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Chemically driven isothermal closed space vapor transport of MoO$_2$: thin films, flakes and in-situ tellurization

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 Added by Osvaldo De Melo
 Publication date 2019
  fields Physics
and research's language is English




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A novel procedure, based in a closed space vapor transport (CSVT) configuration, has been devised to grow films or flakes of pure MoO2 in a reductive atmosphere, at relatively low temperature and using MoO3 as the source. In contrast with conventional CSVT technique, in the proposed method a temperature gradient is not required for the growth to take place, which occurs through an intermediate volatile transport species that is produced in the complex reduction reaction of MoO3. An added value of this simple method is the possibility of transforming the MoO2 into MoTe2, one of the most interesting members of the transition metal dichalcogenide family. This is achieved in a sequential process that includes the growth of Mo oxide and its (in-situ) tellurization in two consecutive steps.

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Chemically _ driven isothermal close space vapour transport was used to prepare pure MoO2 films which were eventually converted to MoO3 by annealing in air. According to temperature_dependent Raman measurements, the MoO2/MoO3 phase transformation was found to occur in the 225 _ 350 oC range; no other phases were detected during the transition. A clear change in composition and Raman spectra, as well as noticeable modifications of the band gap and the absorption coefficient confirmed the conversion from MoO2 to MoO3. An extensive characterization of films of both pure phases was carried out. In particular, a procedure was developed to determine the dispersion relation of the refractive index of MoO2 from the shift of the interference fringes the used SiO2/Si substrate. The obtained refractive index was corrected taking into account the porosity calculated from elastic backscattering spectrometry. The Debye temperature and the residual resistivity were extracted from the electrical resistivity temperature dependence using the Bloch _ Gruneisen equation. MoO3 converted samples presented very high resistivity and a typical semiconducting behaviour. They also showed intense and broad luminescence spectra, which were deconvoluted considering several contributions; and its behaviour with temperature was examined. Furthermore, surface photovoltage spectra were taken and the relation of these spectra with the photoluminescence is discussed.
The resistance of chemically synthesized polypyrrole (PPy) thin films is investigated as a function of the pressure of various gases as well as of the film thickness. A physical, piezoresistive response is found to coexist with a chemical response if the gas is chemically active, like, e.g., oxygen. The piezoresistance is studied separately by exposing the films to the chemically inert gases such as nitrogen and argon. We observe that the character of the piezoresistive response is a function not only of the film thickness, but also of the pressure. Films of a thickness below 70 nm show a decreasing resistance as pressure is applied, while for thicker films, the piezoresistance is positive. Moreover, in some films of thickness of about 70 nm, the piezoresistive response changes from negative to positive as the gas pressure is increased above 500 mbars. This behavior is interpreted in terms of a total piezoresistance which is composed of a surface and a bulk component, each of which contributes in a characteristic way. These results suggest that in polypyrrole, chemical sensing and piezoresistivity can coexist, which needs to be kept in mind when interpreting resistive responses of such sensors.
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We have studied the structural and superconducting properties of MgB$_2$ thin films made by pulsed laser deposition followed by in situ annealing. The cross-sectional transmission electron microscopy reveals a nanocrystalline mixture of textured MgO and MgB$_2$ with very small grain sizes. A zero-resistance transition temperature ($T_{c0}$) of 34 K and a zero-field critical current density ($J_c$) of $1.3 times 10^6$ A/cm$^2$ were obtained. The irreversibility field was $sim$ 8 T at low temperatures, although severe pinning instability was observed. These bulk-like superconducting properties show that the in situ deposition process can be a viable candidate for MgB$_2$ Josephson junction technologies.
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