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- ItemSingle Molecule Magnetism with Strong Magnetic Anisotropy and Enhanced Dy∙∙∙Dy Coupling in Three Isomers of Dy-Oxide Clusterfullerene Dy2O@C82(Chichester : John Wiley and Sons Ltd, 2019) Yang, W.; Velkos, G.; Liu, F.; Sudarkova, S.M.; Wang, Y.; Zhuang, J.; Zhang, H.; Li, X.; Zhang, X.; Büchner, B.; Avdoshenko, S.M.; Popov, A.A.; Chen, N.A new class of single-molecule magnets (SMMs) based on Dy-oxide clusterfullerenes is synthesized. Three isomers of Dy2O@C82 with Cs(6), C3v(8), and C2v(9) cage symmetries are characterized by single-crystal X-ray diffraction, which shows that the endohedral Dy−(µ2-O)−Dy cluster has bent shape with very short Dy−O bonds. Dy2O@C82 isomers show SMM behavior with broad magnetic hysteresis, but the temperature and magnetization relaxation depend strongly on the fullerene cage. The short Dy−O distances and the large negative charge of the oxide ion in Dy2O@C82 result in the very strong magnetic anisotropy of Dy ions. Their magnetic moments are aligned along the Dy−O bonds and are antiferromagnetically (AFM) coupled. At low temperatures, relaxation of magnetization in Dy2O@C82 proceeds via the ferromagnetically (FM)-coupled excited state, giving Arrhenius behavior with the effective barriers equal to the AFM-FM energy difference. The AFM-FM energy differences of 5.4–12.9 cm−1 in Dy2O@C82 are considerably larger than in SMMs with {Dy2O2} bridges, and the Dy∙∙∙Dy exchange coupling in Dy2O@C82 is the strongest among all dinuclear Dy SMMs with diamagnetic bridges. Dy-oxide clusterfullerenes provide a playground for the further tuning of molecular magnetism via variation of the size and shape of the fullerene cage.
- ItemApplication of Artificial Neural Networks in Crystal Growth of Electronic and Opto-Electronic Materials(Basel : MDPI, 2020) Dropka, Natasha; Holena, MartinIn this review, we summarize the results concerning the application of artificial neural networks (ANNs) in the crystal growth of electronic and opto-electronic materials. The main reason for using ANNs is to detect the patterns and relationships in non-linear static and dynamic data sets which are common in crystal growth processes, all in a real time. The fast forecasting is particularly important for the process control, since common numerical simulations are slow and in situ measurements of key process parameters are not feasible. This important machine learning approach thus makes it possible to determine optimized parameters for high-quality up-scaled crystals in real time. © 2020 by the authors. Licensee MDPI, Basel, Switzerland.
- ItemPolyoxometalates as components of supramolecular assemblies(Cambridge : RSC, 2019) Stuckart, Maria; Monakhov, Kirill Yu.The non-covalent interaction of polyoxometalates (POMs) with inorganic- or organic-based moieties affords hybrid assemblies with specific physicochemical properties that are of high interest for both fundamental and applied studies, including the discovery of conceptually new compounds and unveiling the impact of their intra-supramolecular relationships on the fields of catalysis, molecular electronics, energy storage and medicine. This minireview summarises the recent advances in the synthetic strategies towards the formation of such non-covalent POM-loaded assemblies, shedding light on their key properties and the currently investigated applications. Four main emerging categories according to the nature of the conjugate are described: (i) POMs in metal-organic frameworks, (ii) POMs merged with cationic metal complexes, (iii) architectures generated with solely POM units and (iv) POMs assembled with organic molecular networks. © 2019 The Royal Society of Chemistry.
- ItemDesign of a core-shell catalyst : an effective strategy for suppressing side reactions in syngas for direct selective conversion to light olefins(Cambridge : RSC, 2020) Tan, Li; Wang, Fan; Zhang, Peipe; Suzuki, Yuichi; Wu, Yingquan; Chen, Jiangang; Yang, Guohui; Tsubaki, NoritatsuAn elegant catalyst is designedviathe encapsulation of metallic oxide Zn-Cr inside of zeolite SAPO34 as a core-shell structure (Zn-Cr@SAPO) to realize the coupling of methanol-synthesis and methanol-to-olefin reactions. It can not only break through the limitation of the Anderson-Schulz-Flory distribution but can also overcome the disadvantages of physical mixture catalysts, such as excessive CO2formation. The confinement effect, hierarchical structure and extremely short distance between the two active components result in the Zn-Cr@SAPO capsule catalyst having better mass transfer and diffusion with a boosted synergistic effect. Due to the difference between the adsorption energies of the Zn-Cr metallic oxide/SAPO zeolite physical mixture and capsule catalysts, the produced water and light olefins are easily removed from the Zn-Cr@SAPO capsule catalyst after formation, suppressing the side reactions. The light olefin space time yield (STY) of the capsule catalyst is more than twice that of the typical physical mixture catalyst. The designed capsule catalyst has superior potential for scale-up in industrial applications while simultaneously extending the capabilities of hybrid catalysts for other tandem catalysis reactions through this strategy. © The Royal Society of Chemistry 2020.
- ItemWhen Density Functional Approximations Meet Iron Oxides(Washington, DC : Soc., 2016) Meng, Yu; Liu, Xing-Wu; Huo, Chun-Fang; Guo, Wen-Ping; Cao, Dong-Bo; Peng, Qing; Dearden, Albert; Gonze, Xavier; Yang, Yong; Wang, Jianguo; Jiao, Haijun; Li, Yongwang; Wen, Xiao-DongThree density functional approximations (DFAs), PBE, PBE+U, and Heyd-Scuseria-Ernzerhof screened hybrid functional (HSE), were employed to investigate the geometric, electronic, magnetic, and thermodynamic properties of four iron oxides, namely, α-FeOOH, α-Fe2O3, Fe3O4, and FeO. Comparing our calculated results with available experimental data, we found that HSE (a = 0.15) (containing 15% "screened" Hartree-Fock exchange) can provide reliable values of lattice constants, Fe magnetic moments, band gaps, and formation energies of all four iron oxides, while standard HSE (a = 0.25) seriously overestimates the band gaps and formation energies. For PBE+U, a suitable U value can give quite good results for the electronic properties of each iron oxide, but it is challenging to accurately get other properties of the four iron oxides using the same U value. Subsequently, we calculated the Gibbs free energies of transformation reactions among iron oxides using the HSE (a = 0.15) functional and plotted the equilibrium phase diagrams of the iron oxide system under various conditions, which provide reliable theoretical insight into the phase transformations of iron oxides.
- ItemFaceting and metal-exchange catalysis in (010) β-Ga2O3 thin films homoepitaxially grown by plasma-assisted molecular beam epitaxy(New York : American Institute of Physics, 2018) Mazzolini, P.; Vogt, P.; Schewski, R.; Wouters, C.; Albrecht, M.; Bierwagen, OliverWe here present an experimental study on (010)-oriented -Ga2O3 thin films homoepitaxially grown by plasma assisted molecular beam epitaxy. We study the effect of substrate treatments (i.e., O-plasma and Ga-etching) and several deposition parameters (i.e., growth temperature and metal-to-oxygen flux ratio) on the resulting Ga2O3 surface morphology and growth rate. In situ and ex-situ characterizations identified the formation of (110) and (¯110)-facets on the nominally oriented (010) surface induced by the Ga-etching of the substrate and by several growth conditions, suggesting (110) to be a stable (yet unexplored) substrate orientation. Moreover, we demonstrate how metal-exchange catalysis enabled by an additional In-flux significantly increases the growth rate (>threefold increment) of monoclinic Ga2O3 at high growth temperatures, while maintaining a low surface roughness (rms < 0.5 nm) and preventing the incorporation of In into the deposited layer. This study gives important indications for obtaining device-quality thin films and opens up the possibility to enhance the growth rate in -Ga2O3 homoepitaxy on different surfaces [e.g., (100) and (001)] via molecular beam epitaxy.
- ItemOptical study of orbital excitations in transition-metal oxides(Milton Park : Taylor & Francis, 2005) Rückamp, R.; Benckiser, E.; Haverkort, M.W.; Roth, H.; Lorenz, T.; Freimuth, A.; Jongen, L.; Möller, A.; Meyer, G.; Reutler, P.; Büchner, B.; Revcolevschi, A.; Cheong, S.-W.; Sekar, C.; Krabbes, G.; Grüninger, M.The orbital excitations of a series of transition-metal compounds are studied by means of optical spectroscopy. Our aim was to identify signatures of collective orbital excitations by comparison with experimental and theoretical results for predominantly local crystal-field excitations. To this end, we have studied TiOCl, RTiO3 (R = La, Sm and Y), LaMnO3, Y2BaNiO5, CaCu2O3 and K4Cu4OCl10, ranging from early to late transition-metal ions, from t2g to eg systems, and including systems in which the exchange coupling is predominantly three-dimensional, one-dimensional or zero-dimensional. With the exception of LaMnO3, we find orbital excitations in all compounds. We discuss the competition between orbital fluctuations (for dominant exchange coupling) and crystal-field splitting (for dominant coupling to the lattice). Comparison of our experimental results with configuration-interaction cluster calculations in general yields good agreement, demonstrating that the coupling to the lattice is important for a quantitative description of the orbital excitations in these compounds. However, detailed theoretical predictions for the contribution of collective orbital modes to the optical conductivity (e.g. the line shape or the polarization dependence) are required to decide on a possible contribution of orbital fluctuations at low energies, in particular, in case of the orbital excitations at ≈0.25 eV in RTiO3. Further calculations are called for which take into account the exchange interactions between the orbitals and the coupling to the lattice on an equal footing.
- ItemHidden Charge Order in an Iron Oxide Square-Lattice Compound(College Park, Md. : APS, 2021) Kim, Jung-Hwa; Peets, Darren C.; Reehuis, Manfred; Adler, Peter; Maljuk, Andrey; Ritschel, Tobias; Allison, Morgan C.; Geck, Jochen; Mardegan, Jose R. L.; Bereciartua Perez, Pablo J.; Francoual, Sonia; Walters, Andrew C.; Keller, Thomas; Abdala, Paula M.; Pattison, Philip; Dosanjh, Pinder; Keimer, BernhardSince the discovery of charge disproportionation in the FeO2 square-lattice compound Sr3Fe2O7 by Mössbauer spectroscopy more than fifty years ago, the spatial ordering pattern of the disproportionated charges has remained “hidden” to conventional diffraction probes, despite numerous x-ray and neutron scattering studies. We have used neutron Larmor diffraction and Fe K-edge resonant x-ray scattering to demonstrate checkerboard charge order in the FeO2 planes that vanishes at a sharp second-order phase transition upon heating above 332 K. Stacking disorder of the checkerboard pattern due to frustrated interlayer interactions broadens the corresponding superstructure reflections and greatly reduces their amplitude, thus explaining the difficulty of detecting them by conventional probes. We discuss the implications of these findings for research on “hidden order” in other materials.
- ItemImpact of the precursor chemistry and process conditions on the cell-to-cell variability in 1T-1R based HfO2 RRAM devices(London : Nature Publishing Group, 2018) Grossi, A.; Perez, E.; Zambelli, C.; Olivo, P.; Miranda, E.; Roelofs, R.; Woodruff, J.; Raisanen, P.; Li, W.; Givens, M.; Costina, I.; Schubert, M.A.; Wenger, C.The Resistive RAM (RRAM) technology is currently in a level of maturity that calls for its integration into CMOS compatible memory arrays. This CMOS integration requires a perfect understanding of the cells performance and reliability in relation to the deposition processes used for their manufacturing. In this paper, the impact of the precursor chemistries and process conditions on the performance of HfO2 based memristive cells is studied. An extensive characterization of HfO2 based 1T1R cells, a comparison of the cell-to-cell variability, and reliability study is performed. The cells’ behaviors during forming, set, and reset operations are monitored in order to relate their features to conductive filament properties and process-induced variability of the switching parameters. The modeling of the high resistance state (HRS) is performed by applying the Quantum-Point Contact model to assess the link between the deposition condition and the precursor chemistry with the resulting physical cells characteristics.