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The discovery of various primary ferroic phases in atomically-thin van der Waals crystals have created a new two-dimensional wonderland for exploring and manipulating exotic quantum phases. It may also bring technical breakthroughs in device applications, as evident by prototypical functionalities of giant tunneling magnetoresistance, gate-tunable ferromagnetism and non-volatile ferroelectric memory etc. However, two-dimensional multiferroics with effective magnetoelectric coupling, which ultimately decides the future of multiferroic-based information technology, has not been realized yet. Here, we show that an unconventional magnetoelectric coupling mechanism interlocked with heterogeneous ferrielectric transitions emerges at the two-dimensional limit in van der Waals multiferroic CuCrP 2 S 6 with inherent antiferromagnetism and antiferroelectricity. Distinct from the homogeneous antiferroelectric bulk, thin-layer CuCrP 2 S 6 under external electric field makes layer-dependent heterogeneous ferrielectric transitions, minimizing the depolarization effect introduced by the rearrangements of Cu + ions within the ferromagnetic van der Waals cages of CrS 6 and P 2 S 6 octahedrons. The resulting ferrielectric phases are characterized by substantially reduced interlayer magnetic coupling energy of nearly 50% with a moderate electric field of 0.3 V nm -1 , producing widely-tunable magnetoelectric coupling which can be further engineered by asymmetrical electrode work functions., (© 2024. The Author(s).)

Pressure engineering has attracted growing interest in the understanding of structural changes and structure-property relations of layered materials. In this study, we investigated the effect of pressure on the crystal structure of Mn 3 Sn. In-situ high-pressure x-ray diffraction experiments revealed that Mn 3 Sn maintained hexagonal lattice symmetry within the pressure range of ambient to 50.4 GPa. The ratio of lattice constants c/a is almost independent of the pressure and remains constant at 0.80, indicating a stable cell shape. Density functional theory calculations revealed the strong correlation between the crystal structure and the localization of d electrons. The Mn 3 Sn has been found in flat energy bands near the Fermi level, exhibiting a large density of states (DOS) primarily contributed by the d electrons. This large DOS near the Fermi level increases the energy barrier for a phase transition, making the transition from the hexagonal phase to the tetragonal phase challenging. Our results confirm the structural stability of Mn 3 Sn under high pressure, which is beneficial to the robustness of spintronic devices., (© 2024 IOP Publishing Ltd.)

An improved fundamental understanding of active site structures can unlock opportunities for catalysis from conceptual design to industrial practice. Herein, we present the computational discovery and experimental demonstration of a highly active surface-phosphorylated ceria catalyst that exhibits robust chlorine tolerance for catalysis. Ab initio molecular dynamics (AIMD) calculations and in situ near-ambient pressure X-ray photoelectron spectroscopy ( in situ NAP-XPS) identified a predominantly HPO 4 active structure on CeO 2 (110) and CeO 2 (111) facets at room temperature. Importantly, further elevating the temperature led to a unique hydrogen (H) atom hopping between coordinatively unsaturated oxygen and the adjacent P═O group of HPO 4 . Such a mobile H on the catalyst surface can effectively quench the chlorine radicals (Cl • ) via an orientated reaction analogous to hydrogen atom transfer (HAT), enabling the surface-phosphorylated CeO 2 -supported monolithic catalyst to exhibit both expected activity and stability for over 68 days during a pilot test, catalyzing the destruction of a complex chlorinated volatile organic compound industrial off-gas.

Foodborne pathogenic infection has brought multifaceted issues to human life, leading to an urgent demand for advanced detection technologies. CRISPR/Cas-based biosensors have the potential to address various challenges that exist in conventional assays such as insensitivity, long turnaround time and complex pretreatments. In this perspective, we review the relevant strategies of CRISPR/Cas-assisted diagnostics on foodborne pathogens, focusing on biosensing platforms for foodborne pathogens based on fluorescence, colorimetric, (electro)chemiluminescence, electrochemical, and surface-enhanced Raman scattering detection. It summarizes their detection principles by the clarification of foodborne pathogenic bacteria, fungi, and viruses. Finally, we discuss the current challenges or technical barriers of these methods against broad application, and put forward alternative solutions to improve CRISPR/Cas potential for food safety.

Titanium nitride as a typical transition metal nitride (TMN) has attracted increasing interest for its fascinating characteristics and widespread applications. However, the synthesis of two-dimensional (2D) atomically thin titanium nitride is still challenging which hinders its further research in electronic and optoelectronic fields. Here, 2D titanium nitride with a large area was prepared via in situ topochemical conversion of the titanate monolayer. The titanium nitride reveals a thickness-dependent metallic-to-semiconducting transition, where the atomically thin titanium nitride with a thickness of ∼1 nm exhibits an n-type semiconducting behavior and a highly sensitive photoresponse and displays photoswitchable resistance by repeated light irradiation. First-principles calculations confirm that the chemisorbed oxygen on the surface of the titanium nitride nanosheet depletes its electrons, while the light irradiation induced desorption of oxygen leads to increased electron doping and hence the conductance of titanium nitride. These results may allow the scalable synthesis of ultrathin TMNs and facilitate their fundamental physics research and next-generation optoelectronic applications.

Materials with negative longitudinal piezoelectric response have been a focus of recent research. So far, reported examples are mostly three-dimensional bulk materials, either compounds with strong ionic bonds or layered materials with van der Waals interlayer gaps. Here, we report the first example in two-dimensional elemental materials-the class of group-Va monolayers. From first-principles calculations, we show that these materials possess giant negative longitudinal piezoelectric coefficient e_{11}. Importantly, its physical mechanism is also distinct from all previous proposals, connected with the special buckling driven polarization in these elemental systems. As a result, the usually positive internal strain contribution to piezoelectricity becomes negative and even dominates over the clamped ion contribution in Bi monolayers. Based on this new mechanism, we also find several 2D crystal structures that may support negative longitudinal piezoelectricity. As another consequence, piezoelectric response in Bi monolayers exhibits a significant nonanalytic behavior, namely, the e_{11} coefficient takes sizably different values (differed by ∼18%) under tensile and compressive strains, a phenomenon not known before and helpful for the development of novel electromechanical devices.

Ferroelectricity in ultrathin two-dimensional (2D) materials has attracted broad interest due to potential applications in nonvolatile memory, nanoelectronics and optoelectronics. However, ferroelectricity is barely explored in materials with native centro or mirror symmetry, especially in the 2D limit. Here, we report the first experimental realization of room-temperature ferroelectricity in van der Waals layered GaSe down to monolayer with mirror symmetric structures, which exhibits strong intercorrelated out-of-plane and in-plane electric polarization. The origin of ferroelectricity in GaSe comes from intralayer sliding of the Se atomic sublayers, which breaks the local structural mirror symmetry and forms dipole moment alignment. Ferroelectric switching is demonstrated in nano devices fabricated with GaSe nanoflakes, which exhibit exotic nonvolatile memory behavior with a high channel current on/off ratio. Our work reveals that intralayer sliding is a new approach to generate ferroelectricity within mirror symmetric monolayer, and offers great opportunity for novel nonvolatile memory devices and optoelectronics applications., (© 2023. The Author(s).)

Ferroelectric materials are fascinating for their non-volatile switchable electric polarizations induced by the spontaneous inversion-symmetry breaking. However, in all of the conventional ferroelectric compounds, at least two constituent ions are required to support the polarization switching 1,2 . Here, we report the observation of a single-element ferroelectric state in a black phosphorus-like bismuth layer 3 , in which the ordered charge transfer and the regular atom distortion between sublattices happen simultaneously. Instead of a homogenous orbital configuration that ordinarily occurs in elementary substances, we found the Bi atoms in a black phosphorous-like Bi monolayer maintain a weak and anisotropic sp orbital hybridization, giving rise to the inversion-symmetry-broken buckled structure accompanied with charge redistribution in the unit cell. As a result, the in-plane electric polarization emerges in the Bi monolayer. Using the in-plane electric field produced by scanning probe microscopy, ferroelectric switching is further visualized experimentally. Owing to the conjugative locking between the charge transfer and atom displacement, we also observe the anomalous electric potential profile at the 180° tail-to-tail domain wall induced by competition between the electronic structure and electric polarization. This emergent single-element ferroelectricity broadens the mechanism of ferroelectrics and may enrich the applications of ferroelectronics in the future., (© 2023. The Author(s).)

Solution growth of single-crystal ferroelectric oxide films has long been pursued for the low-cost development of high-performance electronic and optoelectronic devices. However, the established principles of vapor-phase epitaxy cannot be directly applied to solution epitaxy, as the interactions between the substrates and the grown materials in solution are quite different. Here, we report the successful epitaxy of single-domain ferroelectric oxide films on Nb-doped SrTiO 3 single-crystal substrates by solution reaction at a low temperature of ~200  o C. The epitaxy is mainly driven by an electronic polarization screening effect at the interface between the substrates and the as-grown ferroelectric oxide films, which is realized by the electrons from the doped substrates. Atomic-level characterization reveals a nontrivial polarization gradient throughout the films in a long range up to ~500 nm because of a possible structural transition from the monoclinic phase to the tetragonal phase. This polarization gradient generates an extremely high photovoltaic short-circuit current density of ~2.153 mA/cm 2 and open-circuit voltage of ~1.15 V under 375 nm light illumination with power intensity of 500 mW/cm 2 , corresponding to the highest photoresponsivity of ~4.306×10 -3  A/W among all known ferroelectrics. Our results establish a general low-temperature solution route to produce single-crystal gradient films of ferroelectric oxides and thus open the avenue for their broad applications in self-powered photo-detectors, photovoltaic and optoelectronic devices., (© 2023. The Author(s).)

The quantum spin Hall (QSH) effect has attracted extensive research interest because of the potential applications in spintronics and quantum computing, which is attributable to two conducting edge channels with opposite spin polarization and the quantized electronic conductance of 2 e 2 / h . Recently, 2M-WS 2 , a new stable phase of transition metal dichalcogenides with a 2M structure showing a layer configuration identical to that of the monolayer 1T' TMDs, was suggested to be a QSH insulator as well as a superconductor with a critical transition temperature of around 8 K. Here, high-resolution angle-resolved photoemission spectroscopy (ARPES) and spin-resolved ARPES are applied to investigate the electronic and spin structure of the topological surface states (TSS) in the superconducting 2M-WS 2 . The TSS exhibit characteristic spin-momentum-locking behavior, suggesting the existence of long-sought nontrivial Z 2 topological states therein. We expect that 2M-WS 2 with coexisting superconductivity and TSS might host the promising Majorana bound states.

The electrical control of two-dimensional (2D) van der Waals ferromagnets is a step forward for the realization of spintronic devices. However, using this approach for practical applications remains challenging due to its volatile memory. Herein, we adopt an alternative strategy, where the bistable ferroelectric switches (P↑ and P↓) of Sc 2 CO 2 (SCO) assist the ferromagnetic states of Cr 2 Ge 2 Te 6 (CGT) in order to achieve non-volatile memories. Moreover, MXene SCO, being an aided layer in multiferroic CGT/SCO hetero-structures, also modifies the electronic properties of CGT to half metal by its polarized P↓ state. In contrast, the P↑ state does not change the semiconducting nature of CGT. Hence, non-volatile, electrical-controlled switching of ferromagnetic CGT can be engineered by the two opposite ferroelectric states of single layer SCO. Importantly, the magnetic easy axis of CGT switches from in-plane to out-of-plane when the direction of electric polarization of SCO is altered from P↓ to P↑.

The development of efficient technologies to prevent the emission of hazardous chlorinated organics from industrial sources without forming harmful byproducts, such as dioxins, is a major challenge in environmental chemistry. Herein, we report a new hydrolytic destruction route for efficient chlorinated organics elimination and demonstrate that phosphoric acid-modified CeO 2 (HP-CeO 2 ) can decompose chlorobenzene (CB) without forming polychlorinated congeners under the industry-relevant reaction conditions. The active site and reaction pathway were investigated, and it was found that surface phosphate groups initially react with CB and water to form phenol and HCl, followed by deep oxidation. The high on-stream stability of the catalyst was due to the efficient generation of HCl, which removes Cl from the catalyst surface and ensures O 2 activation and therefore deep oxidation of the hydrocarbons. Subsequent density functional theory calculations revealed a distinctly decreased formation energy of an oxygen vacancy at nearest (V O-1 ) and next-nearest (V O-2 ) surface sites to the bonded phosphate groups, which likely contributes to the high rate of oxidation observed over the catalyst. Significantly, no dioxins, which are frequently formed in the conventional oxidation route, were observed. This work not only reports an efficient route and corresponding phosphate active site for chlorinated organics elimination but also illustrates that the rational design of the reaction route can solve some of the most important challenges in environmental catalysis.

Facet engineering of anatase TiO 2 by controlling the {001} exposure ratio has been the focus of numerous investigations to optimize photocatalytic activity. In particular, an introduction of fluoride ions during the crystal growth has been demonstrated to be very effective and decisive in realizing the facet exposure of the crystals. However, a key role of fluoride ions in stabilizing {001} exposure and improving subsequent photocatalytic activity of anatase TiO 2 remains unclear up to date. Herein, a controlled thickness of anatase TiO 2 nanosheets has been realized by introducing different amounts of ethanol into a HF acid-assisted hydrothermal reaction. The thinnest nanosheets with a thickness of ∼2.9 nm were evaluated to have the highest H 2 production rate of 41.04 mmol·h -1 ·g -1 under ultraviolet light irradiation, and the corresponding quantum efficiency was determined to be 41.6% (λ = 365 nm). Moreover, it is proved for the first time that fluoride ions are bonded with Ti vacancies on {001} facets, and such defects are crucial for stabilizing the ultrathin nanosheets and improving their electron-hole separation, therefore leading to a highly efficient photocatalytic activity. The findings offer an opportunity to engineer facets and functionality of anatase TiO 2 by controlling surface defects.

Transition metal compounds are one of the highly efficient types of catalyst for improving the reaction kinetics of hydrogen storage materials. Among all the transition metals, titanium and its compounds show great catalytic effects on magnesium hydride. In this study, for the first time, TiO2 nanosheets with exposed {001} facets were synthesized and doped into MgH2. The TiO2 nanosheet (NS)-doped MgH2 showed superior kinetic performance and the lowest desorption temperature. The onset temperature of MgH2 + 5 wt% TiO2 NS for the release of hydrogen was 180.5 °C and the corresponding peak temperature was 220.4 °C, which are much lower than those of pure MgH2 and also distinctly lower than those of MgH2 + 5 wt% TiO2 nanoparticles (NP). For the isothermal dehydrogenation analysis, the MgH2 + 5 wt% TiO2 NS could release 6.0 wt% hydrogen within 3.2 min at 260 °C and desorb 5.8 wt% hydrogen within 6 min at 240 °C. It is worth noting that the MgH2 + 5 wt% TiO2 NS can even release 1.2 wt% hydrogen at a temperature as low as 180 °C within 300 min. The hydrogenation kinetics of MgH2 + 5 wt% TiO2 NS is also greatly improved, which could absorb hydrogen within only a few seconds at mild temperature. It can take up 3.3 wt% hydrogen at 50 °C and 5.4 wt% at 100 °C within 10 s. It is demonstrated that the tremendous enhancement in reaction kinetics of MgH2 can be ascribed to the nanometer size and highly active {001} facets of anatase TiO2. The higher average surface energy can significantly reduce the hydrogen desorption activation energy of MgH2 to 67.6 kJ mol-1, thus easily improving the hydrogen desorption properties.

The electromagnetic properties at the interface of heterostructure are sensitive to the interfacial crystal structure and external field. For example, the two-dimensional magnetic states at the interface of LaAlO 3 /SrTiO 3 are discovered and can further be controlled by electric field. Here, we study two types of heterostructures, TiO 2 /PbTiO 3 and SrTiO 3 /PbTiO 3 , using first-principle electronic structure calculations. We find that the ferroelectric polarization discontinuity at the interface leads to partially occupied Ti 3d states and the magnetic moments. The magnitude of the magnetic moments and the ground-state magnetic coupling are sensitive to the polarization intensity of PbTiO 3 . As the ferroelectric polarization of PbTiO 3 increases, the two heterostructures show different magnetic ordering that strongly depends on the electron occupation of the Ti t 2g orbitals. For the TiO 2 /PbTiO 3 interface, the magnetic moments are mostly contributed by degenerated d yz /d xz orbitals of interfacial Ti atoms and the neighboring interfacial Ti atoms form ferromagnetic coupling. For SrTiO 3 /PbTiO 3 interface, the interfacial magnetic moments are mainly contributed by occupied d xy orbital because of the increased polarization intensity, and as the electron occupation increases, there exists a transition of the magnetic coupling between neighboring Ti atoms from ferromagnetism to antiferromagnetism via the superexchange interaction. Our study suggests that manipulating the polarization intensity is one effective way to control interfacial magnetic ordering in the perovskite oxide heterostructures.

Freestanding and single-crystal BiFeO 3 (BFO) nanoplates have been successfully synthesized by a fluoride ion-assisted hydrothermal method, and the thickness of the nanoplates can be effectively tailored from 80 to 380 nm by the concentration of fluoride ions. It is revealed that BFO nanoplates grew via an oriented attachment of layer by layer, giving rise to the formation of the inner interface within the nanoplates. In particular, antiferromagnetic (AFM) phase-transition temperature (Néel temperature, T N ) of the BFO nanoplates is significantly enhanced from typical 370 to ∼512 °C, whereas the Curie temperature (T C ) of the BFO nanoplates is determined to be ∼830 °C, in good agreement with a bulk value. The combination of scanning transmission electron microscopy, electron energy loss spectroscopy, and the first-principle calculations reveals that the interfacial tensile strain remarkably improves the stability of AFM ordering, accounting for the significant enhancement in T N of BFO plates. Correspondingly, the tensile strain induced the polarization and oxygen octahedral tilting has been observed near the interface. The findings presented here suggest that single-crystal BFO nanoplate is an ideal system for exploring an intrinsic magnetoelectric property, where a tensile strain can be a very promising approach to tailor AFM ordering and polarization rotation for an enhanced coupling effect.

A class of one-dimensional hollow microstructure is described, which was formed by a kinetically controlled crystal growth process. A hexagonal-phase NaYbF 4 microrod comprising isolated holes along the longitudinal axis was synthesized by a one-pot hydrothermal method with the assistance of citrate ligands. The structural void feature modulates light intensity across the microrods as a result of interference arising from light scattering and reflection by the inner walls. A single crystal comprising a structural void was doped with upconverting lanthanide ions. Upon near-infrared excitation of the doped crystal spatially resolvable optical codes were produced., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Perovskite oxide materials have been attracting significant attention due to their rich physical and chemical properties. With its proven stability and bio-compatibility, we suggest the lanthanide-doped perovskite to be a promising material for biological luminescence applications. Here, taking CaTiO 3 as a concrete example, we systematically investigate its doping properties using first-principles computational methods. We determine the conditions allowing the growth of CaTiO 3 against various competing phases. We obtain the formation energies of various intrinsic point defects in the material. The doping configuration and the charge state of the lanthanide dopants are determined. We find that for heavier elements in the lanthanide family, the substitution at the Ca site is favored under p-type growth conditions and tends to be trivalent, whereas the substitution at the Ti site is favored under n-type growth conditions and tends to be divalent. And for lighter elements in the family, the substitution at the Ca site is more favored for most cases and the dopant is more likely to be trivalent. By tuning the growth conditions, one could control the valence state of the lanthanide dopant, which in turn controls the luminescence spectra. We collect and identify the emission peaks in the infrared biological window, based on which possible doping schemes are suggested for bio-labeling and imaging applications.

Novel phenomena appear when two different oxide materials are combined together to form an interface. For example, at the interface of LaAlO 3 /SrTiO 3 , two-dimensional conductive states form to avoid the polar discontinuity, and magnetic properties are found at such an interface. In this work, we propose a new type of interface between two nonmagnetic and nonpolar oxides that could host a magnetic state, where it is the ferroelectric polarization discontinuity instead of the polar discontinuity that leads to the charge transfer, forming the interfacial magnetic state. As a concrete example, we investigate by first-principles calculations the heterostructures made of ferroelectric perovskite oxide PbTiO 3 and nonferroelectric polarized oxide TiO 2 . We show that charge is transferred to the interfacial layer forming an interfacial ferromagnetic ordering that may persist up to room temperature. Especially, the strong coupling between bulk ferroelectric polarization and interface ferromagnetism represents a new type of magnetoelectric effect, which provides an ideal platform for exploring the intriguing interfacial multiferroics. The findings here are important not only for fundamental science but also for promising applications in nanoscale electronics and spintronics.

α-MnO2 nanotubes were fabricated using a hydrothermal technique. Li, Na and K ions were introduced into MnO2 nanotubes to tailor their magnetic properties. It was found that with a doping concentration lower than 12 at%, the nanotubes showed ferromagnetic-like ordering at low temperature (<50 K), while antiferromagnetic coupling dominated their physical behavior with doping concentrations beyond 12 at%. Such experimental phenomenon was in very good agreement with associated first principle calculations. The ferromagnetic-like ordering originates from the breaking of equivalence between two different Mn-O octahedrals in α-MnO2 due to the filling of alkaline ions in the tunnels. Both small charge transfer and lattice distortion play important roles in the ferromagnetic ordering.

Engineering silicon into nanostructures has been a well-adopted strategy to improve the cyclic performance of silicon as a lithium-ion battery anode. Here, we show that the electrode performance can be further improved by alloying silicon with germanium. We have evaluated the electrode performance of SixGe1-x nanoparticles (NPs) with different compositions. Experimentally, SixGe1-x NPs with compositions approaching Si50Ge50 are found to have better cyclic retention than both Si-rich and Ge-rich NPs. During the charge/discharge process, NP merging and Si-Ge homogenization are observed. In addition, a distinct morphology difference is observed after 100 cycles, which is believed to be responsible for the different capacity retention behavior. The present study on SixGe1-x alloy NPs sheds light on the development of Si-based electrode materials for stable operation in lithium-ion batteries (e.g., through a comprehensive design of material structure and chemical composition). The investigation of composition-dependent morphology evolution in the delithiated Li-SiGe ternary alloy also significantly broadens our understanding of dealloying in complex systems, and it is complementary to the well-established understanding of dealloying behavior in binary systems (e.g., Au-Ag alloys).

A two-step doping process, magnetic followed by charge or vice versa, is required to produce massive topological surface states (TSS) in topological insulators for many physics and device applications. Here, we demonstrate simultaneous magnetic and hole doping achieved with a single dopant, carbon, in Bi2Se3 by first-principles calculations. Carbon substitution for Se (C(Se)) results in an opening of a sizable surface Dirac gap (up to 82 meV), while the Fermi level remains inside the bulk gap and close to the Dirac point at moderate doping concentrations. The strong localization of 2p states of C(Se) favors spontaneous spin polarization via a p-p interaction and formation of ordered magnetic moments mediated by surface states. Meanwhile, holes are introduced into the system by C(Se). This dual function of carbon doping suggests a simple way to realize insulating massive TSS.

The process of templating a manganese nanocluster with the 12 × 12 moiré and other two slightly distorted graphene/Ru(0001) moirés was investigated by scanning tunneling microscopy (STM). At the initial stage of nucleation, different adsorption modes for Mn monomer, dimer and trimer guided by various moiré periodicities were observed. Upon Mn coverage increasing, STM measurements revealed that Mn clusters exhibit a detectable preference for adsorption sites on all the three different moirés. The most favorable adsorption sites for Mn clusters are the fcc regions, where ordering of Mn clusters was observable, and the lateral size of the clusters are tunable with coverage. A density functional theory calculation also showed that magnetism appears with a magnetic moment of 3.79μ(B) for Mn monomer on MLG/Ru(0001).

Electron-phonon coupling plays a key role in a variety of elemental excitations and their interactions in semiconductor nanostructures. Here we demonstrate that the relaxation rate of free excitons in a single ZnTe nanobelt (NB) is considerably enhanced via a nonthermalized hot-exciton emission process as a result of an ultrastrong electron-phonon coupling. Using time-resolved photoluminescence (PL) spectroscopy and resonant Raman spectroscopy (RRS), we present a comprehensive study on the identification and the dynamics of free/bound exciton recombination and the electron-phonon interactions in crystalline ZnTe NBs. Up to tenth-order longitudinal optical (LO) phonons are observed in Raman spectroscopy, indicating an ultrastrong electron-phonon coupling strength. Temperature-dependent PL and RRS spectra suggest that electron-phonon coupling is mainly contributed from Light hole (LH) free excitons. With the presence of hot-exciton emission, two time constants (∼80 and ∼18 ps) are found in photoluminescence decay curves, which are much faster than those in many typical semiconductor nanostructures. Finally we prove that under high excitation power amplified spontaneous emission (ASE) originating from the electron-hole plasma occurs, thereby opening another radiative decay channel with an ultrashort lifetime of few picoseconds.

Making electronic devices using a single molecule has been the ultimate goal of molecular electronics. For binary data storage in particular, the challenge has been the ability to switch a single molecule in between bistable states in a simple and repeatable manner. The reversible switching of single molecules of chloroaluminum phthalocyanine (ClAlPc) dipolar molecules within a close-packed monolayer is demonstrated. By pulsing an scanning tunneling microscopy tip, read-write operations of single-molecular binary bits at ~40 Tb/cm(2) (~250 Tb/in(2)) are demonstrated., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Carbon can exist in various structural forms (graphite, graphene, graphene-nanoribbon and flake) and these are technologically very important materials. On the other hand, hydrogen incorporation in these materials can significantly affect their structural and electronic properties. As it is difficult to observe hydrogenation processes directly in experiment and to measure the electronic states at atomic scale, first-principle calculations are widely used to investigate the interaction between hydrogen and various carbon-based structures in past years. In this article, we briefly review work done in recent years, theoretical understanding on the interaction between hydrogen and different forms of carbon materials and present a number of strategies to modify the properties of carbon-based systems.

Intrinsic defects such as vacancies, interstitials, and anti-sites often introduce rich luminescent properties in II-VI semiconductor nanomaterials. A clear understanding of the dynamics of the defect-related excitons is particularly important for the design and optimization of nanoscale optoelectronic devices. In this paper, low-temperature steady-state and time-resolved photoluminescence (PL) spectroscopies have been carried out to investigate the emission of cadmium sulfide (CdS) nanobelts that originates from the radiative recombination of excitons bound to neutral donors (I(2)) and the spatially localized donor-acceptor pairs (DAP), in which the assignment is supported by first principle calculations. Our results verify that the shallow donors in CdS are contributed by sulfur vacancies while the acceptors are contributed by cadmium vacancies. At high excitation intensities, the DAP emission saturates and the PL is dominated by I(2) emission. Beyond a threshold power of approximately 5 μW, amplified spontaneous emission (ASE) of I(2) occurs. Further analysis shows that these intrinsic defects created long-lived (spin triplet) DAP trap states due to spin-polarized Cd vacancies which become saturated at intense carrier excitations.

Doping is a widely applied technological process in materials science that involves incorporating atoms or ions of appropriate elements into host lattices to yield hybrid materials with desirable properties and functions. For nanocrystalline materials, doping is of fundamental importance in stabilizing a specific crystallographic phase, modifying electronic properties, modulating magnetism as well as tuning emission properties. Here we describe a material system in which doping influences the growth process to give simultaneous control over the crystallographic phase, size and optical emission properties of the resulting nanocrystals. We show that NaYF(4) nanocrystals can be rationally tuned in size (down to ten nanometres), phase (cubic or hexagonal) and upconversion emission colour (green to blue) through use of trivalent lanthanide dopant ions introduced at precisely defined concentrations. We use first-principles calculations to confirm that the influence of lanthanide doping on crystal phase and size arises from a strong dependence on the size and dipole polarizability of the substitutional dopant ion. Our results suggest that the doping-induced structural and size transition, demonstrated here in NaYF(4) upconversion nanocrystals, could be extended to other lanthanide-doped nanocrystal systems for applications ranging from luminescent biological labels to volumetric three-dimensional displays.