.

Strongly correlated perovskite fuel cells

Fuel cells convert chemical energy directly into electrical energy with high efficiencies and environmental benefits, as compared with traditional heat engines. Yttria-stabilized zirconia is perhaps the material with the most potential as an electrolyte in solid oxide fuel cells (SOFCs), owing to its stability and near-unity ionic transference number. Although there exist materials with superior ionic conductivity, they are often limited by their ability to suppress electronic leakage when exposed to the reducing environment at the fuel interface. Such electronic leakage reduces fuel cell power output and the associated chemo-mechanical stresses can also lead to catastrophic fracture of electrolyte membranes. Here we depart from traditional electrolyte design that relies on cation substitution to sustain ionic conduction. Instead, we use a perovskite nickelate as an electrolyte with high initial ionic and electronic conductivity. Since many such oxides are also correlated electron systems, we can suppress the electronic conduction through a filling-controlled Mott transition induced by spontaneous hydrogen incorporation. Using such a nickelate as the electrolyte in free-standing membrane geometry, we demonstrate a low-temperature micro-fabricated SOFC with high performance. The ionic conductivity of the nickelate perovskite is comparable to the best-performing solid electrolytes in the same temperature range, with a very low activation energy. The results present a design strategy for high-performance materials exhibiting emergent properties arising from strong electron correlations.

Colossal resistance switching and band gap modulation in a perovskite nickelate by electron doping

The electronic properties of correlated oxides are exceptionally sensitive to the orbital occupancy of electrons. Here we report an electron doping strategy via a chemical route, where interstitial dopants (for example, hydrogen) can be reversibly intercalated, realizing a sharp phase transition in a model correlated perovskite nickelate SmNiO3. The electron configuration of eg orbital of Ni(3+) t2g(6)eg(1) in SmNiO3 is modified by injecting and anchoring an extra electron, forming a strongly correlated Ni(2+) t2g(6)eg(2) structure leading to the emergence of a new insulating phase. A reversible resistivity modulation greater than eight orders of magnitude is demonstrated at room temperature. A solid-state room temperature non-volatile proton-gated phase-change transistor is demonstrated based on this principle, which may inform new materials design for correlated oxide devices. Electron doping-driven phase transition accompanied by large conductance changes and band gap modulation opens up new directions to explore emerging electronic and photonic devices with correlated oxide systems.

Band Structure Engineering at Heterojunction Interfaces via the Piezotronic Effect

Engineering the electronic band structure using the piezopotential is an important aspect of piezotronics, which describes the coupling between the piezoelectric property and semiconducting behavior and functionalities. The time-independent band structure change under short-circuit condition is believed to be due to the remnant piezopotential present at the interface, a result of the finite charge-screening depth at the interface. A series of materials, including metals, semiconductors and electrolytes, are selected to investigate the interfacial band structure engineered by remnant piezopotential when they are in contact with a strained piezoelectric semiconductor. The remnant piezopotential at the interface can switch the junction between Ohmic and Schottky characters, enhance charge combination/separation, regulate barrier height, and modulate reaction kinetics. The difference between the regular time-dependent, pulse-type piezopotential and constant remnant piezopotential is also discussed in detail using a ZnO-based photoelectrochemical anode as an example. The piezotronic effect offers a new pathway for engineering the interface band structure without altering the interface structure or chemical composition, which is promising for improving the performance of many electronics, optoelectronics, and photovoltaic devices.