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Phase growth control in low temperature PLD Co:TiO2 films by pressure

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 Added by A. J. Silvestre
 Publication date 2013
  fields Physics
and research's language is English




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This paper reports on the structural and optical properties of Co-doped TiO2 thin films grown onto (0001) Al2O3 substrates by non-reactive pulsed laser deposition (PLD) using argon as buffer gas. It is shown that by keeping constant the substrate temperature at as low as 310 C and varying only the background gas pressure between 7 Pa and 70 Pa, it is possible to grow either epitaxial rutile or pure anatase thin films, as well as films with a mixture of both polymorphs. The optical band gaps of the films are red shifted in comparison to the values usually reported for undoped TiO2, which is consistent with n-type doping of the TiO2 matrix. Such band gap red shift brings the absorption edge of the Co-doped TiO2 films into the visible region, which might favour their photocatalytic activity. Furthermore, the band gap red shift depends on the films phase composition, increasing with the increase of the Urbach energy for increasing rutile content.



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The properties of epitaxial Bi2FeCrO6 thin films, recently synthesized by pulsed laser deposition, have partially confirmed the theoretical predictions (i.e. a magnetic moment of 2 muB per formula unit and a polarization of ~80 microC/cm2 at 0K). The existence of magnetic ordering at room temperature for this material is an unexpected but very promising result that needs to be further investigated. Since magnetism is assumed to arise from the exchange interaction between the Fe and Cr cations, the magnetic behaviour is strongly dependent on both their ordering and the distance between them. We present here the successful synthesis of epitaxial Bi2FexCryO6 (BFCO x/y) films grown on SrTiO3 substrates using dual crossed beam pulsed laser deposition. The crystal structure of the films has different types of (111)-oriented superstructures depending on the deposition conditions. The multiferroic character of BFCO (x/y) films is proven by the presence of both ferroelectric and magnetic hysteresis at room temperature. The oxidation state of Fe and Cr ions in the films is shown to be 3+ only and the difference in macroscopic magnetization with Fe/Cr ratio composition could only be due to ordering of the Cr3+ and Fe3+ cations therefore to the modification of the exchange interaction between them.
Metal-insulator transition is observed in the La0.8Sr0.2MnO3 thin films with thickness larger than 5 unit cells. Insulating phase at lower temperature appeared in the ultrathin films with thickness ranging from 6 unit cells to 10 unit cells and it is found that the Mott variable range hopping conduction dominates in this insulating phase at low temperature with a decrease of localization length in thinner films. A deficiency of oxygen content and a resulted decrease of the Mn valence have been observed in the ultrathin films with thickness smaller than or equal to 10 unit cells by studying the aberration-corrected scanning transmission electron microscopy and electron energy loss spectroscopy of the films. These results suggest that the existence of the oxygen vacancies in thinner films suppresses the double-exchange mechanism and contributes to the enhancement of disorder, leading to a decrease of the Curie temperature and the low temperature insulating phase in the ultrathin films. In addition, the suppression of the magnetic properties in thinner films indicates stronger disorder of magnetic moments, which is considered to be the reason for this decrease of the localization length.
Chromia (Cr2O3) has been extensively explored for the purpose of developing widespread industrial applications, owing to the convergence of a variety of mechanical, physical and chemical properties in one single oxide material. Various methods have been used for large area synthesis of Cr2O3 films. However, for selective area growth and growth on thermally sensitive materials, laser-assisted chemical vapour deposition (LCVD) can be applied advantageously. Here we report on the growth of single layers of pure Cr2O3 onto sapphire substrates at room temperature by low pressure photolytic LCVD, using UV laser radiation and Cr(CO)6 as chromium precursor. The feasibility of the LCVD technique to access selective area deposition of chromia thin films is demonstrated. Best results were obtained for a laser fluence of 120 mJ cm-2 and a partial pressure ratio of O2 to Cr(CO)6 of 1.0. Samples grown with these experimental parameters are polycrystalline and their microstructure is characterised by a high density of particles whose size follows a lognormal distribution. Deposition rates of 0.1 nm s-1 and mean particle sizes of 1.85 {mu}m were measured for these films.
227 - P. Ferriani , I. Turek , S. Heinze 2007
We propose to tailor exchange interactions in magnetic monolayer films by tuning the adjacent non-magnetic substrate. As an example, we demonstrate a ferromagnetic-antiferromagnetic phase transition for one monolayer Fe on a Ta(x)W(1-x)(001) surface as a function of the Ta concentration. At the critical Ta concentration, the nearest-neighbor exchange interaction is small and the magnetic phase space is dramatically broadened. Complex magnetic order such as spin-spirals, multiple-Q, or even disordered local moment states can occur, offering the possibility to store information in terms of ferromagnetic dots in an otherwise zero-magnetization state matrix.
In many transition metal oxides (TMOs), oxygen stoichiometry is one of the most critical parameters that plays a key role in determining the structural, physical, optical, and electrochemical properties of the material. However, controlling the growth to obtain high quality single crystal films having the right oxygen stoichiometry, especially in a high vacuum environment, has been viewed as a challenge. In this work, we show that through proper control of the plume kinetic energy, stoichiometric crystalline films can be synthesized without generating oxygen defects, even in high vacuum. We use a model homoepitaxial system of SrTiO3 (STO) thin films on single crystal STO substrates. Physical property measurements indicate that oxygen vacancy generation in high vacuum is strongly influenced by the energetics of the laser plume, and it can be controlled by proper laser beam delivery. Therefore, our finding not only provides essential insight into oxygen stoichiometry control in high vacuum for understanding the fundamental properties of STO-based thin films and heterostructures, but expands the utility of pulsed laser epitaxy of other materials as well.
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