Nitrogen doping-mediated room-temperature ferromagnetism in insulating Co-doped SnO2 films

Co-doped SnO₂ films codoped with nitrogen (N) have been prepared by magnetron sputtering to investigate the effect of p-type defects on magnetic properties. The incorporation of N modifies the preferential growth orientation of the films. Multiple characterization techniques reveal that the incorporated Co²⁺ and N³⁻ ions substitute for Sn⁴⁺ and O²⁻ sites in SnO₂ lattice, respectively. As N concentration increases, the band gap of the films decreases because of the formation of Sn-N bond. Room-temperature ferromagnetism is observed in (Co, N)-codoped SnO₂ films, and the saturated magnetic moment is sensitive to the incorporated N concentration. The variations in the magnetic properties as a function of N concentration are discussed on the basis of bound magnetic polaron model.     

First-principle study of electronic structure and stability of Sn0.5Sb0.5O2

A theoretical study on Sb-doped SnO₂ has been carried out by means of periodic density functional theory (DFT) at generalized gradient approximation (GGA) level. Stability and conductivity analyses were performed based on the formation energy and electronic structures. The results show that Sn_0.5Sb_0.5O₂ solid solution is stable because the formation energy of Sn_0.5Sb_0.5O₂ is −0.06 eV. The calculated energy band structure and density of states showed that the band gap of SnO₂ narrowed due to the presence of the Sb impurity energy levels in the bottom of the conduction band, namely there is Sb 5s distribution of electronic states from the Fermi level to the bottom of conduction band after the doping of antimony. The studies provide a theoretical basis to the development and application of Sn_1−xSb_xO₂ solid solution electrode.     

Comparative photoemission study of the electronic properties of L-CVD SnO2 thin films

In this work we present the results of comparative XPS and PYS studies of electronic properties of the space charge layer of the L-CVD SnO₂ thin films after air exposure and subsequent UHV annealing at 400 °C, with a special emphasis on the interface Fermi level position.From the centre of gravity of binding energy of the main XPS Sn 3d_5/2 line the interface Fermi level position E_F − E_v in the band gap has been determined. It was in a good correlation with the value estimated from the offset of valence band region of the XPS spectrum, as well as from the photoemission yield spectroscopy (PYS) measurements. Moreover, from the valence band region of the XPS spectrum and PYS spectrum two different types of filled electronic band gap states of the L-CVD SnO₂ thin films have been derived, located at 6 and 3 eV with respect to the Fermi level.     

The influence of nickel dopant on the microstructure and optical properties of SnO2 nano-powders

The microstructure and optical properties of Ni-doped SnO2 nano-powders are studied in detail. By Ni-doping, not only the grain size reduces, but also the grain shape changes from nano-rods to spherical particles. The crystallization becomes better with annealing temperature increasing. The band gap energy decreases as nickel doping level increases. The sp-d hybridization and alloying effect due to amorphous SnO2-x phase should be responsible for the band gap narrowing effect. Nickel dopant does not change the photoluminescence （PL） peak positions.     

Enhanced gas-sensing behaviour of Ru-doped SnO2 surface: A periodic density functional approach

A theoretical study on Ru-doped rutile SnO₂(1 1 0) surface has been carried out by means of periodic density functional theory (DFT) at generalized gradient approximation (GGA-RPBE) level with a periodic supercell approach. Electronic structure analysis was performed based on the band structure and partial density of states. The results provide evidence that the electronic structures of SnO₂(1 1 0) surface are modified by the surface Ru dopant, in which Ru 4d orbital are located at the edge of the band gap region. It is demonstrated that molecular oxygen adsorption characteristics on stoichiometric SnO₂(1 1 0) surface are changed from endothermic to exothermic due to the existence of surface Ru dopant. The dissociative adsorption of molecular oxygen on the Ru_5c/SnO₂(1 1 0) surface is exothermic, which indicates that Ru could act as an active site to increase the oxygen atom species on SnO₂(1 1 0) surface. Our present study reveals that the Ru dopant on surface is playing both electronic and chemical role in promoting the SnO₂ gas-sensing property.     

Electronic structural properties and formation energy of Sn1−xPbxO2 solid solutions electrode

First-principles calculations based on density functional theory within the generalized gradient approximation have been performed for the Sn_1−xPb_xO₂ solid solution. The doped formation energies and electronic structures are also analyzed. Results show that the Sn_0.9375Pb_0.0625O₂ solid solution has the highest stability because of its minimum formation energy value of 0.04589 eV at a doping ratio of 0.0625. The SnO₂ lattice constants expand in a distorted rutile structure after Pb doping. The band structure and density of states calculations indicate that the band gap of SnO₂ narrowed due to the presence of the Pb impurity energy levels in the forbidden band, namely, Pb 6s energy band overlaps with the conductivity band in the F–Q direction. In addition, the number of electrons filled at the bottom of the conduction band increases from 0.13 to 3.96 after doping, resulting in the strengthening of the conductivity of the solid solution after doping of plumbum. The results provide a theoretical basis for the development and application of the Sn_1−xPb_xO₂ solid solution electrode.     

Sn1−xBixO2 and Sn1−xTaxO2 (0≤x≤0.75): A first-principles study

The structural, elastic, electronic and optical (x=0) properties of doped Sn_1−xBi_xO₂ and Sn_1−xTa_xO₂ (0≤x≤0.75) are studied using the first-principles pseudopotential plane-wave method within the local density approximation. The independent elastic constants C_ij and other elastic parameters of these compounds have been calculated for the first time. The mechanical stability of the compounds with different doping concentrations has also been studied. The electronic band structure and density of states are calculated and the effect of doping on these properties is also analyzed. It is seen that the band gap of the undoped compound narrowed with dopant concentration, which disappeared for x=0.26 for Bi doping and 0.36 for Ta doping. The materials thus become conductive oxides through the change in the electronic properties of the compound for x≤0.75, which may be useful for potential application. The calculated optical properties, e.g. dielectric function, refractive index, absorption spectrum, loss-function, reflectivity and conductivity of the undoped SnO₂ in two polarization directions are compared with both previous calculations and measurements.     

A study of room-temperature ferromagnetism in transition metal and fluorine-doped spray-pyrolyzed SnO2 thin films

Room-temperature ferromagnetism has been observed in Co- or Mn-doped SnO₂ and Co- and F-co-doped SnO₂ thin films. A maximum magnetic moment of 0.80μ_B/Co ion has been observed for Sn_0.90Co_0.10O_1.925−δF_0.075 thin films, whereas in the case of Sn_1−xMn_xO_2−δ it was 0.18μ_B/Mn ion for x=0.10. The magnetization of both Sn_1−xCo_xO_2−δ and Sn_1−xCo_xO_2−y−δF_y thin films depends on the free carrier concentration. An anomalous Hall effect has been observed in the case of Co-doped SnO₂ films. However, the same was not observed in the case of Mn-doped SnO₂ thin films. Carrier-mediated interaction is convincingly proved to be the cause of ferromagnetism in the case of Co:SnO₂. It is, however, proposed that no carrier-mediated interaction exists in the case of Mn:SnO₂. Present studies indicate that dopants and hence electronic cloud-lattice interaction plays an important role in inducing ferromagnetism.     

Investigation of nonlinear optical parameters of zinc based amorphous chalcogenide films

Third order nonlinear optical properties of amorphous Zn_x–S_y–Se_100−x−y chalcogenide films have been investigated using single beam transmission z-scan technique at 1064 nm of Nd:YAG laser. Measurement of optical properties of amorphous Zn_x–S_y–Se_100−x−y chalcogenide films prepared by thermal evaporation technique has been made. X-ray diffraction patterns of chalcogenide films confirm the amorphous nature. Optical band gap (E_g) has been estimated using Tauc's plot method from transmission spectra that is found to decrease with increase in content due to valence band broadening and band tailing the system. Nonlinear refractive index (n₂), nonlinear absorption coefficient (β) and third order nonlinear susceptibility (χ³) of chalcogenide films have been estimated. Self-focusing effect has been observed in closed aperture and reverse saturable absorption in open aperture scheme. Limiting threshold and dynamic range have been calculated from optical limiting studies. The increase in nonlinearity with increase in Zn content has been observed that is understood to be due to decrease in band gap on Zn doping. High nonlinearity makes these films a potential candidate for waveguides, fibers and two photon absorption in optical limiters.     

Correlation between electrical and optical properties of Cr:ZnO thin films grown by pulsed laser deposition

Highly transparent and conducting Chromium doped ZnO (Cr:ZnO) thin films with preferential c-axis orientation were grown on (0 0 0 1) sapphire substrates using buffer assisted pulsed laser deposition. The resistivity of Cr:ZnO thin films was found to decrease to a minimum value of ∼1.13×10⁻³Ω cm with the increasing Cr concentration up to ∼1.9 at.% and then increase with further increase of Cr concentration. On the contrary, the band gap and carrier concentration of Cr:ZnO thin films increased up to ∼3.37 eV and ∼2×10²⁰ cm⁻³, respectively, with the increase of Cr concentration up to ∼1.9 at.%, then decreased with further increase of Cr concentration. The increase of carrier concentration and conductivity with Cr doping at low Cr concentrations (<1.9 at.%) could be attributed to the presence of Cr in +3 valence state in ZnO thus acting as donor while decrease of carrier concentration beyond ∼1.9 at.% of Cr concentration could be attributed to the charge compensating effect due to the presence of acceptor like point defects such as oxygen interstitials. This was experimentally confirmed using x-ray photoelectron spectroscopy. The observed variation in the band gap of Cr:ZnO thin films with increasing Cr doping was attributed to the competing effects of the high free carrier concentration induced Burstein-Moss blue shift and band gap narrowing.     

Synthesis, physical and photo electrochemical characterization of La-doped SrSnO3

The transport properties of Sr_0.98La_0.02SnO_3−δ in the system Sr_1−xLa_xSnO_3−δ, after which the pyrochlore La₂Sn₂O₇ appears, were investigated over the temperature range 4.2-300 K. The oxide was found to be n-type semiconductor with concomitant reduction of Sn⁴⁺ into Sn²⁺. The magnetic susceptibility was measured down to 4.2 K and is less than 3×10⁻⁵ emu cgs mol⁻¹ consistent with itinerant electron behavior. The electron is believed to travel in a narrow band of Sn:5s character with an effective mass ∼4 m_o. The highest band gap is 4.32 eV and the optical transition is directly allowed. A further indirect transition occurs at 4.04 eV. The electrical conductivity follows an Arrhenius-type law with a thermal activation of 40 meV and occurs by small polaron hopping between nominal states Sn^4+/2+. The linear increase of thermo-power with temperature yields an electron mobility μ_300 K (2×10⁻⁴ cm² V⁻¹ s⁻¹) thermally activated. The insulating-metal transition seems to be of Anderson type resulting from random positions of lanthanum sites and oxygen vacancies. At low temperatures, the conduction mechanism changes to a variable range hopping with a linear plot Ln ρ⁻¹ vs. T⁻⁴. The photo electrochemical (PEC) measurements confirm the n-type conductivity and give an onset potential of −0.46 V_SCE in KOH (1 M). The Mott-Schottky plot C⁻²-V shows a linear behavior from which the flat band potential V_fb=+0.01 V_SCE at pH 7 and the doping density N_D=1.04×10²¹ cm⁻³ were determined.     

Controlling the electronic structure of SnO2 nanowires by Mo-doping

Mo-doped SnO2 (MTO) nanowires are synthesized by an in-situ doping chemical vapour deposition method. Raman scattering spectra indicate that the lattice symmetry of MTO nanowires lowers with the increase of Mo doping, which implies that Mo ions do enter into the lattice of SnO2 nanowire. Ultraviolet-visible diffuse reflectance spectra show that the band gap of MTO nanowires decreases with the increase of Mo concentration. The photoluminescence emission of SnO2 nanowires around 580 nm at room temperature can also be controlled accurately by Mo-doping, and it is extremely sensitive to Mo ions and will disappear when the atomic ratio reaches 0.46%.     

The study of optical properties of amorphous thin films of mixed oxides In<Subscript>2</Subscript>O<Subscript>3</Subscript>—SnO<Subscript>2</Subscript> system,deposited by co-evaporation

A discussion of optical properties of mixed oxides In₂O₃—SnO₂ system is presented. Film thickness, substrate temperature, composition (in molar %) and annealing have a profound effect on the structure and optical properties of these films. Initially the increase in band gap with the increase of SnO₂ content in In₂O₃ is due to the increase in carrier density as a result of donor electrons from tin. The decrease in band gap above the critical Sn content is caused by the defects formed by Sn atoms, which act as carrier traps rather than electron donors. The increase in band gap with film thickness is caused by the increase in free carrier density which is generated by (i) Sn atom substitution of In atom, giving out one extra electron and (ii) oxygen vacancy acting as two electrons donor. The decrease in band gap with substrate temperature and annealing is due either to the severe deficiency of oxygen, which deteriorate the film properties and reduce the mobility of the carriers, or to the formation of indium species of lower oxidation state (In²⁺).     

Band gap energy and bowing parameter of In-rich InAlN films grown by magnetron sputtering

The crystal structure, band gap energy and bowing parameter of In-rich In_xAl_1−xN (0.7 < x < 1.0) films grown by magnetron sputtering were investigated. Band gap energies of In_xAl_1−xN films were obtained from absorption spectra. Band gap tailing due to compositional fluctuation in the films was observed. The band gap of the as-grown InN measured by optical absorption method is 1.34 eV, which is larger than the reported 0.7 eV for pure InN prepared by molecular beam epitaxy (MBE) method. This could be explained by the Burstein-Moss effect under carrier concentration of 10²⁰ cm⁻³ of our sputtered films. The bowing parameter of 3.68 eV is obtained for our In_xAl_1−xN film which is consistent with the previous experimental reports and theoretical calculations.     

Visible-light photocatalytic activity of nitrogen-doped TiO2 thin film prepared by pulsed laser deposition

Nitrogen-doped titanium dioxide (TiO_2−xN_x) thin films have been prepared by pulse laser deposition on quartz glass substrates by ablated titanium dioxide (rutile) target in nitrogen atmosphere. The x value (nitrogen concentration) is 0.567 as determined by X-ray photoelectron spectroscopy measurements. UV-vis spectroscopy measurements revealed two characteristic deep levels located at 1.0 and 2.5 eV below the conduction band. The 1.0 eV level is attributable to the O vacancy state and the 2.5 eV level is introduced by N doping, which contributes to narrowing the band-gap by mixing with the O2p valence band. The enhanced degradation efficiency in a broad visible-light range was observed from the degradation of methylene blue and methylene orange by the TiO_2−xN_x film.     

Unravelling the effect of Ni doping on the structural,optical and dielectric properties of nanocrystalline SnO2

Nanocrystalline pristine and Ni doped (x= 0.05, 0.10 and 0.15) SnO₂ samples are synthesized via sol-gel process. An extensive microstructure, optical and dielectric studies are performed through several analytical techniques. Analysis of the x-ray diffraction (XRD) data through Rietveld refinement confirms tetragonal crystal structure with P4₂/mnm space group for all the samples without any impurity or secondary phase. Scanning electron microscopy (SEM) images exhibit smooth surface morphology with agglomeration of the particles and energy dispersive x-ray spectra (EDS) confirm elemental composition of the samples. The average crystallite/particles size of the samples is found to increase for 5% Ni doped SnO₂ but reduces on further increase in the Ni content. Fourier transform infrared (FTIR) spectra show vibrational modes of the functional groups present in the samples. UV-visible absorption spectra indicate a red shift on Ni doping in SnO_2, ascribed to the trapping of excitons by the oxygen vacancies and thereby creating extra energy states within the bandgap. The band gap is found to diminish from 3.81 eV for pristine SnO₂ to 3.57 eV for the sample with 15% Ni concentration. Frequency dependent dielectric measurements at room temperature reveal higher values of the dielectric constant at lower frequencies that can be described on the basis of Maxwell-Wagner theory. The results demonstrate that the oxygen vacancies play a crucial role and concentration of Ni has strong influence on the microstructure, optical and dielectric behaviour of SnO₂.     

Effect of environment and heat treatment on the optical properties of RF-sputtered SnO2 thin films

Thin films of SnO₂ were deposited by RF-magnetron sputtering on quartz substrates at room temperature in an environment of Ar and O₂. The XRD pattern shows amorphous nature of the as-deposited films. The optical properties were studied using the reflectance and transmittance spectra. The estimated optical band gap (E_g) values increase from 4.15 to 4.3 eV as the Ar gas content decreases in the process gas environment. The refractive index exhibits an oscillatory behavior that is strongly dependent on the sputtering gas environment. The Urbach energy is found to decrease with increase in band gap. The band gap is found to decrease on annealing the film. The role of oxygen defects is explored in explaining the variation of optical parameters.     

Optical properties of SnO2 nanoparticles

In recent times, considerable research efforts have been focused on the exploration of novel optical properties of nanocrystalline SnO₂ particles such as photoluminescence (PL). In the present work, spherical SnO₂ nanoparticles are synthesized by solid state reaction at different temperatures using tin chloride dihydrate and sodium hydroxide flakes as precursors. Transmission electron micrograph shows uniform and spherical SnO₂ nanoparticles of diameter 30–40 nm. Micro-Raman spectra show an inverse relationship of line-width with SnO₂ particle size. The band gap of SnO₂ is calculated by plotting (αhν)² vs. hν and extrapolating the linear portion of it to α = 0 and found it to be 3.76–4.24 eV. Photoluminescence intensity increases with the increase of solid state reaction temperature up to 873 K. This is attributed to the generation of the oxygen ion vacancies in SnO₂.     

Conversion of covalent to ionic character of V2O5–CeO2–PbO–B2O3 glasses for solid state ionic devices

xV₂O₅–xCeO₂–(30−x)PbO–(70−x) B₂O₃ glasses are synthesized by using the melt quench technique. The number of studies such as XRD, density, molar volume, optical band gap, refractive index and FTIR spectroscopy are employed to characterize the glasses. The band gap decreases from 2.20 to 1.78 eV and density increases from 3.49 to 4.25 g/cm³. FTIR spectroscopy reveals that incorporation of V₂O₅ in glass network helps to convert the structural units of [BO₃] into [BO₄]. At higher concentration of vanadium, VO vibration of [VO₅] structural units and V–O–V vibration are present. The bond ionicity of glasses increases with incorporation of V₂O₅ contents.     

(Mo + N) codoped TiO2 for enhanced visible-light photoactivity

A series of Ti_1−xMo_xO_2−yN_y samples were prepared by using sol-gel method and characterized by X-ray diffraction, transmission electron microscopy and UV-vis absorption spectroscopy. All Ti_1−xMo_xO_2−yN_y samples are anatase phase. It is found that Mo, N mono-doping can increase visible light absorption, while (Mo + N) co-doping can greatly enhance absorption in whole visible region. Results of our first-principles band structure calculations reveal that (Mo + N)-doping, especially passivated co-doping can increase the up-limit of dopant concentration and create more impurity bands in the band gap of TiO₂, which leads to a greatly increase of its visible-light absorption without a decrease of its redox potential. It reveals that (Mo + N) co-doped TiO₂ is promising for a photocatalyst with high photocalystic activity under visible light.