Experimental and theoretical study of electronic and hyperfine properties of hydrogenated anatase (TiO2_2): defects interplay and thermal stability

In this study we report on the results from emission $^{57}$Fe M${\"o}$ssbauer Spectroscopy experiments, using dilute $^{57}$Mn implantation into pristine (TiO$_2$) and hydrogenated anatase held at temperatures between 300-700 K. Results of the electronic structure and local environment are complemented with ab-initio calculations. Upon implantation both Fe$^{2+}$ and Fe$^{3+}$ are observed in pristine anatase, where the latter demonstrates the spin-lattice relaxation. The spectra obtained for hydrogenated anatase show no Fe$^{3+}$ contribution, suggesting that hydrogen acts as a donor. Due to the low threshold, hydrogen diffuses out of the lattice. Thus showing a dynamic behavior on the time scale of the $^{57}$Fe 14.4 keV state. The surrounding oxygen vacancies favor the high-spin Fe$^{2+}$ state. The sample treated at room temperature shows two distinct processes of hydrogen motion. The motion commences with the interstitial hydrogen, followed by switching to the covalently bound state. Hydrogen out-diffusion is hindered by bulk defects, which could cause both processes to overlap. Supplementary UV-Vis and electrical conductivity measurements show an improved electrical conductivity and higher optical absorption after the hydrogenation. X-ray photoelectron spectroscopy at room temperature reveals that the sample hydrogenated at 573 K shows presence of both Ti$^{3+}$ and Ti$^{2+}$ states. This could imply that a significant amount of oxygen vacancies and -OH bonds are present in the samples. Theory suggests that in the anatase sample implanted with Mn(Fe), probes were located near equatorial vacancies as next-nearest-neighbours, whilst a metastable hydrogen configuration is responsible for the annealing behavior

Defect annealing in Mn/Fe-implanted TiO2(rutile)

A study of the annealing processes and charge state of dilute Fe in rutile TiO2 single crystals was performed in the temperature range 143-662 K, utilizing online 57Fe emission Mossbauer spectroscopy following low concentrations ( 350 K

Lattice sites, charge states and spin–lattice relaxation of Fe ions in 57Mn+ implanted GaN and AlN

The lattice sites, valence states, resulting magnetic behaviour and spin–lattice relaxation of Fe ions in GaN and AlN were investigated by emission Mössbauer spectroscopy following the implantation of radioactive $^{57}Mn^+$ ions at ISOLDE/CERN. Angle dependent measurements performed at room temperature on the 14.4 keV γ-rays from the 57Fe Mössbauer state (populated from the $^{57}$Mn $β ^−$ decay) reveal that the majority of the Fe ions are in the 2+ valence state nearly substituting the Ga and Al cations, and/or associated with vacancy type defects. Emission Mössbauer spectroscopy experiments conducted over a temperature range of 100–800 K show the presence of magnetically split sextets in the “wings” of the spectra for both materials. The temperature dependence of the sextets relates these spectral features to paramagnetic $Fe^{3+}$ with rather slow spin–lattice relaxation rates which follow a $T^2$ temperature dependence characteristic of a two-phonon Raman process

Annealing studies combined with low temperature emission Mössbauer spectroscopy of short-lived parent isotopes: Determination of local Debye–Waller factors

An extension of the online implantation chamber used for emission Mössbauer Spectroscopy (eMS) at ISOLDE/CERN that allows for quick removal of samples for offline low temperature studies is briefly described. We demonstrate how online eMS data obtained during implantation at temperatures between 300 K and 650 K of short-lived parent isotopes combined with rapid cooling and offline eMS measurements during the decay of the parent isotope can give detailed information on the binding properties of the Mössbauer probe in the lattice. This approach has been applied to study the properties of Sn impurities in ZnO following implantation of $^{119}$In ($T_{½}$ = 2.4 min). Sn in the 4+ and 2+ charge states is observed. Above $T$ > 600 K, Sn$^{2+}$ is observed and is ascribed to Sn on regular Zn sites, while Sn$^{2+}$ detected at $T$ < 600 K is due to Sn in local amorphous regions. A new annealing stage is reported at $T$ ≈ 550 K, characterized by changes in the Sn$^{4+}$ emission profile, and is attributed to the annihilation of close Frenkel pairs

Temperature and dose dependence of defect complex formation with ion implanted Mn/Fe in ZnO

57Fe Mössbauer spectroscopy following ion implantation of radioactive 57Mn+ ( T1/2=85.4 s) has been applied to study the formation of Fe/Mn implantation-induced defects in ZnO at temperatures between 319 and 390 K. The formation of ferric iron–vacancy complexes is found to depend strongly on the implanted dose and to be faster and more efficient at higher temperatures. The results at these temperatures suggest the mobility of the Zn vacancy, together with vacancy trapping at the substitutional Mn/Fe impurities are responsible for the formation of Fe–VZn complexe