N. V. Gavrilov

Electronic band gap reduction and intense luminescence in Co and Mn ion-implanted SiO2

Cobalt and manganese ions are implanted into SiO2 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 concentrations. 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 SiO2 valence band, finding it comparable to Mn and Co monoxides. Further, we find an increasing reduction in the SiO2 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.

The formation of Ti–O tetrahedra and band gap reduction in SiO2 via pulsed ion implantation

Titanium ions are implanted into amorphous SiO2 at two different fluences using pulsed ion implantation, and the resulting samples are annealed. Bulk sensitive soft X-ray absorption spectroscopy of the Ti L2,3 edge reveal strikingly different spectra for the two fluences. Spectral simulations using multiplet crystal field theory show clearly that for low fluence the Ti ions have a local octahedral coordination, while at higher fluence the formation of Ti4+–O tetrahedra dominates. Using O K-edge X-ray absorption and emission, the effect of the Ti states on the valence and conduction bands of the host SiO2 is revealed. With the introduction of Ti tetrahedra, the band gap reduces from about 8 eV to just over 4 eV, due entirely to the Ti 3d conduction band states. These results demonstrate the possibility to obtain Ti–O tetrahedra in silica by Ti ion implantation and a suitable thermal treatment, clarify the mechanism of band gap reduction with Ti doping in SiO2, and demonstrate the sensitivity of L-edge X-ra...

Structural defects induced by Fe-ion implantation in TiO2

X-ray photoelectron spectroscopy and resonant x-ray emission spectroscopy measurements of pellet and thin film forms of TiO2 with implanted Fe ions are presented and discussed. The findings indicate that Fe-implantation in a TiO2 pellet sample induces heterovalent cation substitution (Fe2+ → Ti4+) 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 Fe3+ are detected on the surface of all doped samples due to oxygen exposure. These experimental findings are compared with density functional theory calculations of formation energies for different configurations of structural defects in the implanted TiO2:Fe system. According to our calculations, the clustering of Fe-atoms in TiO2: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 ...

Structural ordering in a silica glass matrix under Mn ion implantation

Mn(+)-implanted, amorphous SiO(2) samples were synthesized using pulsed-ion implantation without thermal annealing. The crystal and electronic structures have been studied using x-ray diffraction and synchrotron-based soft x-ray absorption and emission spectroscopy at the Si and Mn L(2,3) edges. We find a combination of small MnO clusters and Si crystallites at shallow depths while tetrahedral Mn coordination is found deeper in the host target. Through a combination of techniques, we find that the implantation process simultaneously decreases the long-range order in the near-surface region and increases order deeper in the SiO(2) host. Our results suggest Mn substitution into Si sites at deep levels catalyzes the formation of α-quartz, providing insight into the complex interactions that determine the local structure around the impurities as well as the overall changes to the crystallinity of implanted SiO(2).