Julien P.A. Makongo

Microstructural and thermal investigations of HfO2 nanoparticles

Monodispersed HfO2 nanoparticles can be readily prepared at room temperature by the ammonia catalyzed hydrolysis and condensation of hafnium(IV) tert-butoxide in the presence of a surfactant. The nanoparticles are faceted with an average diameter of about 4 nm. The as-synthesized amorphous nanoparticles crystallize upon post-synthesis heat treatment. The crystallization temperature of the nanoparticles can be controlled by adjusting the annealing atmosphere. The HfO2 nanoparticles have a narrow size distribution, large specific surface area and the thermal conductivity of pressed pellets is drastically reduced compared to the bulk counterpart. The specific surface area was about 239 m2 g−1 on as-prepared samples while those annealed at 500 °C have a surface area of 221 m2 g−1 showing that the heat treatment produced no significant increase in particle size. Transmission electron microscopy (TEM) further confirmed that the nanoparticles annealed at different temperatures while X-ray diffraction studies of the crystallized nanoparticles revealed that HfO2 nanoparticles were monoclinic in structure. High density pellets of the as-synthesized HfO2 nanoparticles were obtained, using both spark plasma sintering and uniaxial hot pressing, and their thermal conductivity was measured in the temperature range from 300 to 775 K. A large reduction of the thermal conductivity was observed for HfO2 nanoparticles as compared to that of bulk HfO2. The decrease in thermal conductivity is discussed in terms of the microstructure of the compacted samples. The synthetic procedure used in this work can be readily modified for large scale production of monodispersed HfO2 nanoparticles.

Geometrical spin frustration and ferromagnetic ordering in (MnxPb2-x)Pb2Sb4Se10.

Engineering the atomic structure of an inorganic semiconductor to create isolated one-dimensional (1D) magnetic subunits that are embedded within the semiconducting crystal lattice can enable chemical and electronic manipulation of magnetic ordering within the magnetic domains, paving the way for (1) the investigation of new physical phenomena such as the interactions between electron transport and localized magnetic moments at the atomic scale and (2) the design and fabrication of geometrically frustrated magnetic materials featuring cooperative long-range ordering with large magnetic moments. We report the design, synthesis, crystal structure and magnetic behavior of (MnxPb2-x)Pb2Sb4Se10, a family of three-dimensional manganese-bearing main-group metal selenides featuring quasi-isolated [(MnxPb2-x)3Se30]∞ hexanuclear magnetic ladders coherently embedded and uniformly distributed within a purely inorganic semiconducting framework, [Pb2Sb4Se10]. Careful structural analysis of the magnetic subunit, [(MnxPb2-x)3Se30]∞ and the temperature dependent magnetic susceptibility of (MnxPb2-x)Pb2Sb4Se10, indicate that the compounds are geometrically frustrated 1D ferromagnets. Interestingly, the degree of geometrical spin frustration (f) within the magnetic ladders and the strength of the intrachain antiferromagnetic (AFM) interactions strongly depend on the concentration (x value) and the distribution of the Mn atom within the magnetic substructure. The combination of strong intrachain AFM interactions and geometrical spin frustration in the [(MnxPb2-x)3Se30]∞ ladders results in a cooperative ferromagnetic order with exceptionally high magnetic moment at around 125 K. Magnetotransport study of the Mn2Pb2Sb4Se10 composition over the temperature range from 100 to 200 K revealed negative magnetoresistance (NMR) values and also suggested a strong contribution of magnetic polarons to the observed large effective magnetic moments.

Synthesis and thermal stability of HfO2 nanoparticles

A simple method is reported for the synthesis of monodispersed HfO 2 nanoparticles by the ammonia catalyzed hydrolysis and condensation of hafnium (IV) tert-butoxide in the presence of surfactants at room temperature. Transmission electron microscopy shows faceted nanoparticles with an average diameter of 3-4 nm. As-synthesized nanoparticles are amorphous in nature and crystallize upon moderate heat treatment. The HfO 2 nanoparticles have a narrow size distribution, large specific surface area and good thermal stability. Specific surface area was about 239 m 2 /g on as-prepared nanoparticle samples while those annealed at 500 °C have specific surface area of 221 m 2 /g indicating that there was no significant increase in particle size. This result was further confirmed by TEM images of nanoparticles annealed at 300 °C and 500 °C. X-ray diffraction studies of the crystallized nanoparticles revealed that HfO 2 nanoparticles were monoclinic in structure. The synthetic procedure used in this work can be readily modified for large scale production of monodispersed HfO 2 nanoparticles.

Distribution of impurity states and charge transport in Zr{sub 0.25}Hf{sub 0.75}Ni{sub 1+x}Sn{sub 1−y}Sb{sub y} nanocomposites

Abstract Energy filtering of charge carriers in a semiconducting matrix using atomically coherent nanostructures can lead to a significant improvement of the thermoelectric figure of merit of the resulting composite. In this work, several half-Heusler/full-Heusler (HH/FH) nanocomposites with general compositions Zr 0.25 Hf 0.75 Ni 1+ x Sn 1− y Sb y (0≤ x ≤0.15 and y =0.005, 0.01 and 0.025) were synthesized in order to investigate the behavior of extrinsic carriers at the HH/FH interfaces. Electronic transport data showed that energy filtering of carriers at the HH/FH interfaces in Zr 0.25 Hf 0.75 Ni 1+ x Sn 1− y Sb y samples strongly depends on the doping level ( y value) as well as the energy levels occupied by impurity states in the samples. For example, it was found that carrier filtering at HH/FH interfaces is negligible in Zr 0.25 Hf 0.75 Ni 1+ x Sn 1− y Sb y ( y =0.01 and 0.025) composites where donor states originating from Sb dopant dominate electronic conduction. However, we observed a drastic decrease in the effective carrier density upon introduction of HH/FH interfaces for the mechanically alloyed Zr 0.25 Hf 0.75 Ni 1+ x Sn 0.995 Sb 0.005 samples where donor states from unintentional Fe impurities contribute the largest fraction of conduction electrons. This work demonstrates the ability to synergistically integrate the concepts of doping and energy filtering through nanostructuring for the optimization of electronic transport in semiconductors.

Lithium‐Containing Pnictides with Supertetrahedral Cluster Chains

Invited for the cover of this issue is the group of Svilen Bobev at the University of Delaware, USA. The cover image shows the crystal structure of Ba4Li2Cd3Pn6 (Pn = P, As, Sb), which is based on infinite chains of supertetrahedral T2 clusters.