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Superconducting niobium (Nb) thin films have recently attracted significant attention due to their utility for quantum information technologies. In the processing of Nb thin films, fluoride‐based chemical etchants are commonly used to remove surface oxides that are known to affect superconducting quantum devices adversely. However, these same etchants can also introduce hydrogen to form Nb hydrides, potentially negatively impacting microwave loss performance. Here, comprehensive materials characterization of Nb hydrides formed in Nb thin films as a function of fluoride chemical treatments is presented. In particular, secondary‐ion mass spectrometry, X‐ray scattering, and transmission electron microscopy reveal the spatial distribution and phase transformation of Nb hydrides. The rate of hydride formation is determined by the fluoride solution acidity and the etch rate of Nb2O5, which acts as a diffusion barrier for hydrogen into Nb. The resulting Nb hydrides are detrimental to Nb superconducting properties and lead to increased power‐independent microwave loss in coplanar waveguide resonators. However, Nb hydrides do not correlate with two‐level system loss or device aging mechanisms. Overall, this work provides insight into the formation of Nb hydrides and their role in microwave loss, thus guiding ongoing efforts to maximize coherence time in superconducting quantum devices. [ABSTRACT FROM AUTHOR]

The crystal structure and transport properties of GeBi2Te4 are investigated as a layered compound with potential applications as thermoelectric materials. A disordered arrangement of Ge and Bi atoms in a septuple‐layer structure is discovered through synchrotron radiation X‐ray diffraction and transmission electron microscopy. Neutron pair distribution function analysis revealed the presence of discordant Ge atoms with an off‐centering distance of 0.12 Å at 300 K. The thermal conductivity of GeBi2Te4 is very low due to the strong phonon scattering. This is a result of the three Einstein local oscillators coupled with the disordered arrangement of atoms. This study also explores further the structural characteristics of these materials and their associated phonon scattering processes. The effect of Sb substitution for Ge on the electrical transport properties of the sample is profound, resulting in a change from p‐type to n‐type conduction. An enhanced thermoelectric figure of merit (ZT) of 0.45 at 523 K in the in‐plane direction is obtained. This research provides valuable insights into the crystal structure and transport properties of GeBi2Te4, showcasing its promising role as a thermoelectric material with potential for near‐room‐temperature applications. [ABSTRACT FROM AUTHOR]

The severe capacity loss of spinel LiMn2O4 (LMO) limits the utility of this otherwise promising lithium ion battery cathode material. One of the strategies to mitigate capacity fade is applying a coating on LMO particle surfaces. While this approach yields promising results, there is limited understanding of mechanisms whereby coatings improve LMO capacity retention. Herein, the effects of a new protective coating material, La0.5Sr0.5CoO3 (LSCO), in a thin‐film battery geometry that is amenable to fundamental studies of electrode processes, are reported. RF sputtering deposition is used to produce high quality 25–100 nm LMO cathodes on Al2O3 substrates with an intervening Pt/Ti back‐side contact layer. Cycling of the un‐coated cathodes results in capacity loss of 18% over 300 cycles. Adding a 2 nm LSCO layer reduces the capacity loss to 3%. While this may be due in part to reduced Mn dissolution, scanning transmission electron microscopy results indicate that the coating helps to preserve crystallinity and reduce lattice structure distortion due to inhibited formation of defect tetragonal spinel. Three‐electrode electrochemical impedance spectroscopy results reveal that the LSCO coating increases charge transfer and ohmic resistances, but the increases are generally too small to significantly impact cell performance even at high C‐rates. [ABSTRACT FROM AUTHOR]

NO3− is a prominent waste byproduct in ammunition industries, and valorization of NO3− into NH3 is desired. NH3 synthesized from waste using renewable energy could be used as an energy storage medium. For such a process, higher selectivity, stability, and enhanced activity per unit mass of catalyst is required. This work reports CoO nanoclusters functionalized on graphene as an efficient catalyst for electrochemical NO3− reduction to NH3 with >98% NH3 Faradaic efficiency and an NH3 current density (geometric) of ≈400 mA cm−2. A highest NH3 yield of 25.63 mol g−1 h−1 is obtained. The developed catalyst prevents the NN coupling step which is required for promoting the selectivity of NH3 over N2. Density functional theory calculations reveal that CoO NC/graphene has similar selectivity to that of polycrystalline Co and that higher activity can be obtained with lower catalyst loading. [ABSTRACT FROM AUTHOR]

Low‐symmetry van der Waals materials are promising candidates for the next generation of polarization‐sensitive on‐chip photonics since they do not require lattice matching for growth and integration. Due to their low‐symmetry crystal behavior, such materials exhibit anisotropic and polarization‐dependent optical properties for a wide range of optical frequencies. Here, depolarization characteristics of orthorhombic α‐MoO3 is studied in the visible range. Using polarizers and analyzers, it is demonstrated that α‐MoO3 has negligible loss and that birefringence values as high as 0.15 and 0.12 at 532 nm and 633 nm, respectively, are achievable. With such a high birefringence, quarter‐ and half‐wave plate actions are demonstrated for a 1400 nm α‐MoO3 flake at green (532 nm) and red (633 nm) wavelengths, and polarizability as high as 90% is reported. Furthermore, a system of double α‐MoO3 heterostructure layer is investigated that provides the possibility of tuning polarization as a function of rotation angle between the α‐MoO3 layers. These findings pave the way to the promising future of on‐chip photonic heterostructures and twist‐optics that can dictate the polarization state of light. [ABSTRACT FROM AUTHOR]

This study investigates Ga‐doped n‐type PbTe thermoelectric materials and the dynamic phase conversion process of the second phases via Cu2Se alloying. Introducing Cu2Se enhances its electrical transport properties while reducing its lattice thermal conductivity (κlat) via weak electron–phonon coupling. Cu2Te and CuGa(Te/Se)2 (tetragonal phase) nanocrystals precipitate during the alloying process, resulting in Te vacancies and interstitial Cu in the PbTe matrix. At room temperature, Te vacancies and interstitial Cu atoms serve as n‐type dopants, increasing the carrier concentration and electrical conductivity from ≈1.18 × 1019 cm−3 and ≈1870 S cm−1 to ≈2.26 × 1019 cm−3 and ≈3029 S cm−1, respectively. With increasing temperature, the sample exhibits a dynamic change in Cu2Te content and the generation of a new phase of CuGa(Te/Se)2 (cubic phase), strengthening the phonon scattering and obtaining an ultralow κlat. Pb0.975Ga0.025Te‐3%CuSe exhibits a maximum figure of merit of ≈1.63 at 823 K, making it promising for intermediate‐temperature device applications. [ABSTRACT FROM AUTHOR]

Corrosion is a significant problem for the stability of structural metals and potentially for functional nanomaterials in operating environments. When two metals with different electrochemical potentials form a junction, galvanic corrosion occurs, resulting in the sacrificial dissolution of the metal with a higher oxidation potential (lower electrode potential). Here, it is shown that bimetallic hetero‐nanostructures composed of phase‐segregated metals undergo galvanic corrosion in aqueous environments. Such selective etching of the sacrificial metal in heterojunction particles leads to the formation of unusual and kinetically stabilized half‐spheroid particles. By using a fluid cell and in situ scanning transmission electron microscopy, a two‐stage corrosion process can be observed where the Cu experiences a fractal breakdown before the Ag corrodes due to the lack of a protective oxide layer. However, when treated with a mild Ar plasma, the stability of these structures against corrosion is enhanced due to the conversion of the amorphous native oxide to a denser, thin layer of CuO on the Cu surface. Taken together, this work highlights the importance of considering the effects of galvanic corrosion on the stability of multicomponent nanoparticles, and it shows how mass transport in a nanoscale system is influenced by redox processes. [ABSTRACT FROM AUTHOR]

The octahedral structure of 2D molybdenum disulfide (1T‐MoS2) has attracted attention as a high‐efficiency and low‐cost electrocatalyst for hydrogen production. However, the large‐scale synthesis of 1T‐MoS2 films has not been realized because of higher formation energy compared to that of the trigonal prismatic phase (2H)‐MoS2. In this study, a uniform wafer‐scale synthesis of the metastable 1T‐MoS2 film is performed by sulfidation of the Mo metal layer using a plasma‐enhanced chemical vapor deposition (PE‐CVD) system. Thus, plasma‐containing highly reactive ions and radicals of the sulfurization precursor enable the synthesis of 1T‐MoS2 at 150 °C. Electrochemical analysis of 1T‐MoS2 shows enhanced catalytic activity for the hydrogen evolution reaction (HER) compared to that of previously reported MoS2 electrocatalysts 1T‐MoS2 does not transform into stable 2H‐MoS2 even after 1000 cycles of HER. The proposed low‐temperature synthesis approach may offer a promising solution for the facile production of various metastable‐phase 2D materials. [ABSTRACT FROM AUTHOR]

High‐temperature pyrolysis of nitrogen (N)‐rich, crystalline porous organic architectures in the presence of a metal precursor is an important chemical process in heterogeneous catalysis for the fabrication of highly porous N‐carbon‐supported metal catalysts. Herein, covalent triazine framework (CTF) and CTF‐I (that is, CTF after charge modulation with iodomethane) are presented as sacrificial templates, for the synthesis of carbon‐supported Ru catalysts—Ru‐CTF‐900 and Ru‐CTF‐I‐900 respectively, following high‐temperature pyrolysis at 900 °C under N2 atmosphere. Predictably, the dispersed Ru on pristine CTF carrier suffered severe sintering of the Ru nanoparticles (NPs) during heat treatment at 900 °C. However, the Ru‐CTF‐I‐900 catalyst is composed of ultra‐small Ru NPs and abundant Ru single atoms which may have resulted from much stronger RuN interactions. Through modification of the micro‐environment within the CTF architecture, Ru precursor interacted on charged‐modulated CTF framework shows electrostatic repulsion and steric hindrance, thus contributing toward the high density of single Ru atoms and even smaller Ru NPs after pyrolysis. A RuRu coordination number of only 1.3 is observed in the novel Ru‐CTF‐I‐900 catalyst, which exhibits significantly higher catalytic activity than Ru‐CTF‐900 for transfer hydrogenation of acetophenone. [ABSTRACT FROM AUTHOR]

This paper describes a new, high‐performance, Pb‐based nanocomposite anode material for lithium‐ion batteries. A unique nanocomposite structure of Pb@PbO core‐shell nanoparticles in a carbon matrix is obtained by using a simple high‐energy ball milling method using the low‐cost starting materials PbO and carbon black. Electrochemical performance tests show its excellent reversible capacity (≈600 mAh g−1) and cycle stability (92% retention at 100th cycle), which are one of the best values reported for Pb‐based anodes in the literature. Synchrotron X‐ray diffraction and absorption techniques revealed the detailed lithium storage mechanism that can be highlighted with the unexpectedly wide reversible Pb redox range (between Pb2+ and Pb4−) and the evolution of Zintl‐type LiyPb structures during the electrochemical lithium reaction. The results provide new insights into the lithium storage mechanism of these Pb‐based materials and their potential as low‐cost, high‐performance anodes. [ABSTRACT FROM AUTHOR]

We present an effective approach to favorably modify the electronic structure of PbSe using Ag doping coupled with SrSe or BaSe alloying. The Ag 4d states make a contribution to in the top of the heavy hole valence band and raise its energy. The Sr and Ba atoms diminish the contribution of Pb 6s2 states and decrease the energy of the light hole valence band. This electronic structure modification increases the density‐of‐states effective mass, and strongly enhances the thermoelectric performance. Moreover, the Ag‐rich nanoscale precipitates, discordant Ag atoms, and Pb/Sr, Pb/Ba point defects in the PbSe matrix work together to reduce the lattice thermal conductivity, resulting a record high average ZTavg of around 0.86 over 400–923 K. [ABSTRACT FROM AUTHOR]

Here, a new approach to the layer‐by‐layer solution‐processed fabrication of organic/inorganic hybrid self‐assembled nanodielectrics (SANDs) is reported and it is demonstrated that these ultrathin gate dielectric films can be printed. The organic SAND component, named P‐PAE, consists of polarizable π‐electron phosphonic acid‐based units bound to a polymeric backbone. Thus, the new polymeric SAND (PSAND) can be fabricated either by spin‐coating or blade‐coating in air, by alternating P‐PAE, a capping reagent layer, and an ultrathin ZrOx layer. The new PSANDs thickness vary from 6 to 15 nm depending on the number of organic‐ZrOx bilayers, exhibit tunable film thickness, well‐defined nanostructures, large electrical capacitance (up to 558 nF cm−2), and good insulating properties (leakage current densities as low as 10−6 A cm−2). Organic thin‐film transistors that are fabricated with representative p‐/n‐type organic molecular/polymeric semiconducting materials, function well at low voltages (<3.0 V). Furthermore, flexible TFTs fabricated with PSAND exhibit excellent mechanical flexibility and good stress stability, offering a promising route to low operating voltage flexible electronics. Finally, printable PSANDs are also demonstrated and afford TFTs with electrical properties comparable to those achieved with the spin‐coated PSAND‐based devices. [ABSTRACT FROM AUTHOR]

The development of materials capable of varying macroscale ligand distributions can emulate an extracellular matrix (ECM) remodeling and regulate the adhesion and polarization of macrophages. In this report, negatively charged slidable nano‐ligands are assembled and then conjugated to a positively charged substrate via electrostatic interaction. The negatively charged slidable nano‐ligands are prepared by coating magnetic nanoparticles with a polymer linker and negatively charged RGD ligand. The nano‐ligand sliding is characterized under an external magnetic field, which spatiotemporally alters macroscale ligand density. To the best of knowledge, this is the first demonstration that magnetic maipulation of the macroscale ligand density inhibits inflammatory M1 phenotype but stimulates the adhesion and regenerative M2 phenotype of host macrophages. Furthermore, it is elucidated that the magnetic attraction of the slidable nano‐ligand facilitates the assembly of adhesion structures in macrophages, thereby stimulating their regenerative M2 phenotype. The design of ECM‐emulating materials that allow remote, spatiotemporal, and reversible controllability of macroscale ligand density provides an appealing strategy in the spatiotemporal regulation of immunomodulatory tissue‐regenerative responses to implants in vivo. [ABSTRACT FROM AUTHOR]

Magnetic nanostructures (MNS) in their superparamagnetic form are promising materials systems for contrast enhancement in magnetic resonance imaging (MRI) and thermal‐activation therapeutics via RF heating. These biomedical applications and associated properties are very much dependent on the structure, composition and size/shape of MNS. Although there are many speculations on the effect of various parameters on MNS, the size dependent properties are not well understood, largely due to challenges in size‐selective large‐scale synthesis for precise measurements and interference from typical large surface coating. Herein we report the size effect of iron oxide MNS on hydrodynamic radius, zeta potential, magnetic property and relaxivity. For this study, we have synthesized a wide range of monodispersed iron oxide MNS, from 7 nm to 20 nm nominal size and phase transferred to aqueous media with very thin layer of silica coating using Polyhedral Oligomeric Selesquioxanes (POSS). The dynamic light scattering (DLS) study and zeta potential measurement were carried out to determine the hydrodynamic radius and surface charges. The hydrodynamic radius follow the linear correlation but the zeta potential does not maintain it due to nonlinear mass/charge ratio relations with varying size. We have also conducted correlative studies of magnetic saturation (Ms) and T2 relaxivities. This work will highlight the size dependent correlation and tailoring of MNS properties for desired biomedical applications. [ABSTRACT FROM AUTHOR]

2D van der Waals materials have attracted increasing attention in recent years due to their exciting physical properties and offer new opportunities for creating devices with enhanced or novel functionalities. In particular, α‐MoO3 is an emerging member of the fast‐growing 2D family with strong natural anisotropic optical properties. However, anisotropic optical properties of ‐MoO3 in the visible frequency range remain elusive. Here, α‐MoO3 is investigated as an optical material at the visible frequency (450–750 nm), which exhibits a polarization‐dependent complex refractive index due to the anisotropic crystal structure. As a proof of concept, polarization‐sensitive photonic devices including polarization reflectors and polarization color filters are designed and realized by constructing metal–insulator–metal Fabry–Perot cavities. It is observed that resonance frequencies for designed transmission and reflection filters change up to 25 nm with incident polarization which stems from the polarization‐dependent complex refractive indices of α‐MoO3. The largest contrasts are observed for two orthogonal polarization states parallel to the two orthogonal in‐plane crystal directions. The approach in this study offers new directions for potential applications in the development of polarization‐dependent devices based on 2D van der Waals materials for visible frequencies. [ABSTRACT FROM AUTHOR]

Abstract: Sb‐doped and GeTe‐alloyed n‐type thermoelectric materials that show an excellent figure of merit ZT in the intermediate temperature range (400–800 K) are reported. The synergistic effect of favorable changes to the band structure resulting in high Seebeck coefficient and enhanced phonon scattering by point defects and nanoscale precipitates resulting in reduction of thermal conductivity are demonstrated. The samples can be tuned as single‐phase solid solution (SS) or two‐phase system with nanoscale precipitates (Nano) based on the annealing processes. The GeTe alloying results in band structure modification by widening the bandgap and increasing the density‐of‐states effective mass of PbTe, resulting in significantly enhanced Seebeck coefficients. The nanoscale precipitates can improve the power factor in the low temperature range and further reduce the lattice thermal conductivity (κlat). Specifically, the Seebeck coefficient of Pb0.988Sb0.012Te–13%GeTe–Nano approaches −280 µV K−1 at 673 K with a low κlat of 0.56 W m−1 K−1 at 573 K. Consequently, a peak ZT value of 1.38 is achieved at 623 K. Moreover, a high average ZTavg value of ≈1.04 is obtained in the temperature range from 300 to 773 K for n‐type Pb0.988Sb0.012Te–13%GeTe–Nano. [ABSTRACT FROM AUTHOR]

Abstract: Controlled design and patterning of layered transition metal dichalcogenides (TMDs) into specific dimensions and geometries hold great potential for next‐generation micro/nanoscale electronic applications. Herein, the large‐scale fabrication of MoS2 ribbons with widths ranging from micro‐ to nanoscale is reported. Their unique electric and thermal properties introduced by the shape change and defect creation are also demonstrated, with particular focus on the performance associated with light–matter interactions. The theoretical calculation indicates significantly increased absorption and scattering efficiency of the MoS2 ribbons with decreasing width. As a result, enhanced photocarrier generation ability is detected on their phototransistors with defect‐modulated light‐response behavior. The light‐induced thermal transport properties of the MoS2 ribbons are further studied. A decreased thermal conductivity is observed on narrower ribbons, attributed to the defects created during fabrication. It is also found that the effect of phonon scattering at ribbon edges on their thermal conductivity is insignificant, and the thermal transport has no obvious dependence on the ribbon direction at such width scale. This study evaluates the prospects for designing and fabricating TMD semiconductors with specific geometries for future optoelectronic applications. [ABSTRACT FROM AUTHOR]

Multicomponent nanoparticles can be synthesized with either homogeneous or phase-segregated architectures depending on the synthesis conditions and elements incorporated. To understand the parameters that determine their structural fate, multicomponent metal-oxide nanoparticles consisting of combinations of Co, Ni, and Cu were synthesized by using scanning probe block copolymer lithography and characterized using correlated electron microscopy. These studies revealed that the miscibility, ratio of the metallic components, and the synthesis temperature determine the crystal structure and architecture of the nanoparticles. A Co-Ni-O system forms a rock salt structure largely owing to the miscibility of CoO and NiO, while Cu-Ni-O, which has large miscibility gaps, forms either homogeneous oxides, heterojunctions, or alloys depending on the annealing temperature and composition. Moreover, a higher-ordered structure, Co-Ni-Cu-O, was found to follow the behavior of lower ordered systems. [ABSTRACT FROM AUTHOR]

Bulk and nanoscale molybdenum trioxide (MoO3) has shown impressive technologically relevant properties, but deeper investigation into 2D MoO3 has been prevented by the lack of reliable vapor-based synthesis and doping techniques. Herein, the successful synthesis of high-quality, few-layer MoO3 down to bilayer thickness via physical vapor deposition is reported. The electronic structure of MoO3 can be strongly modified by introducing oxygen substoichiometry (MoO3− x), which introduces gap states and increases conductivity. A dose-controlled electron irradiation technique to introduce oxygen vacancies into the few-layer MoO3 structure is presented, thereby adding n-type doping. By combining in situ transport with core-loss and monochromated low-loss scanning transmission electron microscopy-electron energy-loss spectroscopy studies, a detailed structure-property relationship is developed between Mo-oxidation state and resistance. Transport properties are reported for MoO3− x down to three layers thick, the most 2D-like MoO3− x transport hitherto reported. Combining these results with density functional theory calculations, a radiolysis-based mechanism for the irradiation-induced oxygen vacancy introduction is developed, including insights into favorable configurations of oxygen defects. These systematic studies represent an important step forward in bringing few-layer MoO3 and MoO3− x into the 2D family, as well as highlight the promise of MoO3− x as a functional, tunable electronic material. [ABSTRACT FROM AUTHOR]

Development of low-cost, high-performance, and bifunctional electrocatalysts for water splitting is essential for renewable and clean energy technologies. Although binary phosphides are inexpensive, their performance is not as good as noble metals. Adding a third metal element to binary phosphides (Ni-P, Co-P) provides the opportunity to tune their crystalline and electronic structures and thus their electrocatalytic properties. Here, ternary phosphide (NiCoP) films with different nickel to cobalt ratios via an electrodeposition technique are synthesized. The films have a triple-layered and hierarchical morphology, consisting of nanosheets in the bottom layer, ≈90-120 nm nanospheres in the middle layer, and larger spherical particles on the top layer. The ternary phosphides exhibit versatile activities that are strongly dependent on the Ni/Co ratios and Ni0.51Co0.49P film is found to have the best electrocatalytic activities for both hydrogen evolution reactions and oxygen evolution reactions. The high performance of the ternary phosphide film is attributed to enhanced electric conductivity so that reaction kinetics is accelerated, enlarged surface area due to the hierarchical and three-layered morphology, and increased local electric dipole so that the energy barrier for the water splitting reaction is lowered. [ABSTRACT FROM AUTHOR]

Spinel-structured LiMn2O4 (LMO) is a desirable cathode material for Li-ion batteries due to its low cost, abundance, and high power capability. However, LMO suffers from limited cycle life that is triggered by manganese dissolution into the electrolyte during electrochemical cycling. Here, it is shown that single-layer graphene coatings suppress manganese dissolution, thus enhancing the performance and lifetime of LMO cathodes. Relative to lithium cells with uncoated LMO cathodes, cells with graphene-coated LMO cathodes provide improved capacity retention with enhanced cycling stability. X-ray photoelectron spectroscopy reveals that graphene coatings inhibit manganese depletion from the LMO surface. Additionally, transmission electron microscopy demonstrates that a stable solid electrolyte interphase is formed on graphene, which screens the LMO from direct contact with the electrolyte. Density functional theory calculations provide two mechanisms for the role of graphene in the suppression of manganese dissolution. First, common defects in single-layer graphene are found to allow the transport of lithium while concurrently acting as barriers for manganese diffusion. Second, graphene can chemically interact with Mn3+ at the LMO electrode surface, promoting an oxidation state change to Mn4+, which suppresses dissolution. [ABSTRACT FROM AUTHOR]

The thermoelectric properties of crystalline melt-grown ingots of p-type PbTe- xMgTe ( x = 1-3 mol%) doped with Na2Te (1-2 mol%) were investigated over the temperature range of 300 K to 810 K. While the powder X-ray diffraction patterns show that all samples crystallize in the NaCl-type structure with no MgTe or other phases present, transmission electron microscopy reveals ubiquitous MgTe nanoprecipitates in the PbTe. The very small amounts of MgTe in PbTe have only a small effect on the electrical transport properties of the system, while they have a large effect on thermal transport significantly reducing the lattice thermal conductivity. A ZT of 1.6 at 780 K is achieved for the PbTe containing 2% MgTe doped with 2% Na2Te. [ABSTRACT FROM AUTHOR]

Interphase interfaces in Ni xCo1− xO/ZrO2(CaO) directionally solidified eutectics (DSEs) are modified by selective chemical reduction of the Ni xCo1− xO oxide phase. Scanning electron microscopy studies of such Ni xCo1− xO/ZrO2(CaO) DSEs show formation of a thin layer of metallic Ni(Co) interphase (∼100 nm) and interfacial porosity upon reduction at high temperatures. A significant change is observed in the mechanical behavior of the reduced Ni xCo1− xO/ZrO2(CaO) DSEs compared with its pristine counterpart, which is largely attributed to the formation of metallic Ni(Co) interphases. Indentation fracture studies indicate that the presence of metallic interphases in the DSEs enhance the stress energy release mechanism through plastic deformation, interfacial delamination, crack arrest, and crack bridging across the metallic interphase after reduction. [ABSTRACT FROM AUTHOR]