STEM in situ thermal wave observations for investigating thermal diffusivity in nanoscale materials and devices.

Practical techniques to identify heat routes at the nanoscale are required for the thermal control of microelectronic, thermoelectric, and photonic devices. Nanoscale thermometry using various approaches has been extensively investigated, yet a reliable method has not been finalized. We developed an original technique using thermal waves induced by a pulsed convergent electron beam in a scanning transmission electron microscopy (STEM) mode at room temperature. By quantifying the relative phase delay at each irradiated position, we demonstrate the heat transport within various samples with a spatial resolution of ~10 nm and a temperature resolution of 0.01 K. Phonon-surface scatterings were quantitatively confirmed due to the suppression of thermal diffusivity. The phonon-grain boundary scatterings and ballistic phonon transport near the pulsed convergent electron beam were also visualized.

Adenocarcinoma in situ admixed with small cell neuroendocrine carcinoma of the cervix: A case report with cytological features.

Primary cervical small cell neuroendocrine carcinoma (SCNEC) is a rare and aggressive tumor. Herein, we describe the first cytological case of adenocarcinoma in situ (AIS) admixed with SCNEC. A 65-year-old postmenopausal Japanese female presented with abnormal genital bleeding. The Papanicolaou smear of the cervix demonstrated the presence of 2 distinct neoplastic components in an inflammatory background. One component consisted of aggregates of small round cells with a high nuclear/cytoplasmic ratio and round to oval nuclei with powdery chromatin, and inconspicuous nucleoli. Nuclear molding was characteristic. The other component consisted of irregular overlapping clusters of tall columnar cells with large round to oval nuclei containing coarse chromatin, and relatively rich cytoplasm. Accordingly, AIS admixed with SCNEC was suspected. Although the cytological features of cervical SCNEC are characteristic, the cytodiagnosis of this type of tumor may be difficult because of the rarity of the tumor. The presence of non-neuroendocrine tumor components in cervical SCNEC is not unusual, therefore careful observation is needed not to miss SCNEC components in the diagnosis of squamous cell carcinoma and/or adenocarcinoma in cervical cytological specimens.

Surfactant-Triggered Nanoarchitectonics of Fullerene C60 Crystals at a Liquid-Liquid Interface.

Here, we report the structural and morphological modulation of fullerene C60 crystals induced by nonionic surfactants diglycerol monolaurate (C12G2) and monomyristate (C14G2). C60 crystals synthesized at a liquid-liquid interface comprising isopropyl alcohol (IPA) and a saturated solution of C60 in ethylbenzene (EB) exhibited a one-dimensional (1D) morphology with well-defined faceted structure. Average length and diameter of the faceted rods were ca. 4.8 µm and 747 nm, respectively. Powder X-ray diffraction pattern (pXRD) confirmed a hexagonal-close packed (hcp) structure with cell dimensions ca. a = 2.394 nm and c = 1.388 nm. The 1D rod morphology of C60 crystals was transformed into "Konpeito candy-like" crystals (average diameter ca. 1.2 µm) when the C60 crystals were grown in the presence of C12G2 or C14G2 surfactant (1%) in EB. The pXRD spectra of "Konpeito-like" crystals could be assigned to the face-centered cubic (fcc) phase with cell dimensions ca. a = 1.4309 nm (for C12G2) and a = 1.4318 nm (for C14G2). However, clusters or aggregates of C60 lacking a uniform morphology were observed at lower surfactant concentrations (0.1%), although these crystals exhibited an fcc crystal structure. The self-assembled 1D faceted C60 crystals and "Konpeito-like" C60 crystals exhibited intense photoluminescence (PL) (∼35 times greater than pC60) and a blue-shifted PL intensity maximum (∼15 nm) compared to those of pC60, demonstrating the potential use of this method for the control of the optoelectronic properties of fullerene nanostructures. The "Konpeito-like" crystals were transformed into high surface area nanoporous carbon with a graphitic microstructure upon heat-treatment at 2000 °C. The heat-treated samples showed enhanced electrochemical supercapacitance performance (specific capacitance is ca. 175 F g-1, which is about 20 times greater than pC60) with long cyclic stability demonstrating the potential of the materials in supercapacitor device fabrication.

Nanoporous carbon tubes from fullerene crystals as the π-electron carbon source.

Here we report the thermal conversion of one-dimensional (1D) fullerene (C60) single-crystal nanorods and nanotubes to nanoporous carbon materials with retention of the initial 1D morphology. The 1D C60 crystals are heated directly at very high temperature (up to 2000 °C) in vacuum, yielding a new family of nanoporous carbons having π-electron conjugation within the sp(2)-carbon robust frameworks. These new nanoporous carbon materials show excellent electrochemical capacitance and superior sensing properties for aromatic compounds compared to commercial activated carbons.

The origin of the n-type behavior in rare earth borocarbide Y1-xB28.5C4.

Synthesis conditions, morphology, and thermoelectric properties of Y1-xB28.5C4 were investigated. Y1-xB28.5C4 is the compound with the lowest metal content in a series of homologous rare earth borocarbonitrides, which have been attracting interest as high temperature thermoelectric materials because they can embody the long-awaited counterpart to boron carbide, one of the few thermoelectric materials with a history of commercialization. It was revealed that the presence of boron carbide inclusions was the origin of the p-type behavior previously observed for Y1-xB28.5C4 in contrast to Y1-xB15.5CN and Y1-xB22C2N. In comparison with that of previous small flux-grown single crystals, a metal-poor composition of YB40C6 (Y0.71B28.5C4) in the synthesis successfully yielded sintered bulk Y1-xB28.5C4 samples apparently free of boron carbide inclusions. "Pure" Y1-xB28.5C4 was found to exhibit the same attractive n-type behavior as the other rare earth borocarbonitrides even though it is the most metal-poor compound among the series. Calculations of the electronic structure were carried out for Y1-xB28.5C4 as a representative of the series of homologous compounds and reveal a pseudo gap-like electronic density of states near the Fermi level mainly originating from the covalent borocarbonitride network.

Microstructure and high-temperature strength of textured and non-textured ZrB2 ceramics.

Zirconium diboride (ZrB2) ceramic possesses a unique combination of nice mechanical performance, high melting point (> 3000 °C) and great high-temperature oxidation resistance (up to 1600 °C), which makes it a promising material system for ever-increasing ultra-high temperature (UHT) applications. However, ZrB2 suffers from poor mechanical performance at UHTs, which could strongly limit its applications at UHT. Here, we successfully demonstrate that texturing is an effective strategy to greatly enhance the flexural strength of monolithic ZrB2, reaching a high value of 810 ± 60 MPa at 1600 °C when loaded in c-axis direction. We thoroughly discuss the strengthening mechanism by in-depth microstructural observations and analysis. Our discovery has technological and scientific implications for other UHT ceramic systems, especially those using ZrB2 as a matrix.

Physical and mechanical properties of highly textured polycrystalline Nb4AlC3 ceramic.

Highly textured polycrystalline Nb4AlC3 ceramic was fabricated by slip casting in a strong magnetic field followed by spark plasma sintering. Its Lotgering orientation factor was determined on the textured top and side surfaces as f(00l) ∼1.0 and f(hk0)=0.36, respectively. This ceramic showed layered microstructure at the scales ranging from nanometers to millimeters. The as-prepared ceramic had excellent anisotropic physical properties. Along the c-axis direction, it showed higher hardness, bending strength, and fracture toughness of 7.0 GPa, 881 MPa and 14.1 MPa m1/2, respectively, whereas higher values of electrical conductivity (0.81×106 Ω-1 m-1), thermal conductivity (21.20 W m-1 K-1) and Young's modulus (365 GPa) were obtained along the a- or b-axis direction.

Effect of Zn doping on improving crystal quality and thermoelectric properties of borosilicides.

Transition-metal (Mo, Mn, Fe, Rh, Ti, Cu, Zn) doping was carried out on the borosilicide compound REB(44)Si(2) (RE = rare earth). REB(44)Si(2) compounds exhibit Seebeck coefficients greater than 200 microV K(-1) at high temperatures and unlike most compounds, the figure of merit shows a steep increase at T > 1000 K making them promising high-temperature thermoelectric materials. Although zinc itself does not remain in the final product, zinc doping was found to improve the crystal quality, which has been a long-standing problem for the borosilicides. As a result, a significant increase of the thermoelectric power factor by more than 30% was achieved.

Aqueous colloidal processing of single-wall carbon nanotubes and their composites with ceramics.

A unique combination of acid treatment, aqueous colloidal processing, and spark-plasma sintering (SPS) has been used to fabricate high-density Al2O3 /single-wall carbon nanotube (SWNT) composites with well-distributed SWNTs and other carbon nanostructures ('nano-onions', diamond) at Al2O3 grain boundaries. This approach could be used to obtain well-controlled microstructures of ceramic/SWNT composites for tailored mechanical, electrical, and thermal properties. In addition, the colloidal approach for dispersing SWNTs presented here could be used for the controlled manipulation of SWNTs.