Qionghua Zhou

Light-Induced Ambient Degradation of Few-Layer Black Phosphorus: Mechanism and Protection.

The environmental instability of single- or few-layer black phosphorus (BP) has become a major hurdle for BP-based devices. The degradation mechanism remains unclear and finding ways to protect BP from degradation is still highly challenging. Based on ab initio electronic structure calculations and molecular dynamics simulations, a three-step picture on the ambient degradation of BP is provided: generation of superoxide under light, dissociation of the superoxide, and eventual breakdown under the action of water. The well-matched band gap and band-edge positions for the redox potential accelerates the degradation of thinner BP. Furthermore, it was found that the formation of P-O-P bonds can greatly stabilize the BP framework. A possible protection strategy using a fully oxidized BP layer as the native capping is thus proposed. Such a fully oxidization layer can resist corrosion from water and leave the BP underneath intact with simultaneous high hole mobility.

Switchable Dielectric, Piezoelectric, and Second‐Harmonic Generation Bistability in a New Improper Ferroelectric above Room Temperature

Imidazolium periodate (IPI) is found to be an improper ferroelectric. It shows bistable properties simultaneously in three channels of dielectricity, piezoelectricity, and second-harmonic generation within the temperature window 300-310 K.

Te‐Doped Black Phosphorus Field‐Effect Transistors

Element doping allows manipulation of the electronic properties of 2D materials. Enhanced transport performances and ambient stability of black-phosphorus devices by Te doping are presented. This provides a facile route for achieving airstable black-phosphorus devices.

Passivation of Black Phosphorus via Self‐Assembled Organic Monolayers by van der Waals Epitaxy

An effective passivation approach to protect black phosphorus (BP) from degradation based on multi-scale simulations is proposed. The self-assembly of perylene-3,4,9,10-tetracarboxylic dianhydride monolayers via van der Waals epitaxy on BP does not break the original electronic properties of BP. The passivation layer thickness is only 2 nm. This study opens up a new pathway toward fine passivation of BP.

Dielectric and ferroelectric sensing based on molecular recognition in Cu(1,10-phenlothroline)2SeO4·(diol) systems

The process of molecular recognition is the assembly of two or more molecules through weak interactions. Information in the process of molecular recognition can be transmitted to us via physical signals, which may find applications in sensing and switching. The conventional signals are mainly limited to light signal. Here, we describe the recognition of diols with Cu(1,10-phenlothroline)2SeO4 and the transduction of discrete recognition events into dielectric and/or ferroelectric signals. We observe that systems of Cu(1,10-phenlothroline)2SeO4·(diol) exhibit significant dielectric and/or ferroelectric dependence on different diol molecules. The compounds including ethane-1,2-diol or propane-1,2-diol just show small temperature-dependent dielectric anomalies and no reversible polarization, while the compound including ethane-1,3-diol shows giant temperature-dependent dielectric anomalies as well as ferroelectric reversible spontaneous polarization. This finding shows that dielectricity and/or ferroelectricity has the potential to be used for signalling molecular recognition.

Oxidation Mechanism and Protection Strategy of Ultrathin Indium Selenide: Insight from Theory

Ultrathin indium selenide (InSe), as a newly emerging two-dimensional material with high carrier mobility and a broad absorption spectrum, has been the focus of current research. However, the long-term environmental instability of atomically thin InSe seriously limits its practical applications. To develop an effective strategy to protect InSe, it is crucial to reveal the degradation mechanism at the atomic level. By employing density functional theory and ab initio molecular dynamics simulations, we provide an in-depth understanding of the oxidation mechanism of InSe. The defect-free InSe presents excellent stability against oxidation. Nevertheless, the Se vacancies on the surface can react with water and oxygen in air directly and activate the neighboring In-Se bonds on the basal plane for further oxidation, leading to complete degradation of InSe into oxidation products of In2O3 and elemental Se. Furthermore, we propose an efficient strategy to repair the Se vacancies by thiol chemistry. In this way, the repaired surface can resist oxidation from oxygen and retain the original high electron mobility of pristine InSe simultaneously.

Ultrathin Semiconducting Bi2Te2S and Bi2Te2Se with High Electron Mobilities

High carrier mobility and moderate band gap are two key properties of electronic device applications. Two ultrathin two-dimensional (2D) semiconductors, namely, Bi2Te2S and Bi2Te2Se nanosheets, with novel electronic and optical properties are predicted based on first-principles calculations. The Bi2Te2S and Bi2Te2Se monolayers own moderate band gaps (∼0.7 eV) and high electron mobilities (∼20 000 cm2 V-1 s-1), and they can absorb sunlight efficiently through the whole incident solar spectrum. Meanwhile, layer-dependent exponential decay band gaps are also unveiled. The relatively low interlayer binding energies suggest that these monolayers can be easily exfoliated from bulk structures. Their high dynamical and thermal stabilities are further verified by phonon dispersion calculations and ab initio molecular dynamics simulations. The exceptional properties render Bi2Te2X (X = S, Se) monolayers promising candidates in future high-speed (opto)electronic devices.

Arsenene-Based Heterostructures: Highly Efficient Bifunctional Materials for Photovoltaics and Photocatalytics

Constructing suitable type II heterostructures is a reliable solution for high-efficient photovoltaic and photocatalytic materials. Arsenene, as a rising member of monoelemental two-dimensional materials, shows great potential as a building block of heterostructures because of its suitable band gap, high carrier mobility, and good optical properties. On the basis of accurate band structure calculations by combining the many-body perturbation GW method with an extrapolation technique, we demonstrate that arsenene-based heterostructures paired with molybdenum disulfide, tetracyano-quinodimethane, or tetracyanonaphtho-quinodimethane can form type II band alignments. These arsenene-based heterostructures cannot only satisfy all the requirements as photocatalysts for photocatalytic water splitting but can also show an excellent power conversion efficiency of ∼20% as potential photovoltaics.

Enhancing the Spin–Orbit Coupling in Fe3O4 Epitaxial Thin Films by Interface Engineering

By analyzing the in-plane angular dependence of ferromagnetic resonance linewidth, we show that the Gilbert damping constant in ultrathin Fe3O4 epitaxial films on GaAs substrate can be enhanced by thickness reduction and oxygen vacancies in the interface. At the same time, the uniaxial magnetic anisotropy due to the interface effect becomes significant. Using the element-specific technique of X-ray magnetic circular dichroism, we find that the orbital-to-spin moment ratio increases with decreasing film thickness, in full agreement with the increase in the Gilbert damping obtained for these ultrathin single-crystal films. Combined with the first-principle calculations, the results suggest that the bonding with Fe and Ga or As ions and the ionic distortion near the interface, as well as the FeO defects and oxygen vacancies, may increase the spin-orbit coupling in ultrathin Fe3O4 epitaxial films and in turn provide an enhanced damping.

Surface Vacancy-Induced Switchable Electric Polarization and Enhanced Ferromagnetism in Monolayer Metal Trihalides

Monolayer chromium triiodide (CrI3), as the thinnest ferromagnetic material demonstrated in experiment [ Huang et al. Nature 2017 , 546 , 270 ], opens up new opportunities for the application of two-dimensional (2D) materials in spintronic nanodevices. Atom-thick 2D materials with switchable electric polarization are now urgently needed for their rarity and important roles in nanoelectronics. Herein, we unveil that surface I vacancies not only enhance the intrinsic ferromagnetism of monolayer CrI3 but also induce switchable electric polarization. I vacancies bring about an out-of-plane polarization without breaking the nonmetallic nature of CrI3. Meanwhile, the induced polarization can be reversed in a moderate energy barrier, arising from the unique porosity of CrI3 that contributes to the switch of I vacancies between top and bottom surfaces. Engineering 2D switchable polarization through surface vacancies is also applicable to many other metal trihalides, which opens up a new and general way toward pursuing low-dimensional multifunctional nanodevices.