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Analysis of catalyst surface wetting: The early stage of epitaxial germanium nanowire growth
2020, Ernst, Owen C., Lange, Felix, Uebel, David, Teubner, Thomas, Boeck, Torsten
The dewetting process is crucial for several applications in nanotechnology. Even though not all dewetting phenomena are fully understood yet, especially regarding metallic fluids, it is clear that the formation of nanometre-sized particles, droplets, and clusters as well as their movement are strongly linked to their wetting behaviour. For this reason, the thermodynamic stability of thin metal layers (0.1-100 nm) with respect to their free energy is examined here. The decisive factor for the theoretical considerations is the interfacial energy. In order to achieve a better understanding of the interfacial interactions, three different models for estimating the interfacial energy are presented here: (i) fully theoretical, (ii) empirical, and (iii) semi-empirical models. The formation of nanometre-sized gold particles on silicon and silicon oxide substrates is investigated in detail. In addition, the strengths and weaknesses of the three models are elucidated, the different substrates used are compared, and the possibility to further process the obtained particles as nanocatalysts is verified. The importance of a persistent thin communication wetting layer between the particles and its effects on particle size and number is also clarified here. In particular, the intrinsic reduction of the Laplace pressure of the system due to material re-evaporation and Ostwald ripening describes the theoretically predicted and experimentally obtained results. Thus, dewetting phenomena of thin metal layers can be used to manufacture nanostructured devices. From this point of view, the application of gold droplets as catalysts to grow germanium nanowires on different substrates is described. © 2020 Ernst et al.
A faux hawk fullerene with PCBM-like properties
2014, San, Long K., Bukovsky, Eric V., Larson, Bryon W., Whitaker, James B., Deng, S.H.M., Kopidakis, Nikos, Rumbles, Garry, Popov, Alexey A., Chen, Yu-Sheng, Wang, Xue-Bin, Boltalina, Olga V., Strauss, Steven H.
Reaction of C60, C6F5CF2I, and SnH(n-Bu)3 produced, among other unidentified fullerene derivatives, the two new compounds 1,9-C60(CF2C6F5)H (1) and 1,9-C60(cyclo-CF2(2-C6F4)) (2). The highest isolated yield of 1 was 35% based on C60. Depending on the reaction conditions, the relative amounts of 1 and 2 generated in situ were as high as 85% and 71%, respectively, based on HPLC peak integration and summing over all fullerene species present other than unreacted C60. Compound 1 is thermally stable in 1,2-dichlorobenzene (oDCB) at 160 °C but was rapidly converted to 2 upon addition of Sn2(n-Bu)6 at this temperature. In contrast, complete conversion of 1 to 2 occurred within minutes, or hours, at 25 °C in 90/10 (v/v) PhCN/C6D6 by addition of stoichiometric, or sub-stoichiometric, amounts of proton sponge (PS) or cobaltocene (CoCp2). DFT calculations indicate that when 1 is deprotonated, the anion C60(CF2C6F5)− can undergo facile intramolecular SNAr annulation to form 2 with concomitant loss of F−. To our knowledge this is the first observation of a fullerene-cage carbanion acting as an SNAr nucleophile towards an aromatic C–F bond. The gas-phase electron affinity (EA) of 2 was determined to be 2.805(10) eV by low-temperature PES, higher by 0.12(1) eV than the EA of C60 and higher by 0.18(1) eV than the EA of phenyl-C61-butyric acid methyl ester (PCBM). In contrast, the relative E1/2(0/−) values of 2 and C60, −0.01(1) and 0.00(1) V, respectively, are virtually the same (on this scale, and under the same conditions, the E1/2(0/−) of PCBM is −0.09 V). Time-resolved microwave conductivity charge-carrier yield × mobility values for organic photovoltaic active-layer-type blends of 2 and poly-3-hexylthiophene (P3HT) were comparable to those for equimolar blends of PCBM and P3HT. The structure of solvent-free crystals of 2 was determined by single-crystal X-ray diffraction. The number of nearest-neighbor fullerene–fullerene interactions with centroid⋯centroid (⊙⋯⊙) distances of ≤10.34 Å is significantly greater, and the average ⊙⋯⊙ distance is shorter, for 2 (10 nearest neighbors; ave. ⊙⋯⊙ distance = 10.09 Å) than for solvent-free crystals of PCBM (7 nearest neighbors; ave. ⊙⋯⊙ distance = 10.17 Å). Finally, the thermal stability of 2 was found to be far greater than that of PCBM.
Stability studies of ionic liquid [EMIm][NTf2] under short-term thermal exposure
2016, Neise, Christin, Rautenberg, Christine, Bentrup, Ursula, Beck, Martin, Ahrenberg, Mathias, Schick, Christoph, Keßler, Olaf, Kragl, Udo
Ionic liquids (ILs) as new media for synthesis and as functional fluids in technical applications are still of high interest. Cooling a steel component from an annealing temperature of nearly 850 °C down to room temperature in a liquid bath is a technically important process. The use of ionic liquids offers advantages avoiding film boiling of the quenching medium. However, such a high immersion temperature exceeds the thermal stability of the IL, for example such as [EMIm][NTf2]. To obtain information about formation of potential toxic decomposition products, potential fragments at varied states of decomposition of [EMIm][NTf2] were studied by various spectroscopic and gravimetric methods. For the first time it was possible to quantify fluorine-containing products via mass spectrometry coupled directly with thermogravimetric (TG) measurements. While chemical and spectroscopic analysis of thermally stressed ILs revealed no hints concerning changes of composition after quenching hot steel for several times, the mass-spectrometer (MS) coupled TG analysis gives information by comparing the decomposition behaviour of fresh and used ILs. A number of fragments were detected in low amounts confirming the proposed decomposition mechanism.
Enhanced thermal stability of yttrium oxide-based RRAM devices with inhomogeneous Schottky-barrier
2020, Piros, Eszter, Petzold, Stefan, Zintler, Alexander, Kaiser, Nico, Vogel, Tobias, Eilhardt, Robert, Wenger, Christian, Molina-Luna, Leopoldo, Alff, Lambert
This work addresses the thermal stability of bipolar resistive switching in yttrium oxide-based resistive random access memory revealed through the temperature dependence of the DC switching behavior. The operation voltages, current levels, and charge transport mechanisms are investigated at 25 °C, 85 °C, and 125 °C, and show overall good temperature immunity. The set and reset voltages, as well as the device resistance in both the high and low resistive states, are found to scale inversely with increasing temperatures. The Schottky-barrier height was observed to increase from approximately 1.02 eV at 25 °C to approximately 1.35 eV at 125 °C, an uncommon behavior explained by interface phenomena. © 2020 Author(s).
Mo-La2O3 multilayer metallization systems for high temperature surface acoustic wave sensor devices
2019, Menzel, S.B., Seifert, M., Priyadarshi, A., Rane, G.K., Park, E., Oswald, S., Gemming, T.
Developing advanced thin film materials is the key challenge in high-temperature applications of surface acoustic wave sensor devices. One hundred nanometer thick (Mo-La2O3) multilayer systems were fabricated at room temperature on thermally oxidized (100) Si substrates (SiO2/Si) to study the effect of lanthanum oxide on the electrical resistivity of molybdenum thin films and their high-temperature stability. The multilayer systems were deposited by the magnetron sputter deposition of extremely thin (≤1 nm) La interlayers in between adjacent Mo layers. After deposition of each La layer the process was interrupted for 25 to 60 min to oxidize the La using the residual oxygen in the high vacuum of the deposition chamber. The samples were annealed at 800 °C in high vacuum for up to 120 h. In case of a 1 nm thick La interlayer in-between the Mo a continuous layer of La2O3 is formed. For thinner La layers an interlayer between adjacent Mo layers is observed consisting of a (La2O3-Mo) mixed structure of molybdenum and nm-sized lanthanum oxide particles. Measurements show that the (Mo-La2O3) multilayer systems on SiO2/Si substrates are stable at least up to 800 °C for 120 h in high vacuum conditions.
Comparison of nano-structured transition metal modified tri-metal MgMAl–LDHs (M = Fe, Zn, Cu, Ni, Co) prepared using co-precipitation
2019, Gevers, Bianca R., Naseem, Sajid, Leuteritz, Andreas, Labuschagné, Frederick J. W. J.
Comparison of layered double hydroxides (LDHs) synthesised using different methods, conditions and post-treatment is difficult to achieve because these greatly modify their material properties. This paper aims to provide a comparison of material properties for modified quintinite, where all LDHs were synthesised at the same conditions-thus allowing for direct comparison of the material properties obtained. Nano-structured materials were formed in all cases. The nano-structured transition metal (TM) MgMAl-LDHs were synthesised using constant pH co-precipitation. Five TMs (M = Fe, Co, Ni, Cu, Zn) were included in the LDH layers with molar substitutions of 0.5%, 1%, 5%, 10%, and 25% based on Mg-replacement for divalent TM cations and Al-replacement for trivalent TM cations. The materials were characterised using powder X-ray diffraction (XRD), X-ray fluorescence spectroscopy (XRF), scanning electron microscopy (SEM), attenuated total reflectance Fourier transform infrared analysis (ATR-FTIR), thermogravimetric analysis (TGA) and particle size analysis (PSA). The modified LDHs were synthesised free of major by-products and with similar morphologies. It could be shown that the crystallite dimensions varied between the different TM substitutions, that morphological changes were visible for some of the TMs used, that the processability depended on the TMs substituted, and that the substitution of TMs influenced the thermal stability of the LDHs. This journal is © 2019 The Royal Society of Chemistry.
Aerobic iron-catalyzed site-selective C(sp3)–C(sp3) bond cleavage in N-heterocycles
2021, Leonard, David K., Li, Wu, Rockstroh, Nils, Junge, Kathrin, Beller, Matthias
The kinetic and thermodynamic stability of C(sp3)–C(sp3) bonds makes the site-selective activation of these motifs a real synthetic challenge. In view of this, herein a site-selective method of C(sp3)–C(sp3) bond scission of amines, specifically morpholine and piperazine derivatives, using a cheap iron catalyst and air as a sustainable oxidant is reported. Furthermore, a statistical design of experiments (DoE) is used to evaluate multiple reaction parameters thereby allowing for the rapid development of a catalytic process. © 2021
High temperature behavior of rual thin films on piezoelectric CTGS and LGS substrates
2020, Seifert, M.
This paper reports on a significant further improvement of the high temperature stability of RuAl thin films (110 nm) on the piezoelectric Ca3TaGa3Si2O14 (CTGS) and La3Ga5SiO14 (LGS) substrates. RuAl thin films with AlN or SiO2 cover layers and barriers to the substrate (each 20 nm), as well as a combination of both were prepared on thermally oxidized Si substrates, which serve as a reference for fundamental studies, and the piezoelectric CTGS, as well as LGS substrates. In somefilms, additional Al layers were added. To study their high temperature stability, the samples were annealed in air and in high vacuum up to 900 °C, and subsequently their cross-sections, phase formation, film chemistry, and electrical resistivity were analyzed. It was shown that on thermally oxidized Si substrates, all films were stable after annealing in air up to 800 °C and in high vacuum up to 900 °C. The high temperature stability of RuAl thin films on CTGS substrates was improved up to 900 °C in high vacuum by the application of a combined AlN/SiO2 barrier layer and up to 800 °C in air using a SiO2 barrier. On LGS, the films were only stable up to 600 °C in air; however, a single SiO2 barrier layer was sufficient to prevent oxidation during annealing at 900 °C in high vacuum.