Thermal and Remote Plasma ALD of Ru from CpRu(CO)2Et and O2

Ruthenium (Ru) is regarded as an electrode candidate on ultrahigh-k SrTiO3 dielectric films for future high-density trench capacitors. To achieve conformal film growth, atomic layer deposition (ALD) of Ru is investigated. To this end, the use of an oxidizing reactant is desired to avoid electronic degradation of the interface properties of SrTiO3 as found when using a NH3 plasma for Ru ALD or when using thermal ALD TiN as electrode. Thermal ALD of Ru using O2 gas, however, generally results in a pronounced nucleation delay and high surface roughness. The current work aims at developing ALD of Ru using an O2 plasma in order to improve the film nucleation and to try to obtain smoother films. Using the novel CpRu(CO)2Et precursor and O2, both thermal and remote plasma ALD of Ru were studied in the same reactor at wafers up to 200 mm. Unlike thermal ALD, the Ru film growth by remote plasma ALD does not rely on the dissociative chemisorption of O2 on the Ru surface and good film nucleation is expected by providing O radicals from the gas phase. In situ spectroscopic ellipsometry, x-ray reflectometry and diffractometry, and electrical measurements clearly show this benefit of the O2 plasma. The Ru films almost immediately nucleate for the plasma-based process, whereas the thermal process showed a nucleation delay of approximately 100 cycles. Once the film growth has started, the growth per cycle (1 Å/cycle), the electrical properties (20 µOcm for >5 nm films), and the polycrystalline structure are similar for both ALD processes. However, despite the drastically improved nucleation, the remote plasma ALD Ru films show higher roughness values than the thermal ALD Ru films (roughness of 13 nm and 8 nm for 20 nm thick films, respectively). To elucidate this unexpected phenomenon, the film nucleation and surface reactions were examined. Mass spectrometry provided insight into the reaction products (CO, CO2 and H2O mainly) and, therefore, into the surface chemistry ruling both ALD processes. Optical emission spectroscopy delivered information on the species created during plasma exposure. A reaction mechanism will be proposed for these oxygen-based ALD Ru processes that accounts not only for the differences in nucleation, but also relates to the roughness development of the Ru films

Atomic layer deposition of Ru from CpRu(CO2)Et using O2 gas and O2 plasma

The metalorganic precursor cyclopentadienylethyl(dicarbonyl)ruthenium (CpRu(CO)2Et) was used to develop an atomic layer deposition (ALD) process for ruthenium. O2 gas and O2 plasma were employed as reactants. For both processes, thermal and plasma-assisted ALD, a relatively high growth-per-cycle of - 1 Å was obtained. The Ru films were dense and polycrystalline, regardless of the reactant, yielding a resistivity of - 16 µO¿cm. The O2 plasma not only enhanced the Ru nucleation on the TiN substrates but also led to an increased roughness compared to thermal ALD

Untersuchungen zur Herstellung und zum Abbrandverhalten von Wirbelschichtpyrolysekoksen

Der partielle und selektive Abbrand von Pyrolysekoksen in einem Wirbelbett mit Steinkohlekoks als Bettmaterial könnte die benötigte Wärme erzeugen, um in demselben Reaktor endotherme Pyrolyse- und Vergasungsreaktionen zur Behandlung organischer Reststoffe durchzuführen. Zur Messung der Reaktivitätsunterschiede der Kokse bezüglich Sauerstoff wurde an zwei Laborapparaturen (Thermowaage, Sandwirbelschicht) das Abbrandverhalten von Wirbelschicht-Pyrolysekoksen und Kohlekoksen im chemisch kontrollierten Temperaturbereich untersucht. Zur Bestimmung der formalkinetischen Parameter Aktivierungsenergie EA und Stoßfaktor k0 wurde im Falle der Thermowaage die Massenverlustkurve bei isothermer Reaktionführung ausgewertet. Im Falle der Wirbelschicht wurde der zeitliche CO/ CO2\- Verlauf im Abgas in eine Massenverlustkurve an Kohlenstoff umgerechnet und anschließend analog zur Thermowaage ausgewertet. Zur Beschreibung der Kinetik wurde ein massenbezogener Ansatz erster Ordnung bezüglich der Kohlenstoffmasse und -ter Ordnung bezüglich der Sauerstoffkonzentration verwendet. Die an der Thermowaage bestimmten Reaktivitäten der Kokse werden vergleichend in einem Arrhenius-Diagramm (T=250-600°C) dargestellt. Nach steigender Reaktivität geordnet lautet die Reihenfolge der untersuchten Kokse: Steinkohlenkoks < Braunkohlenkoks < DSD-Koks < Holzkoks < Strohkoks. Durch die an der Thermowaage bestimmten Reaktivitätsunterschiede zwischen Pyrolysekoksen und Bettmaterial ist ein selektiver Abbrand der Pyrolysekokse beim Betrieb einer kontinuierlichen Kokswirbelschicht zu erwarten

Expression of muscle anabolic and metabolic factors in mechanically loaded MLO-Y4 osteocytes

Lack of physical activity results in muscle atrophy and bone loss, which can be counteracted by mechanical loading. Similar molecular signaling pathways are involved in the adaptation of muscle and bone mass to mechanical loading. Whether anabolic and metabolic factors regulating muscle mass, i.e., insulin-like growth factor-I isoforms (IGF-I Ea), mechano growth factor (MGF), myostatin, vascular endothelial growth factor (VEGF), or hepatocyte growth factor (HGF), are also produced by osteocytes in bone in response to mechanical loading is largely unknown. Therefore, we investigated whether mechanical loading by pulsating fluid flow (PFF) modulates the mRNA and/or protein levels of muscle anabolic and metabolic factors in MLO-Y4 osteocytes. Unloaded MLO-Y4 osteocytes expressed mRNA of VEGF, HGF, IGF-I Ea, and MGF, but not myostatin. PFF increased mRNA levels of IGF-I Ea (2.1-fold) and MGF (2.0-fold) at a peak shear stress rate of 44Pa/s, but not at 22Pa/s. PFF at 22 Pa/s increased VEGF mRNA levels (1.8- to 2.5-fold) and VEGF protein release (2.0- to 2.9-fold). Inhibition of nitric oxide production decreased (2.0-fold) PFF-induced VEGF protein release. PFF at 22 Pa/s decreased HGF mRNA levels (1.5-fold) but increased HGF protein release (2.3-fold). PFF-induced HGF protein release was nitric oxide dependent. Our data show that mechanically loaded MLO-Y4 osteocytes differentially express anabolic and metabolic factors involved in the adaptive response of muscle to mechanical loading (i.e., IGF-I Ea, MGF, VEGF, and HGF). Similarly to muscle fibers, mechanical loading enhanced expression levels of these growth factors in MLO-Y4 osteocytes. Although in MLO-Y4 osteocytes expression levels of IGF-I Ea and MGF of myostatin were very low or absent, it is known that the activity of osteoblasts and osteoclasts is strongly affected by them. The abundant expression levels of these factors in muscle cells, in combination with low expression in MLO-Y4 osteocytes, provide a possibility that growth factors expressed in muscle could affect signaling in bone cells

GLONASS CDMA L3 ambiguity resolution and positioning

A first assessment of GLONASS CDMA L3 ambiguity resolution and positioning performance is provided. Our analyses are based on GLONASS L3 data from the satellite pair SVNs 755-801, received by two JAVAD receivers at Curtin University, Perth, Australia. In our analyses, four different versions of the two-satellite model are applied: the geometry-free model, the geometry-based model , the height-constrained geometry-based model, and the geometry-fixed model. We study the noise characteristics (carrier-to-noise density, measurement precision), the integer ambiguity resolution performance (success rates and distribution of the ambiguity residuals), and the positioning performance (ambiguity float and ambiguity fixed). The results show that our empirical outcomes are consistent with their formal counterparts and that the GLONASS data have a lower noise level than that of GPS, particularly in case of the code data. This difference is not only seen in the noise levels but also in their onward propagation to the ambiguity time series and ambiguity residuals distribution

Heterolytic Scission of Hydrogen Within a Crystalline Frustrated Lewis Pair

We report the heterolysis of molecular hydrogen under ambient conditions by the crystalline frustrated Lewis pair (FLP) 1-{2-[bis (pentafluorophenyOboryl] phenyl -2, 2,6,6-tetrame-thylpiperidine (KCAT). The gas-solid reaction provides an approach to prepare the solvent-free, polycrystalline ion pair KCATH2 through a single crystal to single crystal transformation. The crystal lattice of KCATH2 increases in size relative to the parent KCAT by approximately 2%. Microscopy was used to follow the transformation of the highly colored red/orange KCAT to the colorless KCATH2 over a period of 2 h at 300 K under a flow of H-2 gas. There is no evidence of crystal decrepitation during hydrogen uptake. Inelastic neutron scattering employed over a temperature range from 4-200 K did not provide evidence for the formation of polarized H-2 in a precursor complex within the crystal at low temperatures and high pressures. However, at 300 K, the INS spectrum of KCAT transformed to the INS spectrum of KCATH2. Calculations suggest that the driving force is more favorable in the solid state compared to the solution or gas phase, but the addition of H-2 into the KCAT crystal is unfavorable. Ab Initio methods were used to calculate the INS spectra of KCAT, KCATH2, and a possible precursor complex of H-2 in the pocket between the B and N of crystalline KCAT. Ex-situ NMR showed that the transformation from KCAT to KCATH2 is quantitative and our results suggest that the hydrogen heterolysis process occurs via H-2 diffusion into the FLP crystal with a rate-limiting movement of H-2 from inactive positions to reactive sites.Peer reviewe

The Online dating romance scam: The psychological impact on victims – both financial and non-financial

This paper examined the psychological impact of the online dating romance scam. Unlike other mass-marketing fraud victims, these victims experienced a ‘double hit’ of the scam: a financial loss and the loss of a relationship. For most, the loss of the relationship was more upsetting than their financial losses (many described the loss of the relationship as a ‘death’). Some described their experience as traumatic and all were affected negatively by the crime. Most victims had not found ways to cope given the lack of understanding from family and friends. Denial (e.g., not accepting the scam was real or not being able to separate the fake identity with the criminal) was identified as an ineffective means of coping, leaving the victim vulnerable to a second wave of the scam. Suggestions are made as to how to change policy with regards to law enforcement deal with this crime

ANALYTICAL QUALITY ASSESSMENT OF ITERATIVELY REWEIGHTED LEAST-SQUARES (IRLS) METHOD

The iteratively reweighted least-squares (IRLS) technique has been widelyemployed in geodetic and geophysical literature. The reliability measures areimportant diagnostic tools for inferring the strength of the model validation. Anexact analytical method is adopted to obtain insights on how much iterativereweighting can affect the quality indicators. Theoretical analyses and numericalresults show that, when the downweighting procedure is performed, (1) theprecision, all kinds of dilution of precision (DOP) metrics and the minimaldetectable bias (MDB) will become larger; (2) the variations of the bias-to-noiseratio (BNR) are involved, and (3) all these results coincide with those obtained bythe first-order approximation method