ALBERT

Beschreibung: We demonstrate enhanced hydrogen generation rates at high pH using colloidal cadmium sulphide nanorods decorated with Pt nanoparticles. We introduce a simplified procedure for the decoration and subsequent hydrogen generation, reducing both the number of working steps and the materials costs. Different Pt precursor concentrations were tested to reveal the optimal conditions for the efficient hydrogen evolution. A sharp increase in hydrogen evolution rates was measured at pH 13 and above, a condition at which the surface charge transfer was efficiently mediated by the formation of hydroxyl radicals and further consumption by the sacrificial triethanolamine hole scavenger.

Beschreibung: Recently, water-gated organic field-effect transistors (WGOFET) have been intensively studied for their application in the biological field. Surprisingly, a very limited number of conjugated polymers have been reported so far. Here, we systematically explore a series of polythiophene derivatives, presenting different alkyl side chains lengths and orientation, and characterized by various morphologies: comparative evaluation of their performances allows highlighting the critical role played by alkyl side chains, which significantly affects the polymer/water interface capacitance. Reported results provide useful guidelines towards further development of WGOFETs and represent a step forward in the understanding of the polymer/water interface phenomena.

Beschreibung: Soft magnetic alloys at the nanoscale level have long generated a vivid interest as candidate materials for technological and biomedical purposes. Consequently, controlling the structure of bimetallic nanoparticles in order to optimize their magnetic properties, such as high magnetization and low coercivity, can significantly boost their potential for related applications. However, traditional synthesis methods stumble upon the long standing challenge of developing true nanoalloys with effective control over morphology and stability against oxidation. Herein, we report on a single-step approach to the gas phase synthesis of soft magnetic bimetallic iron aluminide nanoparticles, using a versatile co-sputter inert gas condensation technique. This method allowed for precise morphological control of the particles; they consisted of an alloy iron aluminide crystalline core (DO 3 phase) and an alumina shell, which reduced inter-particle interactions and also prevented further oxidation and segregation of the bimetallic core. Remarkably, the as-deposited alloy nanoparticles show interesting soft magnetic properties, in that they combine a high saturation magnetization (170 emu/g) and low coercivity (less than 20 Oe) at room temperature. Additional functionality is tenable by modifying the surface of the particles with a polymer, to ensure their good colloidal dispersion in aqueous environments.

Beschreibung: Lattice resolved and quantitative compositional characterizations of the microstructure in TiCrAlN wear resistant coatings emerging at elevated temperatures are performed to address the spinodal decomposition into nanometer-sized coherent cubic TiCr- and Al-rich domains. The domains coarsen during annealing and at 1100 °C, the Al-rich domains include a metastable cubic Al(Cr)N phase containing 9 at. % Cr and a stable hexagonal AlN phase containing less than 1 at. % Cr. The cubic and the hexagonal phases form strained semi-coherent interfaces with each other.

Beschreibung: Nanocrystals of Mg-MOF-74 have been immobilized into the mesopores of SBA-15 rods to fabricate Mg-MOF-74@SBA-15 hybrid materials. To furnish such composites, a relatively simple synthetic strategy has been adopted by direct dispersion of the metal-organic framework (MOF) precursors in SBA-15 matrix to prepare the hybrid materials in situ . The hybrid materials have been characterized using powder X-ray diffraction and several spectroscopic and microscopic techniques, which suggest growth of the MOF nanocrystals inside the SBA-15 mesopores and the composites exhibit characteristics of both the components. N 2 adsorption isotherms at 77 K reveal that the composites contain additional mesopores, compared to only micropores of pristine MOF nanocrystals. In addition to such combination of both micro and mesoporosity, the composites also demonstrate significant CO 2 adsorption at room temperature.

Beschreibung: Transition metal ion-chelating ordered mesoporous carbon (TM-OMC) materials were recently shown to be efficient polymer electrolyte membrane fuel cell (PEMFC) catalysts. The structure and properties of these catalysts are largely different from conventional catalyst materials, thus rendering membrane electrode assembly (MEA) preparation parameters developed for conventional catalysts not useful for applications of TM-OMC catalysts. This necessitates development of a methodology to incorporate TM-OMC catalysts in the MEA. Here, an efficient method for MEA preparation using TM-OMC catalyst materials for PEMFC is developed including effects of catalyst/ionomer loading and catalyst/ionomer-mixing and application procedures. An optimized protocol for MEA preparation using TM-OMC catalysts is described.

Beschreibung: The development of devices able to detect and record ion fluxes is a crucial point in order to understand the mechanisms that regulate communication and life of organisms. Here, we take advantage of the combined electronic and ionic conduction properties of a conducting polymer to develop a hybrid organic/living device with a three-terminal configuration, using the Physarum polycephalum Cell (PPC) slime mould as a living bio-electrolyte. An over-oxidation process induces a conductivity switch in the polymer, due to the ionic flux taking place at the PPC/polymer interface. This behaviour endows a current-depending memory effect to the device.

Beschreibung: High-efficient ZnO-based nanorod array light-emitting diodes (LEDs) were grown by an oblique-angle deposition scheme. Due to the shadowing effect, the inclined ZnO vapor-flow was selectively deposited on the tip surfaces of pre-fabricated p-GaN nanorod arrays, resulting in the formation of nanosized heterojunctions. The LED architecture composed of the slanted n-ZnO film on p-GaN nanorod arrays exhibits a well-behaving current rectification of junction diode with low turn-on voltage of 4.7 V, and stably emits bluish-white luminescence with dominant peak of 390 nm under the operation of forward injection currents. In general, as the device fabrication does not involve passivation of using a polymer or sophisticated material growth techniques, the revealed scheme might be readily applied on other kinds of nanoscale optoelectronic devices.

Beschreibung: Rare earth metal borides have attracted great interest due to their unusual properties, such as superconductivity and f -electron magnetism. A recent discovery attributes the tunability of magnetism in rare earth aluminoborides to the effect of so-called “building defects.” In this paper, we report data for the effect of building defects on the thermal conductivities of α -TmAlB 4 single crystals. Building defects reduce the thermal conductivity of α -TmAlB 4 by ≈30%. At room temperature, the thermal conductivity of AlB 2 is nearly a factor of 5 higher than that of α -TmAlB 4 . AlB 2 single crystals are thermally anisotropic with the c -axis thermal conductivity nearly twice the thermal conductivity of the a-b plane. Temperature dependence of the thermal conductivity near and above room temperature reveals that both electrons and phonons contribute substantially to thermal transport in AlB 2 with electrons being the dominant heat carriers.

Beschreibung: In this study, the mechanical performance and deformation behavior of various nano-twinned Ag foils were evaluated under two deformation modes. It was generally observed that the addition of nanotwins led to an enhanced strength, but the overall plastic flow and ductility decreased. Using a bimodal distribution of nanotwinned and non-nanotwinned grains was shown to be a possible route for overcoming this limitation. Specifically, some strengthening was observed which can be attributed to the nanotwinned grains, while the ductility was attributed to the contribution from non-nanotwinned grains. The overall deformation behavior is presented and discussed in terms of the nanotwin volume fraction.

Beschreibung: In this short review, we have selected three main subjects: (i) mesoporous materials, (ii) sensing applications, and (iii) the concept of nanoarchitectonics, as examples of recent hot topics in nanomaterials research. Mesoporous materials satisfy the conditions necessary not only for a wide range of applications but also for ease of production, by a variety of simple processes, which yield bulk quantities of materials without loss of their well-defined nanometric structural features. Sensing applications are of general importance because many events arise from interaction with external stimuli. In addition to these important features, nanoarchitectonics is a concept aimed at production of novel functionality of whole units according to concerted interactions within nanostructures. For the combined subject of mesoporous sensor nanoarchitectonics, we present recent examples of research in the corresponding fields categorized according to mechanism of detection including optical, electrical, and piezoelectric sensing.

Beschreibung: We report the growth of crystalline Al 2 O 3 thin films deposited by thermal Atomic Layer Deposition (ALD) at 200 °C, which up to now has always resulted in the amorphous phase. The 5 nm thick films were deposited on Ga 2 O 3 , ZnO, and Si nanowire substrates 100 nm or less in diameter. The crystalline nature of the Al 2 O 3 thin film coating was confirmed using Transmission Electron Microscopy (TEM), including high-resolution TEM lattice imaging, selected area diffraction, and energy filtered TEM. Al 2 O 3 coatings on nanowires with diameters of 10 nm or less formed a fully crystalline phase, while those with diameters in the 20–25 nm range resulted in a partially crystalline coating, and those with diameters in excess of 50 nm were fully amorphous. We suggest that the amorphous Al 2 O 3 phase becomes metastable with respect to a crystalline alumina polymorph, due to the nanometer size scale of the film/substrate combination. Since ALD Al 2 O 3 films are widely used as protective barriers, dielectric layers, as well as potential coatings in energy materials, these findings may have important implications.

Beschreibung: Epitaxial CeO 2 films with different thickness were grown on Y 2 O 3 stabilised Zirconia substrates. Reduction of cerium ions at the interface between CeO 2 films and yttria stabilised zirconia substrates is demonstrated using aberration-corrected scanning transmission electron microscopy combined with electron energy-loss spectroscopy. It is revealed that most of the Ce ions were reduced from Ce 4+ to Ce 3+ at the interface region with a decay of several nanometers. Several possibilities of charge compensations are discussed. Irrespective of the details, such local non-stoichiometries are crucial not only for understanding charge transport in such hetero-structures but also for understanding ceria catalytic properties.

Beschreibung: Low-temperature MnBi (hexagonal NiAs phase) exhibits anomalies in the lattice constants ( a ,  c ) and bulk elastic modulus (B) below 100 K, spin reorientation and magnetic susceptibility maximum near 90 K, and, importantly for high-temperature magnetic applications, an increasing coercivity (unique to MnBi) above 180  K. We calculate the total energy and magneto-anisotropy energy (MAE) versus ( a ,  c ) using DFT+U methods. We reproduce and explain all the above anomalies. We predict that coercivity and MAE increase due to increasing a , suggesting means to improve MnBi permanent magnets.

Beschreibung: We developed an on-chip microfabricated architecture for high-accuracy gate voltage modulated Seebeck coefficient measurements on an organic field-effect transistor (FET). The microfabricated device comprises integrated heaters and temperature sensors that enable simultaneous Seebeck and FET measurements on devices with practical channel lengths on the order of 50 μ m. We exemplify the capabilities of this architecture by investigating the transition from conduction in the semiconductor bulk to conduction in the accumulation layer of a conjugated polymer FET.

Beschreibung: The pyrochlore compounds Ho 2 Ti 2 O 7 and Dy 2 Ti 2 O 7 show an exotic form of magnetism called the spin ice state, resulting from the interplay between geometrical frustration and ferromagnetic coupling. A fascinating feature of this state is the appearance of magnetic monopoles as emergent excitations above the degenerate ground state. Over the past years, strong effort has been devoted to the investigation of these monopoles and other properties of the spin ice state in bulk crystals. Here, we report the fabrication of Ho 2 Ti 2 O 7 thin films using pulsed laser deposition on yttria-stabilized ZrO 2 substrates. We investigated the structural properties of these films by X-ray diffraction, scanning transmission electron microscopy, and atomic force microscopy, and the magnetic properties by vibrating sample magnetometry at 2 K. The films not only show a high crystalline quality, but also exhibit the hallmarks of a spin ice: a pronounced magnetic anisotropy and an intermediate plateau in the magnetization along the [111] crystal direction.

Beschreibung: An unexpected, strong deterioration of crystal quality is observed in epitaxial perovskite BiFeO 3 films in which microscale features have been patterned by focused-ion-beam (FIB) milling. Specifically, synchrotron x-ray microdiffraction shows that the damaged region extends to tens of μ m, but does not result in measureable changes to morphology or stoichiometry. Therefore, this change would go undetected with standard laboratory equipment, but can significantly influence local material properties and must be taken into account when using a FIB to manufacture nanostructures. The damage is significantly reduced when a thin metallic layer is present on top of the film during the milling process, clearly indicating that the reduced crystallinity is caused by ion beam induced charging.

Beschreibung: A dramatically enhanced self-assembly of GeSi quantum dots (QDs) is disclosed on slightly miscut Si (001) substrates, leading to extremely dense QDs and even a growth mode transition. The inherent mechanism is addressed in combination of the thermodynamics and the growth kinetics both affected by steps on the vicinal surface. Moreover, temperature-dependent photoluminescence spectra from dense GeSi QDs on the miscut substrate demonstrate a rather strong peak persistent up to 300 K, which is attributed to the well confinement of excitons in the dense GeSi QDs due to the absence of the wetting layer on the miscut substrate.

Beschreibung: Using in situ scanning transmission electron microscopy heating experiments, we observed the formation of a 3-dimensional (3D) epitaxial Cu-core and Ag-shell equilibrium structure of a Cu-Ag nanoalloy. The structure was formed during the thermal interaction of Cu(∼12 nm) and Ag NPs(∼6 nm) at elevated temperatures (150–300 °C) by the Ag NPs initially wetting the Cu NP along its {111} surfaces at one or multiple locations forming epitaxial Ag/Cu (111) interfaces, followed by Ag atoms diffusing along the Cu surface. This phenomenon was confirmed through Monte Carlo simulations to be a nanoscale effect related to the large surface-to-volume ratio of the NPs.

Beschreibung: We have investigated the Mn-site substitution effect in Nd 0.45 Sr 0.55 MnO 3 single crystal, which has an A -type layered antiferromagnetic ( A -AFM) phase with the 3 d x 2 − y 2 -type orbital-order. Substitution of Fe or Ga for Mn-site suppresses both the A -AFM order and competing ferromagnetic (FM) correlation, whereas Cr substitution suppresses only the A -AFM order but reactivates the underlying FM correlation via double-exchange mechanism along the AFM coupled c -direction. In Nd 0.45 Sr 0.55 Mn 0.95 Cr 0.05 O 3 , the A -AFM state with the orbital-order is changed into the orbital-disordered three-dimensional FM metallic state by applying magnetic field of μ 0 H = 12 T, which is much smaller than that of the parent compound Nd 0.45 Sr 0.55 MnO 3 .

Beschreibung: Cuprous oxide (Cu 2 O) is actively studied as a prototypical material for energy conversion and electronic applications. Here we reduce the growth temperature of phase pure Cu 2 O thin films to 300 °C by intentionally controlling solely the kinetic parameter (total chamber pressure, P tot ) at fixed thermodynamic condition (0.25 mTorr pO 2 ). A strong non-monotonic effect of P tot on Cu-O phase formation is found using high-throughput combinatorial-pulsed laser deposition. This discovery creates new opportunities for the growth of Cu 2 O devices with low thermal budget and illustrates the importance of kinetic effects for the synthesis of metastable materials with useful properties.

Beschreibung: Alloyed silicon-germanium (SiGe) nanostructures are the topic of renewed research due to applications in modern optoelectronics and high-temperature thermoelectric materials. However, common techniques for producing nanostructured SiGe focus on bulk processing; therefore little is known of the physical properties of SiGe nanocrystals (NCs) synthesized from molecular precursors. In this letter, we synthesize and deposit thin films of doped SiGe NCs using a single, flow-through nonthermal plasma reactor and inertial impaction. Using x-ray and vibrational analysis, we show that the SiGe NC structure appears truly alloyed for Si 1−x Ge x for 0.16 〈 x 〈 0.24, and quantify the atomic dopant incorporation within the SiGe NC films.

Beschreibung: In this study, we developed a new neutron-detection device using a boron gallium nitride (BGaN) semiconductor in which the B atom acts as a neutron converter. BGaN and gallium nitride (GaN) samples were grown by metal organic vapor phase epitaxy, and their radiation detection properties were evaluated. GaN exhibited good sensitivity to α-rays but poor sensitivity to γ-rays. Moreover, we confirmed that electrons were generated in the depletion layer under neutron irradiation. This resulted in a neutron-detection signal after α-rays were generated by the capture of neutrons by the B atoms. These results prove that BGaN is useful as a neutron-detecting semiconductor material.

Beschreibung: Many complex oxides display an array of structural instabilities often tied to altered electronic behavior. For oxide heterostructures, several different interfacial effects can dramatically change the nature of these instabilities. Here, we investigate LaAlO 3 /SrTiO 3 (001) heterostructures using synchrotron x-ray scattering. We find that when cooling from high temperature, LaAlO 3 transforms from the to the Imma phase due to strain. Furthermore, the first 4 unit cells of the film adjacent to the substrate exhibit a gradient in rotation angle that can couple with polar displacements in films thinner than that necessary for 2D electron gas formation. P m 3 ¯ m

Beschreibung: We report on real time-resolved Reflectance-difference (RD) spectroscopy of GaAs(001) grown by molecular beam epitaxy, with a time-resolution of 500 ms per spectrum within the 2.3–4.0 eV photon energy range. Through the analysis of transient RD spectra we demonstrated that RD line shapes are comprised of two components with different physical origins and determined their evolution during growth. Such components were ascribed to the subsurface strain induced by surface reconstruction and to surface stoichiometry. Results reported in this paper render RD spectroscopy as a powerful tool for the study of fundamental processes during the epitaxial growth of zincblende semiconductors.

Beschreibung: The internal architecture of polymeric self-assembled chiral micro-particles is studied by exploring the effect of the chirality, of the particle sizes, and of the interface/surface properties in the ordering of the helicoidal planes. The experimental investigations, performed by means of different microscopy techniques, show that the polymeric beads, resulting from light induced polymerization of cholesteric liquid crystal droplets, preserve both the spherical shape and the internal self-organized structures. The method used to create the micro-particles with controlled internal chiral architectures presents great flexibility providing several advantages connected to the acquired optical and photonics capabilities and allowing to envisage novel strategies for the development of chiral colloidal systems and materials.

Beschreibung: Iron sulfide thin films were fabricated by the electrochemical deposition method from an aqueous solution containing FeSO 4 and Na 2 S 2 O 3 . The composition ratio obtained was Fe:S:O = 36:56:8. In the photoelectrochemical measurement, a weak negative photo-current was observed for the iron sulfide films, which indicates that its conduction type is p-type. No peaks were observed in X-ray diffraction pattern, and thus the deposited films were considered to be amorphous. For a heterojunction with ZnO, rectification properties were confirmed in the current-voltage characteristics. Moreover, the current was clearly enhanced under AM1.5 illumination.

Beschreibung: We have performed high field magnetotransport measurements to investigate the interface electron gas in a high mobility SrTiO 3 /SrCuO 2 /LaAlO 3 /SrTiO 3 heterostructure. Shubnikov-de Haas oscillations reveal several 2D conduction subbands with carrier effective masses of 0.9 m e and 2 m e , quantum mobilities of order 2000 cm 2 /V s, and band edges only a few millielectronvolts below the Fermi energy. Measurements in tilted magnetic fields confirm the 2D character of the electron gas, and show evidence of inter-subband scattering.

Beschreibung: To enlighten microscopic origin of visible-light absorption in transparent amorphous semiconducting oxides, the intrinsic optical property of amorphous InGaZnO 4 is investigated by considering dipole transitions within the quasiparticle band structure. In comparison with the crystalline InGaZnO 4 with the optical gap of 3.6 eV, the amorphous InGaZnO 4 has two distinct features developed in the band structure that contribute to significant visible-light absorption. First, the conduction bands are down-shifted by 0.55 eV mainly due to the undercoordinated In atoms, reducing the optical gap between extended states to 2.8 eV. Second, tail states formed by localized oxygen p orbitals are distributed over ∼0.5 eV near the valence edge, which give rise to substantial subgap absorption. The fundamental understanding on the optical property of amorphous semiconducting oxides based on underlying electronic structure will pave the way for resolving instability issues in recent display devices incorporating the semiconducting oxides.

Beschreibung: Nickel oxide (NiO) nanocrystals epitaxially grown on (001) strontium titanate (SrTiO 3 ) single crystal substrates were characterized to investigate interface morphology and chemistry. Aberration corrected high angle annular dark field scanning transmission electron microscopy reveals the interface between the NiO nanocrystals and the underlying SrTiO 3 substrate to be rough, irregular, and have a lower average atomic number than the substrate or the nanocrystal. Energy dispersive x-ray spectroscopy and electron energy loss spectroscopy confirm both chemical disorder and a shift of the energy of the Ti L 2,3 peaks. Analysis of the O K edge profiles in conjunction with this shift, implies the presence of oxygen vacancies at the interface. This sheds light into the origin of the previously postulated minority carriers’ model to explain resistive switching in NiO [J. Sullaphen, K. Bogle, X. Cheng, J. M. Gregg, and N. Valanoor, Appl. Phys. Lett.100, 203115 (2012)].

Beschreibung: Using density functional theory-based calculations, we explore the effects of oxygen vacancies and epitaxial layering on the atomic, magnetic, and electronic structure of (SrTiO 3 ) n (SrFeO 3− x ) 1 superlattices. While structures without oxygen vacancies ( x = 0) possess small or non-existent band gaps and ferromagnetic ordering in their iron layers, those with large vacancy concentrations ( x = 0.5) have much larger gaps and antiferromagnetic ordering. Though the computed gaps depend numerically on the delicate energetic balance of vacancy ordering and on the value of Hubbard U eff used in the calculations, we demonstrate that changes in layering can tune the band gaps of these superlattices below that of SrTiO 3 (3.2 eV) by raising their valence band maxima. This suggests the possibility that these superlattices could absorb in the solar spectrum, and could serve as water-splitting photocatalysts.

Beschreibung: We study the magnetic properties of Ho thin films with different crystallinity (either epitaxial or non-epitaxial) and investigate their proximity effects with Nb thin films. Magnetic measurements show that epitaxial Ho has large anisotropy in two different crystal directions in contrast to non-epitaxial Ho. Transport measurements show that the superconducting transition temperature ( T c ) of Nb thin films can be significantly suppressed at zero field by epitaxial Ho compared with non-epitaxial Ho. We also demonstrate a direct control over T c by changing the magnetic states of the epitaxial Ho layer, and attribute the strong proximity effects to exchange interaction.

Beschreibung: We report the physical behavior of self-biased multi-functional magneto-mechano-electric (MME) laminates simultaneously excited by magnetic and/or mechanical vibrations. The MME laminates composed of Ni and single crystal fiber composite exhibited strong ME coupling under H dc = 0 Oe at both low frequency and at resonance frequency. Depending on the magnetic field direction with respect to the crystal orientation, the energy harvester showed strong in-plane anisotropy in the output voltage and was found to generate open circuit output voltage of 20 V pp and power density of 59.78 mW/Oe 2  g 2  cm 3 under weak magnetic field of 1 Oe and mechanical vibration of 30 mg, at frequency of 21 Hz across 1 MΩ resistance.

Beschreibung: n -type binary compound semiconductors such as InN, InAs, or In 2 O 3 are especial because the branch-point energy or charge neutrality level lies within the conduction band. Their tendency to form a surface electron accumulation layer prevents the formation of rectifying Schottky contacts. Utilizing a reactive sputtering process in an oxygen-containing atmosphere, we demonstrate Schottky barrier diodes on indium oxide thin films with rectifying properties being sufficient for space charge layer spectroscopy. Conventional non-reactive sputtering resulted in ohmic contacts. We compare the rectification of Pt, Pd, and Au Schottky contacts on In 2 O 3 and discuss temperature-dependent current-voltage characteristics of Pt/In 2 O 3 in detail. The results substantiate the picture of oxygen vacancies being the source of electrons accumulating at the surface, however, the position of the charge neutrality level and/or the prediction of Schottky barrier heights from it are questioned.

Beschreibung: Porous titania films with different macrostructures were prepared with precise control of condensation degree and density of the oxide frameworks in the presence of spherical aggregates of polystyrene- block -poly(oxyethylene) (PS- b -PEO) diblock copolymer. Following detailed explanation of the formation mechanisms of three (reticular, spherical, and large spherical) macrostructures by the colloidal PS- b -PEO templating, structural variation of the titania frameworks during calcination were investigated by X-ray diffraction and X-ray photoelectron spectroscopy. Then, photocatalytic performance of the macroporous titania films was evaluated through simple degradation experiments of methylene blue under an UV irradiation. Consequently, absolute surface area of the film and crystallinity of the titania frameworks were important for understanding the photocatalytic performance, but the catalytic performance can be improved further by the macrostructural design that controls diffusivity of the targeted molecules inside the film and their accessibility to active sites.

Beschreibung: Perovskite-containing solar cells were fabricated in a two-step procedure in which PbI 2 is deposited via spin-coating and subsequently converted to the CH 3 NH 3 PbI 3 perovskite by dipping in a solution of CH 3 NH 3 I. By varying the dipping time from 5 s to 2 h, we observe that the device performance shows an unexpectedly remarkable trend. At dipping times below 15 min the current density and voltage of the device are enhanced from 10.1 mA/cm 2 and 933 mV (5 s) to 15.1 mA/cm 2 and 1036 mV (15 min). However, upon further conversion, the current density decreases to 9.7 mA/cm 2 and 846 mV after 2 h. Based on X-ray diffraction data, we determined that remnant PbI 2 is always present in these devices. Work function and dark current measurements showed that the remnant PbI 2 has a beneficial effect and acts as a blocking layer between the TiO 2 semiconductor and the perovskite itself reducing the probability of back electron transfer (charge recombination). Furthermore, we find that increased dipping time leads to an increase in the size of perovskite crystals at the perovskite-hole-transporting material interface. Overall, approximately 15 min dipping time (∼2% unconverted PbI 2 ) is necessary for achieving optimal device efficiency.

Beschreibung: Single- and few-layered transition metal dichalcogenides, such as MoS 2 and WS 2 , are emerging two-dimensional materials exhibiting numerous and unusual physico-chemical properties that could be advantageous in the fabrication of unprecedented optoelectronic devices. Here we report a novel and alternative route to synthesize triangular monocrystals of MoS 2 and Mo x W 1-x S 2 by annealing MoS 2 and MoS 2 /WO 3 precursors, respectively, in the presence of sulfur vapor. In particular, the Mo x W 1-x S 2 triangular monolayers show gradual concentration profiles of W and Mo whereby Mo concentrates in the islands’ center and W is more abundant on the outskirts of the triangular monocrystals. These observations were confirmed by atomic force microscopy, and high-resolution transmission electron microscopy, as well as Raman and photoluminescence spectroscopy. The presence of tunable PL signals depending on the Mo x W 1-x S 2 stoichiometries in 2D monocrystals opens up a wide range of applications in electronics and optoelectronics.

Beschreibung: La 2/3 Sr 1/3 MnO 3 films with uniaxial magnetic anisotropy were coherently grown on NdGaO 3 (110) substrates. The uniaxial anisotropy has strong effect on magnetoresistance (MR). A positive MR was observed when the current is along magnetic easy axis under the current-field perpendicular geometry. In contrast, no positive MR is observed when current is along the magnetic hard axis regardless of the field direction. Our analysis indicates that the anomalous anisotropic MR effect arises from the uniaxial magnetic anisotropy caused stripe domains which contribute to strong anisotropic domain wall resistivity.

Beschreibung: Aluminum nitride (AlN)/boron nitride (BN) bishell hollow nanofibers (HNFs) have been fabricated by successive atomic layer deposition (ALD) of AlN and sequential chemical vapor deposition (CVD) of BN on electrospun polymeric nanofibrous template. A four-step fabrication process was utilized: (i) fabrication of polymeric (nylon 6,6) nanofibers via electrospinning, (ii) hollow cathode plasma-assisted ALD of AlN at 100 °C onto electrospun polymeric nanofibers, (iii) calcination at 500 °C for 2 h in order to remove the polymeric template, and (iv) sequential CVD growth of BN at 450 °C. AlN/BN HNFs have been characterized for their chemical composition, surface morphology, crystal structure, and internal nanostructure using X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy, and selected area electron diffraction. Measurements confirmed the presence of crystalline hexagonal BN and AlN within the three dimensional (3D) network of bishell HNFs with relatively low impurity content. In contrast to the smooth surface of the inner AlN layer, outer BN coating showed a highly rough 3D morphology in the form of BN nano-needle crystallites. It is shown that the combination of electrospinning and plasma-assisted low-temperature ALD/CVD can produce highly controlled multi-layered bishell nitride ceramic hollow nanostructures. While electrospinning enables easy fabrication of nanofibrous template, self-limiting reactions of plasma-assisted ALD and sequential CVD provide control over the wall thicknesses of AlN and BN layers with sub-nanometer accuracy.

Beschreibung: Yttrium iron garnet (YIG, Y 3 Fe 5 O 12 ) films have been epitaxially grown on Gadolinium Gallium Garnet (GGG, Gd 3 Ga 5 O 12 ) substrates with (100) orientation using pulsed laser deposition. The films were single-phase, epitaxial with the GGG substrate, and the root-mean-square surface roughness varied between 0.14 nm and 0.2 nm. Films with thicknesses ranging from 17 to 200 nm exhibited low coercivity (

Beschreibung: Yttrium iron garnet (YIG, Y 3 Fe 5 O 12 ) films have been epitaxially grown on Gadolinium Gallium Garnet (GGG, Gd 3 Ga 5 O 12 ) substrates with (100) orientation using pulsed laser deposition. The films were single-phase, epitaxial with the GGG substrate, and the root-mean-square surface roughness varied between 0.14 nm and 0.2 nm. Films with thicknesses ranging from 17 to 200 nm exhibited low coercivity (

Beschreibung: Monolayer transition metal dichalcogenides are atomically thin direct-gap semiconductors that show a variety of novel electronic and optical properties with an optically accessible valley degree of freedom. While they are ideal materials for developing optical-driven valleytronics, the restrictions of exfoliated samples have limited exploration of their potential. Here, we present a physical vapor transport growth method for triangular WSe 2 sheets of up to 30 μ m in edge length on insulating SiO 2 substrates. Characterization using atomic force microscopy and optical microscopy reveals that they are uniform, monolayer crystals. Low temperature photoluminescence shows well resolved and electrically tunable excitonic features similar to those in exfoliated samples, with substantial valley polarization and valley coherence. The monolayers grown using this method are therefore of high enough optical quality for routine use in the investigation of optoelectronics and valleytronics.

Beschreibung: The important influence of multiple gaps in the superconductivity of MgB 2 and Fe-based compounds, especially because of the possibility that manipulation of a second gap can significantly raise the upper critical field H c2 , has refocused attention on Nb 3 Sn because anomalies in both specific heat and point-contact tunneling studies have led to the proposal that Nb 3 Sn is also a two-gap superconductor. Here, we search for evidence of the second gap in a careful study of the influence of the homogenization temperature on the sample uniformity. We show that it is very difficult to fabricate samples that are both homogeneous and stoichiometric. We find so-called “second-gap” anomalies disappear only after high temperature and long-term annealing. Such a well-annealed sample shows only a strong, electron-phonon-coupled, single-gap behavior. In contrast, samples reacted and annealed at lower temperatures, as in the earlier two-gap studies, show small chemical composition variations of the A15 phase. We propose that the second gap sightings are actually due to variation of T c within very difficult-to-fully homogenize samples. A curiosity of the A15 Nb 3 Sn phase is that almost any mixture of Nb and Sn tries to form a stoichiometric A15 composition, but the residue of course contains off-stoichiometric A15, Nb, and other phases when the Nb:Sn ratio departs from the true 3:1 stoichiometry.

Beschreibung: We report a maximal figure of merit (ZT) value of 1.1 at 600 K was obtained for the sample of which x = 0.03, representing an enhancement greater than 20% compared with a pristine AgSbTe 2 sample. This favorable thermoelectric performance originated from the optimal Sn 2+ substitution for Sb 3+ in AgSbTe 2 , which not only increased electrical conductivity but also led to a substantial reduction in thermal conductivity that was likely caused by an enhanced phonon-scattering mechanism through the combined effects of lattice defects and the presence of Ag 2 Te nanoprecipitates dispersed in the matrix.

Beschreibung: Two dimensional transition metal dichalcogenides (2D TMDs) offer promise as opto-electronic materials due to their direct band gap and reasonably good mobility values. However, most metals form high resistance contacts on semiconducting TMDs such as MoS 2 . The large contact resistance limits the performance of devices. Unlike bulk materials, low contact resistance cannot be stably achieved in 2D materials by doping. Here we build on our previous work in which we demonstrated that it is possible to achieve low contact resistance electrodes by phase transformation. We show that similar to the previously demonstrated mechanically exfoliated samples, it is possible to decrease the contact resistance and enhance the FET performance by locally inducing and patterning the metallic 1T phase of MoS 2 on chemically vapor deposited material. The device properties are substantially improved with 1T phase source/drain electrodes.

Beschreibung: A fully crystalline heterojunction of organo-metal-halide perovskite, CH 3 NH 3 PbI 3−x Cl x (X 〈 0.24), and perylene constitutes a planar photovoltaic cell that yields a photovoltage exceeding 1.2 V with a single junction cell absorbing up to 800 nm. Here, perylene not only works as a hole conductor but also contributes to photovoltage as a photoconductor. The crystalline plane orientation of perovskite prepared on TiO 2 was controlled by thermal annealing such that the lead halide (110) plane that participates in carrier conduction is highly oriented to enhance the photovoltaic performance. The crystal orientation improves the heterojunction structure with perylene. For the best cell with high crystalline orientation, a total voltage loss is significantly minimized to 0.32 V with respect to the absorption band gap of 1.55 eV. The planar crystal cells generate high open-circuit voltages of 1.15–1.22 V, which is close to a theoretical maximal voltage (1.25–1.3 V) described by the Shockley-Queisser efficiency limit. The cell yielded energy conversion efficiency up to 4.96%.

Beschreibung: We have used the fusible tin coating method to detect shear band heating in amorphous Zr 57 Ti 5 Cu 20 Ni 8 Al 10 loaded under quasi-static uniaxial compression. High-rate load data allowed a precise determination of the duration of shearing events and final fracture. When loading was halted prior to fracture we saw no evidence of melted tin despite the presence of shear offsets up to 6 μm on some shear bands. Samples loaded to fracture showed evidence of tin melting near the fracture surface. We attribute the difference to the duration of the events, which is much longer for shear banding (milliseconds) than for fracture (microseconds).

Beschreibung: GaSb quantum dots (QDs) in a GaAs matrix are investigated with cross-sectional scanning tunneling microscopy (X-STM) and photoluminescence (PL). We observe that Al-rich capping materials prevent destabilization of the nanostructures during the capping stage of the molecular beam epitaxy (MBE) growth process and thus preserves the QD height. However, the strain induced by the absence of destabilization causes many structural defects to appear around the preserved QDs. These defects originate from misfit dislocations near the GaSb/GaAs interface and extend into the capping layer as stacking faults. The lack of a red shift in the QD PL suggests that the preserved dots do not contribute to the emission spectra. We suggest that a better control over the emission wavelength and an increase of the PL intensity is attainable by growing smaller QDs with an Al-rich overgrowth.

Beschreibung: The effect of a magnetic field on the ferroelectric switching kinetics of BiFeO 3 (BFO) capacitors with La 0.8 Ca 0.2 MnO 3 (LCMO) bottom electrode and Pt top contact has been investigated. We find a strong dependence of the remnant polarization and coercive field on the magnetic field. The switching time can be systematically tuned by magnetic field and reaches a tenfold reduction around the Curie temperature of LCMO at 4 T. We attribute this behavior to the splitting of the voltage drops across the BFO film and the LCMO bottom electrode, which can be strongly influenced by an external magnetic field due to the magnetoresistance. Further experiments on the BFO capacitors with SrRuO 3 bottom electrodes show little magnetic field dependence of ferroelectric switching confirming our interpretation. Our results provide an efficient route to control the ferroelectric switching speed through the magnetic field, implying potential application in multifunctional devices.

Beschreibung: Sodium diffusion has been studied in p-type 4H-SiC. Heat treatments have been performed from 1200 °C to 1800 °C for 1 min to 4 h. Secondary ion mass spectrometry has been used to measure the sodium distribution. We show that sodium has a considerable mobility at 1200 °C in p-type 4H-SiC. On the other hand for sodium atoms trapped at suitable sites the mobility is limited up to 1800 °C. Trap limited diffusion kinetics is suggested and an effective diffusivity has been extracted with an activation energy of 4 eV for sodium diffusion in p-type 4H-SiC.

Beschreibung: We report on the fabrication and mechanical properties of all-oxide, free-standing, heteroepitaxial, piezoelectric, microelectromechanical systems (MEMS) on silicon, using PbZr 0.52 Ti 0.48 O 3 as the key functional material. The fabrication was enabled by the development of an epitaxial lift-off strategy for the patterning of multilayer oxide heterostructures grown on Si(001), employing a high temperature stable, sacrificial oxide template mask to obtain freestanding cantilever MEMS devices after substrate etching. All cantilevers, with lengths in the range 25–325 μ m, width 50 μ m, and total thickness of 300 nm, can be actuated by an external AC-bias. For lengths 50–125 μ m, the second order bending mode formed the dominant resonance, whereas for the other lengths different or multiple modes were present.

Beschreibung: Monolayer transition metal dichalcogenides are atomically thin direct-gap semiconductors that show a variety of novel electronic and optical properties with an optically accessible valley degree of freedom. While they are ideal materials for developing optical-driven valleytronics, the restrictions of exfoliated samples have limited exploration of their potential. Here, we present a physical vapor transport growth method for triangular WSe 2 sheets of up to 30 μ m in edge length on insulating SiO 2 substrates. Characterization using atomic force microscopy and optical microscopy reveals that they are uniform, monolayer crystals. Low temperature photoluminescence shows well resolved and electrically tunable excitonic features similar to those in exfoliated samples, with substantial valley polarization and valley coherence. The monolayers grown using this method are therefore of high enough optical quality for routine use in the investigation of optoelectronics and valleytronics.

Beschreibung: Improving the conductivity of earth-abundant transparent conductive oxides (TCOs) remains an important challenge that will facilitate the replacement of indium-based TCOs. Here, we show that a hydrogen (H 2 )-plasma post-deposition treatment improves the conductivity of amorphous aluminum-doped zinc tin oxide while retaining its low optical absorption. We found that the H 2 -plasma treatment performed at a substrate temperature of 50 °C reduces the resistivity of the films by 57% and increases the absorptance by only 2%. Additionally, the low substrate temperature delays the known formation of tin particles with the plasma and it allows the application of the process to temperature-sensitive substrates.

Beschreibung: We report measurement of low frequency 1/ f noise in molybdenum di-sulphide (MoS 2 ) field-effect transistors in multiple device configurations including MoS 2 on silicon dioxide as well as MoS 2 -hexagonal boron nitride (hBN) heterostructures. All as-fabricated devices show similar magnitude of noise with number fluctuation as the dominant mechanism at high temperatures and density, although the calculated density of traps is two orders of magnitude higher than that at the SiO 2 interface. Measurements on the heterostructure devices with vacuum annealing and dual gated configuration reveals that along with the channel, metal-MoS 2 contacts also play a significant role in determining noise magnitude in these devices.

Beschreibung: We report superconductivity at an onset critical temperature below 3.1 K in topological insulator ∼200-nm-thick Bi 2 Te 3 thin films grown by pulsed laser deposition. Using energy-dispersive X-ray spectroscopy elemental mapping and Auger electron spectroscopy elemental depth profiling, we clearly identified bismuth (Bi) precipitation and Bi cluster signatures. Superconductivity in the Bi 2 Te 3 films was attributed to the proximity effect of Bi clusters precipitated on the surface of the Bi 2 Te 3 films.

Beschreibung: The existence of pseudo-gap states at energies larger than the coherence energy scale is shown to be at the origin of the difficulties encountered in achieving strong vortex pinning in the high T c cuprates. Reduction or elimination of the pseudo-gap states by overdoping is effective in increasing the condensation energy and the irreversibility field. In YBa 2 Cu 3 O 7 , a full BCS state, with a single energy scale, can be restored, leading to the highest known irreversibility field and pinning strength. In the bismuthates, the detrimental effect of the pseudo-gap states can only be mitigated to some extent by overdoping.

Beschreibung: Silicon atoms deposited on Ag(111) produce various single layer silicene sheets with different buckling patterns and periodicities. Low temperature scanning tunneling microscopy reveals that one of the silicene sheets, the hypothetical √7 × √7 silicene structure, on 2√3 × 2√3 Ag(111), is inherently highly defective and displays no long-range order. Moreover, Auger and photoelectron spectroscopy measurements reveal its sudden death, to end, in a dynamic fating process at ∼300 °C. This result clarifies the real nature of the 2√3 × 2√3R(30°) silicene phase and thus helps to understand the diversity of the silicene sheets grown on Ag(111).

Beschreibung: Metal–organic frameworks (MOFs) have attracted widespread attention owing to their unusual structure and properties produced by their nanospaces. However, many MOFs possess the similar three-dimensional frameworks, limiting their structural variety and operating capacity for hydrogen storage under ambient conditions. Here we report the synthesis and structural characterization of a single-crystal one-dimensional dimer whose structure, operating capacity, and physical mechanism contrast with those of existing MOFs. The hydrogen storage capacity of 2.6 wt.% is comparable to the highest capacity achieved by existing MOFs at room temperature. This exceptional storage capacity is realized by self-organization during crystal growth using a weak base.

Beschreibung: Group-III elements act as donors in ZnO when incorporated on the Zn site. Their incorporation and behavior upon annealing is governed by diffusion, which proceeds mainly through a vacancy-assisted process. We report first-principles calculations for the migration of Al, Ga, and In donors in ZnO, based on density functional theory using a hybrid functional. From the calculated migration barriers and formation energies, we determine diffusion activation energies and estimate annealing temperatures. Impurity-vacancy binding energies and migration barriers decrease from Al to In. Activation energies for vacancy-assisted diffusion are lowest for In and highest for Al.

Beschreibung: We report the growth of GaN micro-rods and coaxial quantum-well heterostructures on graphene films, together with structural and optical characterization, for applications in flexible optical devices. Graphene films were grown on Cu foil by means of chemical vapor deposition, and used as the substrates for the growth of the GaN micro-rods, which were subsequently transferred onto SiO 2 /Si substrates. Highly Si-doped, n -type GaN micro-rods were grown on the graphene films using metal–organic chemical vapor deposition. The growth and vertical alignment of the GaN micro-rods, which is a critical factor for the fabrication of high-performance light-emitting diodes (LEDs), were characterized using electron microscopy and X-ray diffraction. The GaN micro-rods exhibited promising photoluminescence characteristics for optoelectronic device applications, including room-temperature stimulated emission. To fabricate flexible LEDs, In x Ga 1–x N/GaN multiple quantum wells and a p -type GaN layer were deposited coaxially on the GaN micro-rods, and transferred onto Ag-coated polymer substrates using lift-off. Ti/Au and Ni/Au metal layers were formed to provide electrical contacts to the n -type and p -type GaN regions, respectively. The micro-rod LEDs exhibited intense emission of visible light, even after transfer onto the flexible polymer substrate, and reliable operation was achieved following numerous cycles of mechanical deformation.

Beschreibung: Ion rectification is the asymmetrical conduction of ions through a system under different polarities of applied potentials. In this article we report the finding of a novel form of ion rectification in graphene oxide (GO) and reduced graphene oxide (RGO) films which act as an ensemble array of nanochannels. Rectification is imparted by introducing geometric asymmetry in fluidic inlets to the counter-ion selective nanochannels of GO/RGO which creates asymmetry in the enrichment/depletion effects at the macro-/nano-interface. The devices are made simply by cutting a GO or RGO film into a trapezoid and sealing the film within a Polydimethylsiloxane block so that fluid may only enter through one of two inlets. These devices exhibit rectification ratios larger than 20 (in 1 mM NaCl) while operating at modest voltages [−1 V, +1 V].

Beschreibung: We herein perform open circuit voltage decay (OCVD) measurements on methylammonium lead iodide (CH 3 NH 3 PbI 3 ) perovskite solar cells to increase the understanding of the charge carrier recombination dynamics in this emerging technology. Optically pulsed OCVD measurements are conducted on CH 3 NH 3 PbI 3 solar cells and compared to results from another type of thin-film photovoltaics, namely, the two reference polymer–fullerene bulk heterojunction solar cell devices based on P3HT:PC 60 BM and PTB7:PC 70 BM blends. We observe two very different time domains of the voltage transient in the perovskite solar cell with a first drop on a short time scale that is similar to the decay in the studied organic solar cells. However, 65%–70% of the maximum photovoltage persists on much longer timescales in the perovskite solar cell than in the organic devices. In addition, we find that the recombination dynamics in all time regimes are dependent on the starting illumination intensity, which is also not observed in the organic devices. We then discuss the potential origins of these unique behaviors.

Beschreibung: A new MOF-5 homologue compound UTSA-10 has been obtained under solvothermal conditions from a mixture of Zn(NO 3 ) 2 ⋅6H 2 O and commercially available linker, 2-methylfumaric acid, in N , N -dimethylformamide. The moderate surface area and suitable pore sizes enable the activated UTSA-10a to separate methane from C 2 hydrocarbons at room temperature.

Beschreibung: We combined zeolitic imidazolate framework nanoparticles (ZIF-8: ˜150 nm diameter) with Matrimid ® 5218 polymer to form permeable mixed matrix membranes, featuring different weight fractions of nanoparticles (up to 30 wt. % loading). We used ball-on-disc micro-tribological method to measure the frictional coefficient of the nanocomposite membranes, as a function of nanoparticle loading and annealing heat treatment. The tribological results reveal that the friction and wear of the unannealed samples rise steadily with greater nanoparticle loading because ZIF-8 is relatively harder than the matrix, thus promoting abrasive wear mechanism. After annealing, however, we discover that the nanocomposites display an appreciably lower friction and wear damage compared with the unannealed counterparts. Evidence shows that the major improvement in tribological performance is associated with the greater amounts of wear debris derived from the annealed nanocomposite membranes. We propose that detached Matrimid-encapsulated ZIF-8 nanoparticles could function as “spacers,” which are capable of not only reducing direct contact between two rubbing surfaces but also enhancing free-rolling under the action of lateral forces.

Beschreibung: Over the last decade, the development and application of nanotechnology in cancer detection, diagnosis, and therapy have been widely reported. Engineering of vehicles for the simultaneous delivery of chemo- and radiotherapeutics increases the effectiveness of the therapy and reduces the dosage of each individual drug required to produce an observable therapeutic response. We here developed a novel chemoradiotherapeutic 1,2-dioleoyl- sn -glycero-3-phosphocholine lipid coated/uncoated platinum drug loaded, holmium-containing, wrinkled mesoporous silica nanoparticle. The materials were characterized with TEM, FTIR, 1 H NMR, energy dispersive x-ray, inductively coupled plasma-mass spectrometry, and zeta potential measurements. In vitro platinum drug release from both lipid coated and uncoated chemoradiotherapeutic wrinkled mesoporous silica are reported. Various kinetic models were used to analyze the release kinetics. The radioactivity of the chemoradiotherapeutic nanocarriers was measured after neutron-activation.

Beschreibung: A self-assembly template with a photoreduction agent embedded along mesostructured silicate-surfactant channels is prepared at the air-water interface. The unique template allows uniform and continuous uptake of metallic precursors into the silicate-surfactant channels from the solution subphase. Upon UV irradiation, the metallic precursors result in near-monodisperse nanoparticles homogeneously arrayed in the mesostructured polyoxometalated-silicate-surfactant (PSS) channels until saturation. With three dimensionally densely packed Au NPs of ca. 1.7 nm in the PSS template, hence a very high number density of surface-enhanced Raman scattering (SERS) hot-spots and large absorptive volume, we show that impressive SERS can be measured with 4-nitrothiophenol adsorbed to Au-NPs@PSS.

Beschreibung: This manuscript presents the preparation and catalytic application of highly ordered benzene bridged periodic mesoporous organosilicas (PMOs) functionalized with carboxylic acid (–COOH) group at varied density. The COOH-functionalized PMOs were synthesized by one-step condensation of 1,4-bis (triethoxysilyl) benzene and carboxylic group containing organosilane carboxyethylsilanetriol sodium salt using Brij-76 as the template. The obtained materials were characterized by a mean of methods including powder X-ray diffraction, nitrogen adsorption-desorption, scanning- and transmission electron microscopy, and 13 C solid-state nuclear magnetic resonance measurements. The potentials of the obtained PMO materials with ordered mesopores were examined as solid catalysts for the chemical conversion of fructose to 5-hydroxymethylfurfural (HMF) in an organic solvent. The results showed that COOH-functionalized PMO with 10% COOH loading exhibited best results for the fructose to HMF conversion and selectivity. The high surface area, the adequate density acid functional group, and the strength of the PMO materials contributing to a promising catalytic ability were observed.

Beschreibung: In this work, we describe the controlled synthesis of novel heterogeneous nanostructures comprised of mesoporous silica-coated gold nanorods (MSGNRs) in the form of core–shell nanolollipops and nanodumb-bells, using a seed-mediated sol–gel method. Although MSGNR core–shell ( θ -MSGNR) structures have been reported previously by us and others, we herein discuss the first ever fabrication of MSGNR nanolollipops ( φ -MSGNR) and nanodumb-bells ( β -MSGNR), achieved by simply controlling the aging time of gold nanorods (GNRs), the residual cetyltrimethylammonium bromide (CTAB) coating of GNRs, and the addition of dimethyl formamide during incubation, centrifugation, and sonication, respectively. Transmission electron microscopy revealed two bare GNR isoforms, with aspect ratios of approximately 4 and 6, while scanning electron microscopy was used to further elucidate the morphology of φ -MSGNR and β -MSGNR heterostructures. In agreement with the smaller dielectric constants afforded by incomplete silica encasement, spectroscopic studies of φ -MSGNR and β -MSGNR, surface plasmon resonance (SPR) bands revealed 20-40 nm blue shifts relative to the SPR of θ -MSGNR. On the basis of the attributes and applications of more conventional θ -MSGNRs, φ -MSGNRs and β -MSGNRs are anticipated to provide most of the utility of θ -MSGNRs, but with the additional functionalities that accompany their incorporation of both bare gold and mesoporous silica encased tips; with significant/unique implications for biomedical and catalytic applications.

Beschreibung: High photoresponse can be achieved in monolayers of transition metal dichalcogenides. However, the response times are inconveniently limited by defects. Here, we report low temperature photoresponse of monolayer tungsten disulphide prepared by exfoliation and chemical vapour deposition (CVD) method. The exfoliated device exhibits n-type behaviour; while the CVD device exhibits intrinsic behaviour. In off state, the CVD device has four times larger ratio of photoresponse for laser on/off and photoresponse decay–rise times are 0.1 s (limited by our setup), while the exfoliated device has few seconds. These findings are discussed in terms of charge trapping and localization.

Beschreibung: Block copolymers exhibit various nanoscale ordered morphologies induced by microphase separation. Here, we present a method for providing two types of patterned silica films on Si wafer substrates simply by shifting the phase equilibrium of a block copolymer, polystyrene– block –poly(4–vinylpyridine) (PS–P4VP). In this method, siloxane is adsorbed onto poly(4–vinylpyridine) blocks of PS–P4VP whose structure varies with solvent polarity and is calcined to remove the block copolymer. Siloxane is in a dispersed phase with toluene as a solvent resulting in silica nanoparticle arrays, while siloxane is in a continuous phase with N , N -dimethylformamide (DMF) resulting in silica films with ordered mesopores. Since the pore size of silica films prepared in DMF is approximately 20 nm, the film has the ability to serve as a support for enzymes such as laccase.

Beschreibung: We report on the fabrication of large-area, vertically aligned GaN epitaxial core-shell micropillar arrays. The two-step process consists of inductively coupled plasma (ICP) etching of lithographically patterned GaN-on-Si substrate to produce an array of micropillars followed by selective growth of GaN shells over these pillars using Hydride Vapor Phase Epitaxy (HVPE). The most significant aspect of the study is the demonstration of the sidewall facet control in the shells, ranging from {1 1 ̄ 01} semi-polar to {1 1 ̄ 00} non-polar planes, by employing a post-ICP chemical etch and by tuning the HVPE growth temperature. Room-temperature photoluminescence, cathodoluminescence, and Raman scattering measurements reveal substantial reduction of parasitic yellow luminescence as well as strain-relaxation in the core-shell structures. In addition, X-ray diffraction indicates improved crystal quality after the shell formation. This study demonstrates the feasibility of selective epitaxy on micro-/nano- engineered templates for realizing high-quality GaN-on-Si devices.

Beschreibung: Mesoporous materials provide a unique host for controlling interactions between nanoscale guests. Here, we use polymer-templated mesoporous silicas to control magnetic dipole-dipole coupling between soft (superparamagnetic) face-centered-cubic and hard (ferromagnetic) face-centered-tetragonal FePt nanocrystals. We find that mixed soft-hard coupled FePt chains show enhanced magnetic coercivity, compared to single-component chains, while randomly associated nanocrystals show no change. A semi-quantitative analysis of temperature dependent magnetization data indicates that the free-energy barrier to spin flipping has both significant enthalpic and entropic components. Linear channels, thus, appear to be an effective way to organize magnetic nanocrystals with constructive dipolar coupling and tunable magnetic properties.

Beschreibung: The employment of linear di-, tri-, and tetra-ammoniums has generated a hierarchy in the binodal (4 12 ⋅6 3 )(4 9 ⋅6 6 ) n topologies with n = 1, 2, and 3, respectively, for the cobalt formate frameworks with increasing length of the cavities to match the ammoniums. This indicates the length-directing effect of the polyammoniums. The dynamic movements of polyammoniums between favored sites or orientations within the cavities lead to slow dielectric relaxations. All materials are spin-canted antiferromagnets in low temperatures and show reduced spontaneous magnetizations from di- and tri-, to tetra-ammoniums, because of the increased number of unique Co ions or the antiferromagnetically coupled sublattices.

Beschreibung: Metal–organic frameworks (MOFs) have attracted the attention of a variety of researchers because of their structural diversity and designability, and their varied physical properties based on their uniform microporosity. While MOFs are interesting as bulk materials, future applications in functional nanomaterials will require the use of MOFs as thin films, and to achieve this, several thin-film fabrication techniques have been developed. These techniques have provided rational design of a variety of MOF thin films; however, oriented crystal growth of a MOF thin film, which is mainly confirmed by X-ray diffraction, remains a challenge that should be addressed. In this article, we review thin-film fabrications and characterizations, and structural features of MOF thin films with perfect crystalline orientation.

Beschreibung: Partly ordered mesoporous titania films with anatase crystallites incorporated into the pore walls were prepared at low temperature by spin-coating a microemulsion-based reaction solution. The effect of relative humidity employed during aging of the prepared films was studied using SEM, TEM, and grazing incidence small angle X-ray scattering to evaluate the mesoscopic order, porosity, and crystallinity of the films. The study shows unambiguously that crystal growth occurs mainly during storage of the films and proceeds at room temperature largely depending on relative humidity. Porosity, pore size, mesoscopic order, crystallinity, and photocatalytic activity of the films increased with relative humidity up to an optimum around 75%.

Beschreibung: Reaction of styrene oxide with sodium cyanoborohydride and a catalytic amount of Hf-NU-1000 yields the anti-Markovnikov product, 2-phenylethanol, with over 98% regioselectivity. On the other hand, propylene oxide is ring opened in a Markovnikov fashion to form 2-propanol with 95% regioselectivity. Both styrene oxide and propylene oxide failed to react with sodium cyanoborohydride without the addition of Hf-NU-1000 indicative of the crucial role of Hf-NU-1000 as a catalyst in this reaction. To the best of our knowledge, this is the first report of the use of a metal-organic framework material as a catalyst for ring-opening of epoxides with hydrides.

Beschreibung: We investigated the impact of strain relaxation on the current transport of Pr 0.48 Ca 0.52 MnO 3 (PCMO) thin films grown epitaxially on SrTiO 3 single crystals by pulsed laser deposition. The incorporation of misfit dislocations and the formation of cracks are identified as competing mechanisms for the relaxation of the biaxial tensile strain. Crack formation leads to a higher crystal quality within the domains but the cracks disable the macroscopic charge transport through the PCMO layer. Progressive strain relaxation by the incorporation of misfit dislocations, on the other hand, results in a significant decrease of the activation energy for polaron hopping with increasing film thickness.

Beschreibung: The effects of the electric and magnetic field variation on multiferroic heterostructure were studied in this work. Thin films of polycrystalline Fe 50 Pt 50 (FePt) were grown by dc -sputtering on top of the commercial slabs of lead magnesium niobate-lead titanate (PMN-PT). The sample was a (011)-cut single crystal and had one side polished. In this condition, the PMN-PT/FePt operates in the L-T (longitudinal magnetized-transverse polarized) mode. A FePt thin film of 20 nm was used in this study to avoid the characteristic broad microwave absorption line associated with these films above thicknesses of 40 nm. For the in-plane easy magnetization axis (01-1), a microwave magnetoelectric (ME) coupling of 28 Oe cm kV −1 was estimated, whereas a value of 42 Oe cm kV −1 was obtained through the hard magnetization axis (100). Insight into the effects of the in-plane strain anisotropy on the ME coupling is obtained from the dc -magnetization loops. It was observed that the trend was opposite along the easy and hard magnetic directions. In particular, along the easy-magnetic axis (01-1), a square and narrow loop with a factor of M r / M S of 0.96 was measured at 10 kV/cm. Along the hard-magnetic axis, a factor of 0.16 at 10 kV/cm was obtained. Using electric tuning via microwave absorption at X-band (9.78 GHz), we observe completely different trends along the easy and hard magnetic directions; Multiple absorption lines along the latter axis compared to a single and narrower absorption line along the former. In spite of its intrinsic complexity, we propose a model which gives good agreement both for static and microwave properties. These observations are of fundamental interest for future ME microwave components, such as filters, phase-shifters, and resonators.

Beschreibung: Stability of the knee relies on the meniscus, a complex connective tissue with poor healing ability. Current meniscal tissue engineering is inadequate, as the signals for increasing meniscal cell proliferation have not been established. In this study, collagen scaffold structure, isotropic or aligned, and fibrin gel addition were tested. Metabolic activity was promoted by fibrin addition. Cellular proliferation, however, was significantly increased by both aligned architectures and fibrin addition. None of the constructs impaired collagen type I production or triggered adverse inflammatory responses. It was demonstrated that both fibrin gel addition and optimized scaffold architecture effectively promote meniscal cell proliferation.

Beschreibung: The Al/Ni formation reaction is highly exothermic and of both scientific and technological significance. In this report, we study the evolution of intermetallic phases in this reaction at a heating rate of 830 K/s. 100-nm-thick Al/Ni bilayers were deposited onto nanocalorimeter sensors that enable the measurement of temperature and heat flow during rapid heating. Time-resolved transmission electron diffraction patterns captured simultaneously with thermal measurements allow us to identify the intermetallic phases present and reconstruct the phase transformation sequence as a function of time and temperature. The results show a mostly unaltered phase transformation sequence compared to lower heating rates.

Beschreibung: Translating ionic currents into measureable electronic signals is essential for the integration of bioelectronic devices with biological systems. We demonstrate the use of a Pd/PdH x electrode as a bioprotonic transducer that connects H + currents in solution into an electronic signal. This transducer exploits the reversible formation of PdH x in solution according to PdH↔Pd + H + + e − , and the dependence of this formation on solution pH and applied potential. We integrate the protonic transducer with glucose dehydrogenase as an enzymatic AND gate for glucose and NAD + . PdH x formation and associated electronic current monitors the output drop in pH, thus transducing a biological function into a measurable electronic output.

Beschreibung: Energy production from the Sun requires a stable efficient light absorber. Promising candidates in this respect are organometal perovskites (ABX 3 ), which have been intensely investigated during the last years. Here, we have performed electronic structure calculations of 240 perovskites composed of Cs, CH 3 NH 3 , and HC(NH 2 ) 2 as A-cation, Sn and Pb as B-ion, and a combination of Cl, Br, and I as anions. The calculated gaps span over a region from 0.5 to 5.0 eV. In addition, the trends over bandgaps have been investigated: the bandgap increases with an increase of the electronegativities of the constituent species, while it reduces with an increase of the lattice constants of the system.

Beschreibung: The diffusive motion of metal nanoparticles Au and Ag on monolayer and between bilayer heterostructures of transition metal dichalcogenides and graphene are investigated in the framework of density functional theory. We found that the minimum energy barriers for diffusion and the possibility of cluster formation depend strongly on both the type of nanoparticle and the type of monolayers and bilayers. Moreover, the tendency to form clusters of Ag and Au can be tuned by creating various bilayers. Tunability of the diffusion characteristics of adatoms in van der Waals heterostructures holds promise for controllable growth of nanostructures.

Beschreibung: The utilization of tungsten diselenide (WSe 2 ) in electronic and optoelectronic devices depends on the ability to understand and control the process-property relationship during synthesis. We demonstrate that spectroscopic ellipsometry is an excellent technique for accurate, non-destructive determination of ultra-thin (

Beschreibung: Smart materials of magnetorheological (MR) fluids could be turned from a liquid state into a solid state, which solidification extent or shear strength often increases monotonically with the applied magnetic field. In this study, the shear stress of a dilute MR fluid decreased with increasing applied magnetic field at a constant shear rate. The dynamic shear stress was significantly higher than the stable counterpart at medium magnetic fields. They are ascribed to the slow particle structure transformation. A higher shear rate and particle volume fraction could reduce the transient time and the shear strength difference.

Beschreibung: Group-III elements act as donors in ZnO when incorporated on the Zn site. Their incorporation and behavior upon annealing is governed by diffusion, which proceeds mainly through a vacancy-assisted process. We report first-principles calculations for the migration of Al, Ga, and In donors in ZnO, based on density functional theory using a hybrid functional. From the calculated migration barriers and formation energies, we determine diffusion activation energies and estimate annealing temperatures. Impurity-vacancy binding energies and migration barriers decrease from Al to In. Activation energies for vacancy-assisted diffusion are lowest for In and highest for Al.

Beschreibung: The two-dimensional limit of layered materials has recently been realized through the use of van der Waals (vdW) heterostructures composed of weakly interacting layers. In this paper, we describe two different classes of vdW heterostructures: inorganic vdW heterostructures prepared by co-lamination and restacking; and organic-inorganic hetero-epitaxy created by physical vapor deposition of organic molecule crystals on an inorganic vdW substrate. Both types of heterostructures exhibit atomically clean vdW interfaces. Employing such vdW heterostructures, we have demonstrated various novel devices, including graphene/hexagonal boron nitride (hBN) and MoS 2 heterostructures for memory devices; graphene/MoS 2 /WSe 2 /graphene vertical p-n junctions for photovoltaic devices, and organic crystals on hBN with graphene electrodes for high-performance transistors.

Beschreibung: Improving the conductivity of earth-abundant transparent conductive oxides (TCOs) remains an important challenge that will facilitate the replacement of indium-based TCOs. Here, we show that a hydrogen (H 2 )-plasma post-deposition treatment improves the conductivity of amorphous aluminum-doped zinc tin oxide while retaining its low optical absorption. We found that the H 2 -plasma treatment performed at a substrate temperature of 50 °C reduces the resistivity of the films by 57% and increases the absorptance by only 2%. Additionally, the low substrate temperature delays the known formation of tin particles with the plasma and it allows the application of the process to temperature-sensitive substrates.

Beschreibung: Stable n -doping of WSe 2 using thin films of SiN x deposited on the surface via plasma-enhanced chemical vapor deposition is presented. Positive fixed charge centers inside SiN x act to dope WSe 2 thin flakes n -type via field-induced effect. The electron concentration in WSe 2 can be well controlled up to the degenerate limit by simply adjusting the stoichiometry of the SiN x through deposition process parameters. For the high doping limit, the Schottky barrier width at the metal/WSe 2 junction is significantly thinned, allowing for efficient electron injection via tunneling. Using this doping scheme, we demonstrate air-stable WSe 2 n-MOSFETs with a mobility of ∼70 cm 2 /V s.

Beschreibung: The energy level alignment at the CH 3 NH 3 PbI 3 /copper phthalocyanine (CuPc) interface is investigated by X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS). XPS reveal a 0.3 eV downward band bending in the CuPc film. UPS validate this finding and further reveal negligible interfacial dipole formation – verifying the viability of vacuum level alignment. The highest occupied molecular orbital of CuPc is found to be closer to the Fermi level than the valance band maximum of CH 3 NH 3 PbI 3 , facilitating hole transfer from CH 3 NH 3 PbI 3 to CuPc. However, subsequent hole extraction from CuPc may be impeded by the downward band bending in the CuPc layer.

Beschreibung: We report the first demonstration of 200 mm InGaAs-on-insulator (InGaAs-o-I) fabricated by the direct wafer bonding technique with a donor wafer made of III-V heteroepitaxial structure grown on 200 mm silicon wafer. The measured threading dislocation density of the In 0.53 Ga 0.47 As (InGaAs) active layer is equal to 3.5 × 10 9 cm −2 , and it does not degrade after the bonding and the layer transfer steps. The surface roughness of the InGaAs layer can be improved by chemical-mechanical-polishing step, reaching values as low as 0.4 nm root-mean-square. The electron Hall mobility in 450 nm thick InGaAs-o-I layer reaches values of up to 6000 cm 2 /Vs, and working pseudo-MOS transistors are demonstrated with an extracted electron mobility in the range of 2000–3000 cm 2 /Vs. Finally, the fabrication of an InGaAs-o-I substrate with the active layer as thin as 90 nm is achieved with a Buried Oxide of 50 nm. These results open the way to very large scale production of III-V-o-I advanced substrates for future CMOS technology nodes.

Beschreibung: We report on the preparation of mono- and bi-layer molybdenum disulfide (MoS 2 ) from a bulk crystal by facile wet chemical etching. We show that concentrated nitric acid (HNO 3 ) effectively etches thin MoS 2 crystals from their edges via formation of MoO 3 . Interestingly, etching of thin crystals on a substrate leaves behind unreacted mono- and bilayer sheets. The flakes obtained by chemical etching exhibit electronic quality comparable to that of mechanically exfoliated counterparts. Our findings indicate that the self-limiting chemical etching is a promising top-down route to preparing atomically thin crystals from bulk layer compounds.

Beschreibung: Layered two-dimensional (2D) semiconducting transition metal dichalcogenides (TMDs) have been widely isolated, synthesized, and characterized recently. Numerous 2D materials are identified as the potential candidates as channel materials for future thin film technology due to their high mobility and the exhibiting bandgaps. While many TMD filed-effect transistors (FETs) have been widely demonstrated along with a significant progress to clearly understand the device physics, large contact resistance at metal/semiconductor interface still remain a challenge. From 2D device research point of view, how to minimize the Schottky barrier effects on contacts thus reduce the contact resistance of metals on 2D materials is very critical for the further development of the field. Here, we present a review of contact research on molybdenum disulfide and other TMD FETs from the fundamental understanding of metal-semiconductor interfaces on 2D materials. A clear contact research strategy on 2D semiconducting materials is developed for future high-performance 2D FETs with aggressively scaled dimensions.

Beschreibung: We report measurement of low frequency 1/ f noise in molybdenum di-sulphide (MoS 2 ) field-effect transistors in multiple device configurations including MoS 2 on silicon dioxide as well as MoS 2 -hexagonal boron nitride (hBN) heterostructures. All as-fabricated devices show similar magnitude of noise with number fluctuation as the dominant mechanism at high temperatures and density, although the calculated density of traps is two orders of magnitude higher than that at the SiO 2 interface. Measurements on the heterostructure devices with vacuum annealing and dual gated configuration reveals that along with the channel, metal-MoS 2 contacts also play a significant role in determining noise magnitude in these devices.

Beschreibung: Two dimensional transition metal dichalcogenides (2D TMDs) offer promise as opto-electronic materials due to their direct band gap and reasonably good mobility values. However, most metals form high resistance contacts on semiconducting TMDs such as MoS 2 . The large contact resistance limits the performance of devices. Unlike bulk materials, low contact resistance cannot be stably achieved in 2D materials by doping. Here we build on our previous work in which we demonstrated that it is possible to achieve low contact resistance electrodes by phase transformation. We show that similar to the previously demonstrated mechanically exfoliated samples, it is possible to decrease the contact resistance and enhance the FET performance by locally inducing and patterning the metallic 1T phase of MoS 2 on chemically vapor deposited material. The device properties are substantially improved with 1T phase source/drain electrodes.

Beschreibung: We report a maximal figure of merit (ZT) value of 1.1 at 600 K was obtained for the sample of which x = 0.03, representing an enhancement greater than 20% compared with a pristine AgSbTe 2 sample. This favorable thermoelectric performance originated from the optimal Sn 2+ substitution for Sb 3+ in AgSbTe 2 , which not only increased electrical conductivity but also led to a substantial reduction in thermal conductivity that was likely caused by an enhanced phonon-scattering mechanism through the combined effects of lattice defects and the presence of Ag 2 Te nanoprecipitates dispersed in the matrix.

Beschreibung: We present the growth and characterization of layered heterostructures comprised of LaTiO 3 and SrTiO 3 epitaxially grown on Si (001). Magnetotransport measurements show that the sheet carrier densities of the heterostructures scale with the number of LaTiO 3 /SrTiO 3 interfaces, consistent with the presence of an interfacial 2-dimensional electron gas (2DEG) at each interface. Sheet carrier densities of 8.9 × 10 14 cm −2 per interface are observed. Integration of such high density oxide 2DEGs on silicon provides a bridge between the exceptional properties and functionalities of oxide 2DEGs and microelectronic technologies.

Beschreibung: Nickelates are known for their metal to insulator transition (MIT) and an unusual magnetic ordering, occurring at T = T Néel . Here, we investigate thin films of SmNiO 3 subjected to different levels of epitaxial strain. We find that the original bulk behavior (T Néel 〈 T MI ) is strongly affected by applying compressive strain to the films. For small compressive strains, a regime where T Néel = T MI is achieved, the paramagnetic insulating phase characteristic of the bulk compound is suppressed and the MIT becomes 1st order. Further increasing the in-plane compression of the SmNiO 3 lattice leads to the stabilization of a single metallic paramagnetic phase.