Plasma etching of high-k and metal gate materials

Etching characteristics of high-k dielectric materials (HfO₂) and metal electrode materials (Pt, TaN) have been studied in high-density chlorine-containing plasmas at pressures around 10 mTorr. The etching of HfO₂ was performed in BCl₃ without rf biasing, giving an etch rate of about 5 nm/min with a high selectivity of >10 over Si and SiO₂. The etching of Pt and TaN was performed in Ar/O₂ with high rf biasing and in Ar/Cl₂ with low rf biasing, respectively, giving a Pt etch rate of about several tens nm/min and a TaN etch rate of about 200 nm/min with a high selectivity of >8 over HfO₂ and SiO₂. The etched profiles were outwardly tapered for Pt, owing to the redeposition of etch or sputter products on feature sidewalls, while the TaN profiles were almost anisotropic, probably owing to the ion-enhanced etching that occurred.     

Evaluation of absorption of micro-droplets on paper for creation of paper-based microstructures

This study clarifies the absorption behavior of micro-droplets of water on treated paper to support the design of functional microstructures, such as electronics and micro-fluid channels, on paper. The period of time between when a micro-droplet of water ejected from an ink-jet head lands on the paper’s surface and its complete disappearance by absorption was defined as the micro-sizing degree (MSD), and an MSD measurement method was established. The MSD was evaluated using microscopic high-speed video images of the side view recorded every millisecond. Several grades of commercially available ink-jet paper media and laboratory sheets having different levels of water repellency prepared from a pulp and a sizing agent were examined. The MSD of commercial ink-jet papers, which are known to absorb water very quickly, was 3–6 ms. Weakly sized laboratory sheets exhibited a lower MSD of 2–3 ms. The absorption behavior was analyzed in terms of the capillary pressure with and without the Laplace pressure; the theoretical and experimental results agreed moderately well. The results indicated that the Laplace pressure cannot be neglected in the analysis. The MSD of a wet surface where a preceding micro-droplet had already landed was higher than that on a dry or partially wet surface, presumably because water remains inside pores for an unexpectedly long time.     

Persistent chorea following cardiac surgery for congenital heart disease

We describe a 6 year old girl with chorea following cardiac surgery, the first such report in Japan. The radical operation for total anomalous pulmonary venous return was carried out at the age of 11 months under hypothermia. Seven days after the operation, a sudden onset of irritability, dysphagia, chorea, generalized, hypotonia, and complete external ophthalmoplegia were seen. These symptoms diminished gradually, but chorea remained. We speculated that the cause of chorea arose from the cardiac surgery under hypothermia. It is necessary to consider 'cardiac surgery' as one of the triggers of certain movement disorders including chorea. We tried treatment with haloperidol, pimozide, and several other drugs; only pimozide was effective in decreasing chorea without any side-effects.     

Diffusion of vanadium,chromium, and manganese in copper

The diffusion coefficients of vanadium, chromium and manaanese in copper have been determined by the residual activity method with radioactive tracers V⁴⁸, Cr⁵¹ and Mn⁵⁴ in the temperature ranges between 955 and 1342 K, between 999 and 1338 K and between 971 and 1253 K, respectively. The temperature dependence of the diffusion coefficients is expressed by the following Arrhenius equations along with the probable errors:D _V/Cu = (2.48 _-0.44 ^+0.53 ) x 10⁻⁴ exp [-(215 ± 2) kJ mol⁻¹/RT] m² per s,D _Cr/Cu = (0.337 _-0.090 ^+0.124 ) x 10⁻⁴ exp [-(195 ± 3) kJ mol⁻¹/RT] m² per s,D _Mn/Cu = (1.02 _-0.18 ^+0.22 ) x 10⁻⁴ exp [-(200 ± 2) kJ mol⁻¹/RT] m² per s. Anomalous penetration profiles for the diffusion of Cr⁵¹ and Mn⁵⁴ in the present results suggest that experimental results onD _Cr/Cu andD _Mn/Cu in the past have been influenced by oxidation and evaporation of the chemically active radiotracers during annealing for diffusion. formerly Graduate Student, Tohoku University     

Intrinsic diffusion coefficients and the vacancy flow factor in Dilute Cu-Zn Alloys

Interdiffusion coefficients in copper-rich copper-zinc solid solutions containing up to 8 at. pct of Zn at 1168 K have been determined by Matano's analysis using semi-infinite diffusion couples consisting of pure copper and Cu-Zn alloys with Kirkendall markers. From the marker shift and Darken's relation, intrinsic diffusion coefficients, D_Zn and D_Cu, in the alloys containing 3.2 and 4.7 at. pct of Zn have been determined. Further, using thin plate couples, D_Zn and D_Cu in Cu alloys containing 0.9, 2.3, 3.5, and 4.6 at. pct of Zn at 1168 K have been determined by Heumann's method. The ratio of the intrinsic diffusion coefficients, D_Zn/D_Cu, has been found to be about two for all the compositions examined. Using the values of the intrinsic diffusion coefficient of copper at infinite dilution of zinc obtained by extrapolating the concentration dependence of D_Cu, and the self- and impurity diffusion coefficients in pure copper, the vacancy flow factor has been estimated to be - 0.22_-0.15 ^+0.06 at 1168 K. By combining this value of the vacancy flow factor with the solute enhancement factor of solvent diffusion determined by Peterson and Rothman, the correlation factor for impurity diffusion of Zn in Cu at 1168 K has been evaluated to be 0.5, which is in good agreement with the value of 0.47 determined by Peterson and Rothman based on the isotope effect measurement. KAZUTOMO HOSHINO, formerly Graduate Student, Tohoku University is now with Materials Science Division, Argonne National Laboratory, Argonne, IL 60439. YOSHIAKI IIJIMA, Instructor, and KENICHI HIRANO, Professor, are both with the Department of Materials Science, Faculty of Engineering, Tohoku University, Sendai 980, Japan.     

Gentle STEM: ADF imaging and EELS at low primary energies

Aberration correction of the scanning transmission electron microscope (STEM) has made it possible to reach probe sizes close to 1 Å at 60 keV, an operating energy that avoids direct knock-on damage in materials consisting of light atoms such as B, C, N and O. Although greatly reduced, some radiation damage is still present at this energy, and this limits the maximum usable electron dose. Elemental analysis by electron energy loss spectroscopy (EELS) is then usefully supplemented by annular dark field (ADF) imaging, for which the signal is larger. Because of its strong Z dependence, ADF allows the chemical identification of individual atoms, both heavy and light, and it can also record the atomic motion of individual heavy atoms in considerable detail. We illustrate these points by ADF images and EELS of nanotubes containing nanopods filled with single atoms of Er, and by ADF images of graphene with impurity atoms.     

Chemical Growth of 1T‐TaS2 Monolayer and Thin Films: Robust Charge Density Wave Transitions and High Bolometric Responsivity

Ultrathin two‐dimensional (2D) charge density wave (CDW) materials, with sharp resistance change at the phase‐transition temperature, yet with ultrathin thickness, hold great potential for electrical device applications. However, chemical synthesis of high‐quality samples and observation of the CDW states down to the monolayer limit is still of great challenge. Chemical vapor deposition of 1T‐TaS₂ sheets on hexagonal boron nitride (h‐BN) with robust CDW states even down to the monolayer extreme is reported here. Further, based on the near commensurate CDW to incommensurate CDW phase transition with a high temperature coefficient of resistance (TCR), highly responsive room‐temperature bolometers are fabricated by suspending the as‐grown 1T‐TaS₂ sheets.     

Gate effect of vacancy-type defect of fullerene cages on metal-atom migrations in metallofullerenes

Metal-atom migration outside from a defective fullerene cage of a metallofullerene Gd@C(82) (Ca@C(82)), where the Gd(3+) (Ca(2+)) ion is incorporated inside the C(2)(v)()-C(82) cage, is discussed in detail at the B3LYP DFT level of theory. The metal-atom migrations are initiated by the formation of vacancy-type defects involving two coordinatively unsaturated C atoms. This step, which is assumed to proceed due to energy-particle irradiation, leads to the formation of antibonding orbitals between the two C atoms. Since the antibonding orbitals can interact with vacant d-orbitals of the Gd(3)(+)() ion in an in-phase fashion, the attractive interactions allow the Gd ion to insert into the two C atoms in the defect. As a result, the metal ion passes through the defect under energy-particle irradiation. In contrast, the Ca(2+) ion with the vacant s-orbitals does not have such orbital interactions, and thus, a C-C bond is reformed between the two C atoms, which prohibits the Ca ion from penetrating the defected C(82) cage. DFT calculations nicely demonstrate that the orbital interactions control metal-atom migration around the defect site using their orbital symmetries, and therefore, the vacancy-type defect acts as a "gate" that permits a specific atom to go out from a defected fullerene cage.     

Diameter dependent growth mode of carbon nanotubes on nanoporous SiO2 substrates

Two different growth modes of carbon nanotubes (CNTs) are identified in ethylene chemical vapour deposition (CVD) using SiO₂ as support. With a series of electron microscopy observations, we have found that small-diameter nanotubes favor a root-growth mechanism on nanoporous SiO₂ support, while nanotubes with larger diameters prefer a tip-growth. The dependence of growth mode on tube diameter is explained in terms of the porosity of the support and the size distribution of the catalyst. Our results provide clues to control growth of CNTs and obtain well-organized nanotube structures.