Table of contents

In this review, we provide an overview of the development of quantitative structure–property relationships incorporating the impact of data uncertainty from small, limited knowledge data sets from which we rapidly develop new and larger databases. Unlike traditional database development, this informatics based approach is concurrent with the identification and discovery of the key metrics controlling structure–property relationships; and even more importantly we are now in a position to build materials databases based on design 'intent' and not just design parameters. This permits for example to establish materials databases that can be used for targeted multifunctional properties and not just one characteristic at a time as is presently done. This review provides a summary of the computational logic of building such virtual databases and gives some examples in the field of complex inorganic solids for scintillator applications.

Fullerene nanowhiskers (FNWs) are thin crystalline fibers composed of fullerene molecules, including C₆₀, C₇₀, endohedral, or functionalized fullerenes. FNWs display n-type semiconducting behavior and are used in a diverse range of applications, including field-effect transistors, solar cells, chemical sensors, and photocatalysts. Alkali metal-doped C₆₀ (fullerene) nanowhiskers (C₆₀NWs) exhibit superconducting behavior. Potassium-doped C₆₀NWs have realized the highest superconducting volume fraction of the alkali metal-doped C₆₀ crystals and display a high critical current density (J_c) under a high magnetic field of 50 kOe. The growth control of FNWs is important for their success in practical applications. This paper reviews recent FNWs research focusing on their mechanical, electrical and superconducting properties and growth mechanisms in the liquid–liquid interfacial precipitation method.

We show how non-reciprocity and topology are used to construct an optical one-way waveguide in the Voigt geometry. First, we present a traditional approach of the one-way waveguide of light using surface polaritons under a static magnetic field. Second, we explain a recent discovery of a topological approach using photonic crystals with the magneto-optical coupling. Third, we present a combination of the two approaches, toward a broadband one-way waveguide in the microwave range.

Multiferroics, materials in which both magnetic and electric fields can induce each other, resulting in a magnetoelectric response, have been attracting increasing attention, although the induced magnetic susceptibility and dielectric constant are usually small and have typically been reported for low temperatures. The magnetoelectric response usually depends on d-electrons of transition metals. Here we report that in [(GeTe)₂(Sb₂Te₃)_l]_m superlattice films (where l and m are integers) with topological phase transition, strong magnetoelectric response may be induced at temperatures above room temperature when the external fields are applied normal to the film surface. By ab initio computer simulations, it is revealed that the multiferroic properties are induced due to the breaking of spatial inversion symmetry when the p-electrons of Ge atoms change their bonding geometry from octahedral to tetrahedral. Finally, we demonstrate the existence in such structures of spin memory, which paves the way for a future hybrid device combining nonvolatile phase-change memory and magnetic spin memory.

The concept of the topological insulator (TI) has introduced a new point of view to condensed-matter physics, relating a priori unrelated subfields such as quantum (spin, anomalous) Hall effects, spin–orbit coupled materials, some classes of nodal superconductors, superfluid ³He, etc. From a technological point of view, TIs are expected to serve as platforms for realizing dissipationless transport in a non-superconducting context. The TI exhibits a gapless surface state with a characteristic conic dispersion (a surface Dirac cone). Here, we review peculiar finite-size effects applicable to such surface states in TI nanostructures. We highlight the specific electronic properties of TI nanowires and nanoparticles, and in this context we contrast the cases of weak and strong TIs. We study the robustness of the surface and the bulk of TIs against disorder, addressing the physics of Dirac and Weyl semimetals as a new research perspective in the field.

In this article, practical methods for synthesizing Tl-based ternary III-V-VI₂ chalcogenide TlBi(S$_{1-x}$Se_x)₂ are described in detail, along with characterization by x-ray diffraction and charge transport properties. The TlBi(S$_{1-x}$Se_x)₂ system is interesting because it shows a topological phase transition, where a topologically nontrivial phase changes to a trivial phase without changing the crystal structure qualitatively. In addition, Dirac semimetals whose bulk band structure shows a Dirac-like dispersion are considered to exist near the topological phase transition. The technique shown here is also generally applicable for other chalcogenide topological insulators, and will be useful for studying topological insulators and related materials.

This article is meant as a gentle introduction to the topological terms that often play a decisive role in effective theories describing topological quantum effects in condensed matter systems. We first take up several prominent examples, mainly from the area of quantum magnetism and superfluids/superconductors. We then briefly discuss how these ideas are now finding incarnations in the studies of symmetry-protected topological phases, which are in a sense a generalization of the concept of topological insulators to a wider range of materials, including magnets and cold atoms.

Intrinsic short hole diffusion length is a well-known problem for α-Fe₂O₃ as a visible-light photocatalytic material. In this paper, a nanodisk morphology was designed to remarkably enhance separation of electron-hole pairs of α-Fe₂O₃. As expected, α-Fe₂O₃ nanodisks presented superior photocatalytic activity toward methylene blue degradation: more than 90% of the dye could be photodegraded within 30 min in comparison with a degradation efficiency of 50% for conventional Fe₂O₃ powder. The unique multilayer structure is thought to play a key role in the remarkably improved photocatalytic performance. Further experiments involving mechanism investigations revealed that instead of high surface area, ·OH plays a crucial role in methylene blue degradation and that O^·2− may also contribute effectively to the degradation process. This paper demonstrates a facile and energy-saving route to fabricating homogenous α-Fe₂O₃ nanodisks with superior photocatalytic activity that is suitable for the treatment of contaminated water and that meets the requirement of mass production.

Self-propelled micromotors are emerging as important tools that help us understand the fundamentals of motion at the microscale and the nanoscale. Development of the motors for various biomedical and environmental applications is being pursued. Multiple fabrication methods can be used to construct the geometries of different sizes of motors. Here, we present an overview of appropriate methods of fabrication according to both size and shape requirements and the concept of guiding the catalytic motors within the confines of wall. Micromotors have also been incorporated with biological systems for a new type of fabrication method for bioinspired hybrid motors using three-dimensional (3D) printing technology. The 3D printed hybrid and bioinspired motors can be propelled by using ultrasound or live cells, offering a more biocompatible approach when compared to traditional catalytic motors.

Highly stable, cost-effective electrocatalysts facilitating oxygen reduction are crucial for the commercialization of membrane-based fuel cell and battery technologies. Herein, we demonstrate that protein-rich soya chunks with a high content of N, S and P atoms are an excellent precursor for heteroatom-doped highly graphitized carbon materials. The materials are nanoporous, with a surface area exceeding 1000 m² g⁻¹, and they are tunable in doping quantities. These materials exhibit highly efficient catalytic performance toward oxygen reduction reaction (ORR) with an onset potential of −0.045 V and a half-wave potential of −0.211 V (versus a saturated calomel electrode) in a basic medium, which is comparable to commercial Pt catalysts and is better than other recently developed metal-free carbon-based catalysts. These exhibit complete methanol tolerance and a performance degradation of merely ∼5% as compared to ∼14% for a commercial Pt/C catalyst after continuous use for 3000 s at the highest reduction current. We found that the fraction of graphitic N increases at a higher graphitization temperature, leading to the near complete reduction of oxygen. It is believed that due to the easy availability of the precursor and the possibility of genetic engineering to homogeneously control the heteroatom distribution, the synthetic strategy is easily scalable, with further improvement in performance.

Shape-memory polymers (SMPs) are a new class of smart materials, which have the capability to change from a temporary shape 'A' to a memorized permanent shape 'B' upon application of an external stimulus. In recent years, SMPs have attracted much attention from basic and fundamental research to industrial and practical applications due to the cheap and efficient alternative to well-known metallic shape-memory alloys. Since the shape-memory effect in SMPs is not related to a specific material property of single polymers, the control of nanoarchitecture of polymer networks is particularly important for the smart functions of SMPs. Such nanoarchitectonic approaches have enabled us to further create shape-memory surfaces (SMSs) with tunable surface topography at nano scale. The present review aims to bring together the exciting design of SMSs and the ever-expanding range of their uses as tools to control cell functions. The goal for these endeavors is to mimic the surrounding mechanical cues of extracellular environments which have been considered as critical parameters in cell fate determination. The untapped potential of SMSs makes them one of the most exciting interfaces of materials science and cell mechanobiology.

Organic π-conjugated molecules with extremely rich and tailorable electronic and optical properties are frequently utilized for the fabrication of optoelectronic devices. To achieve high solubility for facile solution processing and desirable softness for flexible device fabrication, the rigid π units were in most cases attached by alkyl chains through chemical modification. Considerable numbers of alkylated-π molecular systems with versatile applications have been reported. However, a profound understanding of the molecular state control through proper alkyl chain substitution is still highly demanded because effective applications of these molecules are closely related to their physical states. To explore the underlying rule, we review a large number of alkylated-π molecules with emphasis on the interplay of van der Waals interactions (vdW) of the alkyl chains and π–π interactions of the π moieties. Based on our comprehensive investigations of the two interactions' impacts on the physical states of the molecules, a clear guidance for state control by alkyl-π engineering is proposed. Specifically, either with proper alkyl chain substitution or favorable additives, the vdW and π–π interactions can be adjusted, resulting in modulation of the physical states and optoelectronic properties of the molecules. We believe the strategy summarized here will significantly benefit the alkyl-π chemistry toward wide-spread applications in optoelectronic devices.

Hydrogenation of cyclohexanecarboxamide to aminomethylcyclohexane was conducted with silica-supported bimetallic catalysts composed of noble metal and group 6–7 elements. The combination of rhodium and molybdenum with molar ratio of 1:1 showed the highest activity. The effect of addition of various metal oxides was investigated on the catalysis of Rh–MoO_x/SiO₂, and the addition of CeO₂ much increased the activity and selectivity. Higher hydrogen pressure and higher reaction temperature in the tested range of 2–8 MPa and 393–433 K, respectively, were favorable in view of both activity and selectivity. The highest yield of aminomethylcyclohexane obtained over Rh–MoO_x/SiO₂ + CeO₂ was 63%. The effect of CeO₂ addition was highest when CeO₂ was not calcined, and CeO₂ calcined at >773 K showed a smaller effect. The use of CeO₂ as a support rather decreased the activity in comparison with Rh–MoO_x/SiO₂. The weakly-basic nature of CeO₂ additive can affect the surface structure of Rh–MoO_x/SiO₂, i.e. reducing the ratio of Mo–OH/Mo–O⁻ sites.

This review article summarizes the recent achievements in stabilization of the metastable lattice of gadolinium aluminate garnet (Gd₃Al₅O₁₂, GAG) and the related developments of advanced optical materials, including down-conversion phosphors, up-conversion phosphors, transparent ceramics, and single crystals. Whenever possible, the materials are compared with their better known YAG and LuAG counterparts to demonstrate the merits of the GAG host. It is shown that novel emission features and significantly improved luminescence can be attained for a number of phosphor systems with the more covalent GAG lattice and the efficient energy transfer from Gd³⁺ to the activator. Ce³⁺ doped GAG-based single crystals and transparent ceramics are also shown to simultaneously possess the advantages of high theoretical density, fast scintillation decay, and high light yields, and hold great potential as scintillators for a wide range of applications. The unresolved issues are also pointed out.

A highly topical set of perovskite oxides are high-sensitivity piezoelectric ones, among which Pb(Zr,Ti)O₃ at the morphotropic phase boundary (MPB) between ferroelectric rhombohedral and tetragonal polymorphic phases is reckoned a case study. Piezoelectric ceramics are used in a wide range of mature, electromechanical transduction technologies like piezoelectric sensors, actuators and ultrasound generation, to name only a few examples, and more recently for demonstrating novel applications like magnetoelectric composites. In this case, piezoelectric perovskites are combined with magnetostrictive materials to provide magnetoelectricity as a product property of the piezoelectricity and piezomagnetism of the component phases. Interfaces play a key issue, for they control the mechanical coupling between the piezoresponsive phases. We present here main results of our investigation on the suitability of the high sensitivity MPB piezoelectric perovskite BiScO₃–PbTiO₃ in combination with ferrimagnetic spinel oxides for magnetoelectric composites. Emphasis has been put on the processing at low temperature to control reactions and interdiffusion between the two oxides. The role of the grain size effects is extensively addressed.

Highly textured thin films with small grain boundary regions can be used as model systems to directly measure the bulk conductivity of oxygen ion conducting oxides. Ionic conducting thin films and epitaxial heterostructures are also widely used to probe the effect of strain on the oxygen ion migration in oxide materials. For the purpose of these investigations a good lattice matching between the film and the substrate is required to promote the ordered film growth. Moreover, the substrate should be a good electrical insulator at high temperature to allow a reliable electrical characterization of the deposited film. Here we report the fabrication of an epitaxial heterostructure made with a double buffer layer of BaZrO₃ and SrTiO₃ grown on MgO substrates that fulfills both requirements. Based on such template platform, highly ordered (001) epitaxially oriented thin films of 15% Sm-doped CeO₂ and 8 mol% Y₂O₃ stabilized ZrO₂ are grown. Bulk conductivities as well as activation energies are measured for both materials, confirming the success of the approach. The reported insulating template platform promises potential application also for the electrical characterization of other novel electrolyte materials that still need a thorough understanding of their ionic conductivity.

The reconstructed surface structure of the II–VI semiconductor ZnTe (110), which is a promising material in the research field of semiconductor spintronics, was studied by scanning tunneling microscopy/spectroscopy (STM/STS). First, the surface states formed by reconstruction by the charge transfer of dangling bond electrons from cationic Zn to anionic Te atoms, which are similar to those of IV and III–V semiconductors, were confirmed in real space. Secondly, oscillation in tunneling current between binary states, which is considered to reflect a conformational change in the topmost Zn–Te structure between the reconstructed and bulk-like ideal structures, was directly observed by STM. Third, using the technique of charge injection, a surface atomic structure was successfully fabricated, suggesting the possibility of atomic-scale manipulation of this widely applicable surface of ZnTe.

Polymeric structures with integrated, functional microelectrical mechanical systems (MEMS) elements are increasingly important in various applications such as biomedical systems or wearable smart devices. These applications require highly flexible and elastic polymers with good conductivity, which can be embedded into a matrix that undergoes large deformations. Conductive polydimethylsiloxane (PDMS) is a suitable candidate but is still challenging to fabricate. Conductivity is achieved by filling a nonconductive PDMS matrix with conductive particles. In this work, we present an approach that uses new mixing techniques to fabricate conductive PDMS with different fillers such as carbon black, silver particles, and multiwalled carbon nanotubes. Additionally, the electrical properties of all three composites are examined under continuous mechanical stress. Furthermore, we present a novel, low-cost, simple three-step molding process that transfers a micro patterned silicon master into a polystyrene (PS) polytetrafluoroethylene (PTFE) replica with improved release features. This PS/PTFE mold is used for subsequent structuring of conductive PDMS with high accuracy. The non sticking characteristics enable the fabrication of delicate structures using a very soft PDMS, which is usually hard to release from conventional molds. Moreover, the process can also be applied to polyurethanes and various other material combinations.

Silver nanoparticles (AgNPs) have been widely used in diverse fields due to their superior properties. Currently the biosynthesis of AgNPs is in the limelight of modern nanotechnology because of its green properties. However, relatively low yield and inefficiency diminish the prospect of applying these biosynthesized AgNPs. In this work, a rapid mass AgNP biosynthesis method using the cell-free extract of a novel bacterial strain, Lysinibacillus sphaericus MR-1, which has been isolated from a chemical fertilizer plant, is reported. In addition, the optimum synthesis conditions of AgNPs were investigated. The optimum pH, temperature, dosage, and reaction time were 12, 70 °C, 20 mM AgNO₃, and 75 min, respectively. Finally, AgNPs were characterized by optical absorption spectroscopy, zeta potential and size distribution analysis, x-ray diffraction, electron microscopy, and energy-dispersive x-ray spectroscopy. The results revealed that these biosynthesized AgNPs were bimolecular covered, stable, well-dispersed face centered cubic (fcc) spherical crystalline particles with diameters in the range 5–20 nm. The advantages of this approach are its simplicity, high efficiency, and eco-friendly and cost-effective features.

The joining of macroscopic films of vertically aligned multiwalled carbon nanotubes (CNTs) to titanium substrates is demonstrated by active vacuum brazing at 820 °C with a Ag–Cu–Ti alloy and at 880 °C with a Cu–Sn–Ti–Zr alloy. The brazing methodology was elaborated in order to enable the production of highly electrically and thermally conductive CNT/metal substrate contacts. The interfacial electrical resistances of the joints were measured to be as low as 0.35 Ω. The improved interfacial transport properties in the brazed films lead to superior electron field-emission properties when compared to the as-grown films. An emission current of 150 μA was drawn from the brazed nanotubes at an applied electric field of 0.6 V μm⁻¹. The improvement in electron field-emission is mainly attributed to the reduction of the contact resistance between the nanotubes and the substrate. The joints have high re-melting temperatures up to the solidus temperatures of the alloys; far greater than what is achievable with standard solders, thus expanding the application potential of CNT films to high-current and high-power applications where substantial frictional or resistive heating is expected.

Core@shell and concentration-gradient particles have attracted much attention as improved cathodes for Li-ion batteries (LIBs). However, most of their preparation routes have employed a precisely-controlled co-precipitation method. Here, we report a facile preparation route of core@shell and concentration-gradient spinel particles by dry powder processing. The core@shell particles composed of the MnO₂ core and the Li(Ni,Mn)₂O₄ spinel shell are prepared by mechanical treatment using an attrition-type mill, whereas the concentration-gradient spinel particles with an average composition of LiNi_0.32Mn_1.68O₄ are produced by calcination of their core@shell particles as a precursor. The concentration-gradient LiNi_0.32Mn_1.68O₄ spinel cathode exhibits the high discharge capacity of 135.3 mA h g⁻¹, the wide-range plateau at a high voltage of 4.7 V and the cyclability with a capacity retention of 99.4% after 20 cycles. Thus, the facile preparation route of the core@shell and concentration-gradient particles may provide a new opportunity for the discovery and investigation of functional materials as well as for the cathode materials for LIBs.

We describe a fast and cost-effective process for the growth of carbon nanofibers (CNFs) at a temperature compatible with complementary metal oxide semiconductor technology, using highly stable polymer–Pd nanohybrid colloidal solutions of palladium catalyst nanoparticles (NPs). Two polymer–Pd nanohybrids, namely poly(lauryl methacrylate)-block-poly((2-acetoacetoxy)ethyl methacrylate)/Pd (LauMA_x-b-AEMA_y/Pd) and polyvinylpyrrolidone/Pd were prepared in organic solvents and spin-coated onto silicon substrates. Subsequently, vertically aligned CNFs were grown on these NPs by plasma enhanced chemical vapor deposition at different temperatures. The electrical properties of the grown CNFs were evaluated using an electrochemical method, commonly used for the characterization of supercapacitors. The results show that the polymer–Pd nanohybrid solutions offer the optimum size range of palladium catalyst NPs enabling the growth of CNFs at temperatures as low as 350 °C. Furthermore, the CNFs grown at such a low temperature are vertically aligned similar to the CNFs grown at 550 °C. Finally the capacitive behavior of these CNFs was similar to that of the CNFs grown at high temperature assuring the same electrical properties thus enabling their usage in different applications such as on-chip capacitors, interconnects, thermal heat sink and energy storage solutions.