Browsing by Subject "THERMAL-DECOMPOSITION"

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  • Iivonen, Tomi; Heikkilä, Mikko J.; Popov, Georgi; Nieminen, Heta-Elisa; Kaipio, Mikko; Kemell, Marianna; Mattinen, Miika; Meinander, Kristoffer; Mizohata, Kenichiro; Räisänen, Jyrki; Ritala, Mikko; Leskelä, Markku (2019)
    Herein, we report an atomic layer deposition (ALD) process for Cu2O thin films using copper(II) acetate [Cu(OAc)(2)] and water vapor as precursors. This precursor combination enables the deposition of phase-pure, polycrystalline, and impurity-free Cu2O thin films at temperatures of 180-220 degrees C. The deposition of Cu(I) oxide films from a Cu(II) precursor without the use of a reducing agent is explained by the thermally induced reduction of Cu(OAc)(2) to the volatile copper(I) acetate, CuOAc. In addition to the optimization of ALD process parameters and characterization of film properties, we studied the Cu2O films in the fabrication of photoconductor devices. Our proof-of-concept devices show that approx- imately 20 nm thick Cu2O films can be used for photodetection in the visible wavelength range and that the thin film photoconductors exhibit improved device characteristics in comparison to bulk Cu2O crystals.
  • Silber, Elizabeth A.; Hocking, Wayne K.; Niculescu, Mihai L.; Gritsevich, Maria; Silber, Reynold E. (2017)
    Studies of meteor trails have until now been limited to relatively simple models, with the trail often being treated as a conducting cylinder, and the head (if considered at all) treated as a ball of ionized gas. In this article, we bring the experience gleaned from other fields to the domain of meteor studies, and adapt this prior knowledge to give a much clearer view of the microscale physics and chemistry involved in meteor-trail formation, with particular emphasis on the first 100 or so milliseconds of the trail formation. We discuss and examine the combined physicochemical effects of meteor-generated and ablationally amplified cylindrical shock waves that appear in the ambient atmosphere immediately surrounding the meteor train, as well as the associated hyperthermal chemistry on the boundaries of the high temperature post-adiabatically expanding meteor train. We demonstrate that the cylindrical shock waves produced by overdense meteors are sufficiently strong to dissociate molecules in the ambient atmosphere when it is heated to temperatures in the vicinity of 6000 K, which substantially alters the considerations of the chemical processes in and around the meteor train. We demonstrate that some ambient O-2, along with O-2 that comes from the shock dissociation of O-3, survives the passage of the cylindrical shock wave, and these constituents react thermally with meteor metal ions, thereby subsequently removing electrons from the overdense meteor train boundary through fast, temperature-independent, dissociative recombination governed by the second Damkohler number. Possible implications for trail diffusion and lifetimes are discussed.
  • Eskola, Arrke J.; Blitz, Mark A.; Pilling, Michael J.; Seakins, Paul W.; Shannon, Robin J. (2020)
    The rate coefficient for the unimolecular decomposition of CH3OCH2,k(1), has been measured in time-resolved experiments by monitoring the HCHO product. CH3OCH2 was rapidly and cleanly generated by 248 nm excimer photolysis of oxalyl chloride, (ClCO)(2), in an excess of CH3OCH3, and an excimer pumped dye laser tuned to 353.16 nm was used to probe HCHO via laser induced fluorescence. k(1)(T,p) was measured over the ranges: 573-673 K and 0.1-4.3 x 10(18) molecule cm(-3) with a helium bath gas. In addition, some experiments were carried out with nitrogen as the bath gas. Ab initio calculations on CH3OCH2 decomposition were carried out and a transition-state for decomposition to CH3 and H2CO was identified. This information was used in a master equation rate calculation, using the MESMER code, where the zero-point-energy corrected barrier to reaction, Delta E-0,E-1, and the energy transfer parameters, x T-n, were the adjusted parameters to best fit the experimental data, with helium as the buffer gas. The data were combined with earlier measurements by Loucks and Laidler (Can J. Chem. 1967, 45, 2767), with dimethyl ether as the third body, reinterpreted using current literature for the rate coefficient for recombination of CH3OCH2. This analysis returned Delta E-0,E-1 = (112.3 +/- 0.6) kJ mol(-1), and leads to k(1)(infinity)(T) = 2.9 x 10(12) (T/300)(2)(.5) exp(-106.8 kJ mol(-1)/RT). Using this model, limited experiments with nitrogen as the bath gas allowed N-2 energy transfer parameters to be identified and then further MESMER simulations were carried out, where N-2 was the buffer gas, to generate k(1)(T,p) over a wide range of conditions: 300-1000 K and N-2 = 10(12) -10(25) molecule cm(-3). The resulting k(1)(T,p) has been parameterized using a Troe-expression, so that they can be readily be incorporated into combustion models. In addition, k(1)(T,p) has been parametrized using PLOG for the buffer gases, He, CH3OCH3 and N-2.