Structural, optical and magnetic properties of pure and 3d metal dopant-incorporated SnO2 nanoparticles.

Dilute magnetic oxide semiconductors doped with transition metals have attracted significant attention both theoretically and experimentally due to their interesting and debatable magnetic behavior. In this work, we investigated the influence of Fe, Co and Ni doping on the structural, optical and magnetic properties of SnO2 nanoparticles, which were produced via a simple sol-gel technique. Raman spectroscopy, XRD, XPS, TEM, FT-IR characterizations were performed to study the crystal structure and morphology of the pure and doped nanoparticles, which confirmed the tetragonal rutile structure of the SnO2 nanoparticles. The XPS analysis revealed the incorporation of divalent dopant ions in the host matrix. The Raman plots indicated the generation of the cassiterite crystal structure, structural disorder and oxygen vacancies in the pure and doped SnO2 nanoparticles. The UV-visible plots indicated a decrease in the bandgap for the doped SnO2 nanoparticles because doping introduced defect levels in the band gap. The photoluminescence study showed the creation of oxygen vacancies due to the doping of different charge states of dopants. The magnetic study based on varying the temperature and field of magnetization revealed the diamagnetic nature of SnO2 at 300 K and 5 K respectively, and the concurrence of ferromagnetic (FM) and paramagnetic (PM) nature in doped SnO2 nanoparticles. The bound polaron model was used to explain the co-existence of FM and PM behavior in all the doped SnO2 nanoparticles.

Crystal structure of monoclinic hafnia (HfO2) revisited with synchrotron X-ray, neutron diffraction and first-principles calculations.

A study on the crystal structure of monoclinic HfO2 has been performed using synchrotron X-ray and neutron diffraction data separately, as well as a combination of both. The precision of the structural parameters increases significantly due to application of the neutron diffraction technique. The experimental oxygen positions in HfO2, derived precisely, are visualized only by semi-local density functional calculations in terms of the calculated electronic band gap, but are not captured as accurately by using hybrid functionals.

Visible range optical absorption, Urbach energy estimation and paramagnetic response in Cr-doped TiO2 nanocrystals derived by a sol-gel method.

We have carried out a detailed study of the morphological, structural, optical and magnetic properties of Cr doped TiO2 nanocrystals with doping concentrations varying from 3 to 12 atomic weight%. The results obtained from transmission electron microscopy analysis, size-strain plots of all the Cr-doped samples and crystallite size estimation reveal the particle size of the prepared nanocrystals to be well below 10 nm, which is observed to exhibit a decreasing trend with an increase in the Cr dopant concentration. All the samples crystallize in the anatase tetragonal phase of TiO2, which is confirmed from the Rietveld refinement of the X-ray diffraction patterns and the different modes present in the Raman spectra. The Eg(1) mode shows a clear red shift and broadening with increase in the Cr concentration, which indicates the replacement of Ti ions with Cr ions in the TiO2 lattice. The possibility of the presence of different functional groups present is verified by Fourier transform infra-red spectroscopy. The presence of Cr3+ and Ti4+ is confirmed from the X-ray photoelectron spectroscopy (XPS) results suggesting the formation of oxygen vacancies to compensate for the charge neutrality. The XPS results validate the Cr3+ existence in the Cr:TiO2 system and corroborate with a slight peak shift towards lower diffraction angle and further confirm the substitutional doping in the present case. Enhanced visible range optical absorption and a clear red shift associated with the absorption edge also suggest the incorporation of Cr3+ ions into the host system. The estimated band-gap of Cr-doped TiO2 nanocrystals reveals a decreasing trend with increasing Cr concentration. The Urbach energy associated with all the Cr-doped samples signifies the presence of oxygen vacancy related defects in the present system, which is further verified using photoluminescence (PL) spectra, and the deconvolution of the PL spectra provides an insight into the oxygen vacancy defects associated with the system. Paramagnetic (PM) behaviour is observed with an increase in the PM moment, suggesting the increase in isolated Cr ions with increase in the Cr concentration, which is further explained using a bound magnetic polaron (BMP) model. Isolated BMP formation could be the reason for the observed PM behavior of the present system, where the trapping of 3d electrons associated with Cr3+ in the vacancy sites could ultimately lead to fewer overlapped BMPs, yielding a net PM moment. The present Cr:TiO2 system could be modified with tailored optical and magnetic properties for functional applications such as magneto-optics and optoelectronic devices.

Structural, optical and magnetic behavior of sol-gel derived Ni-doped dilute magnetic semiconductor TiO2 nanocrystals for advanced functional applications.

Dilute magnetic semiconductors based on TiO2 nanocrystals are the most promising class of materials exhibiting unique optical and magnetic properties. In the present investigation, we have performed a systematic study on the structural, morphological, optical and magnetic behavior of Ni-doped TiO2, synthesized via a simple, cost-effective sol-gel route. X-ray diffraction patterns together with Raman spectra confirmed the tetragonal anatase phase of Ni-doped TiO2. High-resolution transmission electron microscopy images indicated the formation of highly crystalline nanocrystals, and the compositional homogeneity of all the samples was confirmed from energy dispersive X-ray fluorescence spectroscopic studies. The functional groups in the samples were identified by Fourier transform infrared spectroscopy. UV-visible and photoluminescence (PL) spectroscopy were performed to provide an insight into the band-gap narrowing in the Ni-doped TiO2 nanocrystals. X-ray photoelectron spectroscopy results signified the existence of Ti4+ and Ni2+ in all the prepared samples. A decrease in coercivity was observed with Ni substitution, and at lower Ni concentration, the magnetic behavior was attributed to the bound magnetic polarons associated with the oxygen vacancy defects arising during the synthesis procedure. PL analysis revealed the presence of defects in the system and Langevin fitting was employed to estimate the concentration of bound magnetic polarons arising as a result of these defects. The band-gap narrowing and the enhanced magnetic moment observed in Ni-doped TiO2 reveal the potential of this semiconductor for advanced functional applications such as magneto-optics and spintronics.

Defect mediated mechanism in undoped, Cu and Zn-doped TiO2 nanocrystals for tailoring the band gap and magnetic properties.

Oxide based dilute magnetic semiconductor materials have been of great interest over the years due to their potential use in spintronic devices. However, the variations in the magnetic behavior of the materials have raised concerns regarding the origin of ferromagnetic properties which still needs to be explored. Manipulation of magnetic behavior in oxide based dilute magnetic semiconductors has become a challenge due to the interplay of intrinsic defects present in the material. TiO2 nanocrystals have been studied largely due to their challenging optical and magnetic properties. The present investigation studies in detail the structural, morphological, optical and magnetic behavior of non-magnetic element (Cu and Zn) doped TiO2, synthesized via a simple sol-gel technique. X-ray diffraction patterns and Raman spectra confirm the anatase phase and high resolution transmission electron microscopic results clearly indicate the formation of highly crystalline nanocrystals in all the samples with particle size ranging from 5-15 nm. Energy dispersive X-ray fluorescence spectroscopic studies reveal the compositional homogeneity of all the investigated samples. The presence of functional groups and molecular interactions were identified by Fourier transform infrared spectroscopy. Optical properties were studied through UV-visible and photoluminescence spectroscopy from which a significant reduction in band gap in Cu-doped TiO2 nanocrystals was found. X-ray photoelectron spectra confirm the presence of Ti3+, Cu2+, Cu+ and Zn2+ in Cu and Zn-doped TiO2 samples. The concept of bound magnetic polarons associated with the vacancy defects at both Ti, Cu, Zn and oxygen sites is used to explain the induced weak ferromagnetic behavior in undoped, Cu and Zn-doped TiO2 at room temperature. The overlapping of bound magnetic polarons could be the source of ferromagnetism irrespective of the non-magnetic nature of the dopant ion. The concentration of bound magnetic polarons is estimated using a Langevin fit and a detailed understanding of the variation of defect mediated magnetic properties is established with the help of PL analysis. A significant reduction in bandgap along with enhanced magnetization observed in the Cu-doped TiO2 material makes it suitable as a potential candidate for spintronics and magneto-optics applications. Room temperature magnetic properties of the Zn doped sample show a diamagnetic tail which is explained based on the defect centers and oxidation states of dopant ions present in the sample which is further verified with the help of XPS results.

Particle size dependence on magnetic and electrical properties of (Ni0.8Fe0.2)10C90 granular composites.

The granular structure and electrical transport behavior of ball milled magnetic permalloy particles and graphite forming (Ni0.8Fe0.2)10C90 granular composites have been reported. Retaining the composite composition to be 90:10 and varying the particle size of permalloy, the electronic transport properties have been carried out down to 4 K under the external applied magnetic field of 50 kOe. All the samples show semiconducting like behavior and positive magnetoresistance (MR) in the temperature range 4-300 K. A strong anisotropic magnetoresistance in these samples has also been observed. The highest 31% longitudinal and 6.8% transverse magnetoresistance values have been observed in 40 hrs ball milled (Ni0.8Fe0.2)10C90 composite. From these studies, we suggest that the magnetic component present in the sample may not be playing a major role in obtaining large positive MR values, which is in deviation with the earlier reports.