Mostra el registre complet de l'element
John Gilliland, Samuel
Segura García del Río, Alfredo (dir.) Universitat de València - FÍSICA APLICADA |
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Aquest document és un/a tesi, creat/da en: 2009 | |
Este documento está disponible también en : http://www.tesisenred.net/TDX-0311110-121121/ |
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Zn1-xMxO (M = Mn, Fe, Ni, Cu) films were deposited at optimal conditions over mica and
sapphire substrates by laser ablation of polycrystalline targets containing stoichiometric mixtures of
chemical compounds. These films were then characterised structurally, electronically, optically and
magnetically.
The structural characterisation was done by plume emission spectroscopy, XRD, XAS, XRF,
electron microscopy and microanalysis to ensure that the expected films had been correctly deposited.
Results indicated a constant chemical composition during the growth process and the resulting films
grown over sapphire were found to be c-oriented. Maximum dilute cation solubilities were determined
at 15%, 2.5%, 0.5% and 1% in the Mn, Fe, Ni and Cu DMSs, respectively. Above these limits,
secondary phases were found in diffractograms, supported by a departure of the XAS spectra from
wurtzite configura...
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Zn1-xMxO (M = Mn, Fe, Ni, Cu) films were deposited at optimal conditions over mica and
sapphire substrates by laser ablation of polycrystalline targets containing stoichiometric mixtures of
chemical compounds. These films were then characterised structurally, electronically, optically and
magnetically.
The structural characterisation was done by plume emission spectroscopy, XRD, XAS, XRF,
electron microscopy and microanalysis to ensure that the expected films had been correctly deposited.
Results indicated a constant chemical composition during the growth process and the resulting films
grown over sapphire were found to be c-oriented. Maximum dilute cation solubilities were determined
at 15%, 2.5%, 0.5% and 1% in the Mn, Fe, Ni and Cu DMSs, respectively. Above these limits,
secondary phases were found in diffractograms, supported by a departure of the XAS spectra from
wurtzite configuration and certain structures observed in SEM images.
Photoelectron spectroscopy measurements were taken to investigate the electronic properties of
the films. He-II UPS and Mg K XPS were done to investigate the electronic states of the valence band
and core electronic levels respectively. In UPS the effects of p-d repulsion could be directly observed
through the energy shift of the O 2p levels, which increased in binding energy in Mn and Fe DMSs but
decreased in the case of Zn1-xCuxO, in agreement with predictions. In XPS spectra, analysis of the
dilute cation 2p levels and their satellites revealed oxidation states in agreement with the results of the
structural characterisation.
Optical absorption measurements were taken to investigate the changes in the absorption edge
caused by the dilute cation type and concentration at low temperature and high pressure. Results were
fitted to a model based on the Elliot-Toyozawa equation to determine the optical properties. Within the
solubility limits, the optical bandgap energies of Zn1-xMnxO and Zn1-xFexO films were found to
increase by 19 ± 2 meV%Mn
-1 and 4 ± 1 meV%Fe
-1 respectively, due to the increase in p-d repulsion.
However, a decrease was observed in Cu and Ni DMSs, confirming the reversal of the p-d repulsion. In
all cases, static disorder increased with dilute cation concentration, shown by the broadening of the
continuum width and a broadening and attenuating of the exciton and its resonance with the LO
phonon. In Zn1-xMnxO films a pre-edge absorption band was observed and identified as a CTT from
Mn 3d levels to the conduction band. Decreasing temperature caused a blue-shift of the absorption
edge, the magnitude of which depended on the combined effects of the electron-phonon interaction and
static disorder. Applying high pressure in the wurtzite phase also caused a blue-shift of the absorption
edge, in agreement with theory for covalently bonded semiconductors. None of the DMSs showed a
bandgap energy variation significantly different to pure ZnO. In the rocksalt phase, the pressure
coefficient of the direct gap at could be studied, obtaining similar values to pure ZnO in all cases.
Transition pressures were explained making reference to chemical pressure effects and metastable
rocksalt Zn1-xMnxO films were recovered for Mn concentrations above 19 ± 3 %.
Finally a magnetic characterisation was done to determine the magnetisation of the DMS films
in function of applied magnetic field and temperature. Results from films grown over mica proved
difficult to analyse due to the large substrate magnetic response, so only results from films grown over
sapphire are reported. No evidence of ferromagnetism was found in single phase Zn1-xMnxO or
Zn1-xFexO. Instead, the films showed paramagnetic behaviour, except in the low temperature limit
(<1.8 K), where signs of the onset of antiferromagnetism were observed.
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RESUMEN
Se depositaron capas de Zn1-xMxO (M = Mn, Fe, Ni, Cu) en condiciones óptimas sobre sustratos
de mica y zafiro por ablación láser de blancos policristalinos compuestos de mezclas estequiométricas
de compuestos químicos. Se caracterizaron las capas estructuralmente, electrónicamente, ópticamente y
magnéticamente. Se hizo la caracterización estructural mediante espectroscopia de emisión de la
pluma, XRD, XAS, XRF, microscopía electrónica y microanálisis para determinar los límites de
solubilidad y asegurarse de que se hubieran depositado las capas esperadas. Se tomaron medidas de
espectroscopia fotoelectrónica para investigar las propiedades electrónicas de las capas. Se hizo UPS y
XPS para investigar los estados electrónicos de la banda de valencia y los estados profundos,
respectivamente. El corrimiento de los niveles O 2p mostró un aumento de repulsión p-d en Zn1-xMnxO
y Zn1-xFexO y una disminución en Zn1-xCuxO. Se tomaron medidas de absorción óptica para investigar
los cambios en el frente de absorción causados por el tipo y la concentración del catión diluido a baja
temperatura y alta presión. Se ajustaron los resultados a un modelo basado en la ecuación Elliot-
Toyozawa para determinar las propiedades ópticas. La repulsión p-d causó un aumento de la energía
del gap de Zn1-xMnxO y Zn1-xFexO en función de la concentración del catión diluido y una disminución
en los casos de Zn1-xCuxO y Zn1-xNixO. Se observó una CTT por debajo del gap en Zn1-xMnxO y un
aumento de desorden en función de la concentración del catión diluido en todos los DMS. Se
explicaron el comportamiento en función de la temperatura haciendo referencia al desorden y la
interacción electrón fonón. En función de la presión, los coeficientes del gap se mantuvieron como los
de ZnO puro en las fases wurzita y NaCl. Se explicaron las presiones de transición haciendo referencia
a la presión química. Finalmente, se hizo una caracterización magnética para determinar la
magnetización de las capas DMS de Mn y Fe en función del campo magnético aplicado y la
temperatura. Las capas no mostraron ferromagnetismo intrínseco, sino paramagnetismo y señales de
antiferromagnetismo en el límite de baja temperatura.
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