This is the abstract. The results of measurements of X-ray photoelectron spectra (XPS) of a-SiO2-host material after pulsed implantation with [Mn+] and [Co+, Mn+]-ions as well as DFT-calculations are presented. The low-energy shift is found in XPS Si
2p and O 1s core-levels of single [Mn+] and dual [Co+, Mn+] pulsed ion-implanted a-SiO2 (E = 30 keV, D = 2*10^17 cm^-2) with respect to those of untreated a-SiO2.The similar changes are found in XPS Si 2p and O 1s of stishovite compared to those of quartz. This means that the pulsed ion-implantation induces the local high pressure effect which leads to an appearance of SiO6-structural units in alpha-SiO2 host, forming stishovite-like local atomic structure. This process can be described within electronic bonding transition from the four-fold quartz-like to six-fold stishovite-like high-pressure phase in SiO2 host-matrix. It is found that such octahedral conversion depends on the fluence and starts with doses higher than D = 3*10^16 cm^-2.
Cobalt and manganese ions are implanted into SiO$_2$ over a wide range of concentrations. For low concentrations, the Co atoms occupy interstitial locations, coordinated with oxygen, while metallic Co clusters form at higher implantation concentratio
ns. For all concentrations studied here, Mn ions remain in interstitial locations and do not cluster. Using resonant x-ray emission spectroscopy and Anderson impurity model calculations, we determine the strength of the covalent interaction between the interstitial ions and the SiO$_2$ valence band, finding it comparable to Mn and Co monoxides. Further, we find an increasing reduction in the SiO$_2$ electronic band gap for increasing implantation concentration, due primarily to the introduction of Mn- and Co-derived conduction band states. We also observe a strong increase in a band of x-ray stimulated luminescence at 2.75 eV after implantation, attributed to oxygen deficient centers formed during implantation.
By studying Fe-doped ZnO pellets and thin films with various x-ray spectroscopic techniques, and complementing this with density functional theory calculations, we find that Fe-doping in bulk ZnO induces isovalent (and isostructural) cation substitut
ion (Fe2+ -> Zn2+). In contrast to this, Fe-doping near the surface produces both isovalent and heterovalent substitution (Fe3+ -> Zn2+). The calculations performed herein suggest that the most likely defect structure is the single or double substitution of Zn with Fe, although, if additional oxygen is available, then Fe substitution with interstitial oxygen is even more energetically favourable. Furthermore, it is found that ferromagnetic states are energetically unfavourable, and ferromagnetic ordering is likely to be realized only through the formation of a secondary phase (i.e. ZnFe2O4), or codoping with Cu.
X-ray photoelectron spectroscopy (XPS) and resonant x-ray emission spectroscopy (RXES) measurements of pellet and thin film forms of TiO$_2$ with implanted Fe ions are presented and discussed. The findings indicate that Fe-implantation in a TiO$_2$ p
ellet sample induces heterovalent cation substitution (Fe$^{2+}rightarrow$ Ti$^{4+}$) beneath the surface region. But in thin film samples, the clustering of Fe atoms is primarily detected. In addition to this, significant amounts of secondary phases of Fe$^{3+}$ are detected on the surface of all doped samples due to oxygen exposure. These experimental findings are compared with density functional theory (DFT) calculations of formation energies for different configurations of structural defects in the implanted TiO$_2$:Fe system. According to our calculations, the clustering of Fe-atoms in TiO$_2$:Fe thin films can be attributed to the formation of combined substitutional and interstitial defects. Further, the differences due to Fe doping in pellet and thin film samples can ultimately be attributed to different surface to volume ratios.
The electronic structures of Sn and Pb implanted SiO2 are studied using soft X-ray absorption (XAS) and emission (XES) spectroscopy. We show, using reference compounds and ab initio calculations, that the presence of Pb-O and Sn-O interactions can be
detected in the pre-edge region of the oxygen K-edge XAS. Via analysis of this interaction-sensitive pre-edge region, we find that Pb implantation results primarily in the clustering of Pb atoms. Conversely, with Sn implantation using identical conditions, strong Sn-O interactions are present, showing that Sn is coordinated with oxygen. The varying results between the two ion types are explained using both ballistic considerations and density functional theory calculations. We find that the substitution of Pb into Si sites in SiO2 requires much more energy than substituting Sn in these same sites, primarily due to the larger size of the Pb ions. From these calculated formation energies it is evident that Pb requires far higher temperatures than Sn to be soluble in SiO2. These results help explain the complex processes which take place upon implantation and determine the final products.
