High-resolution transmission electron microscopy investigation of the nanostructure of undoped and Pt-doped nanocrystalline pulsed laser deposited SnO2 thin films

Pulsed laser deposition (PLD) was used to grow nanocrystalline SnO₂ thin films onto alumina substrates. The reactive PLD process was carried out at different substrate deposition temperatures (T_d) between 20 and 600 °C under an oxygen background pressure of 150 mtorr. The same PLD technique was used to produce SnO₂ films in situ-doped with Pt (at the level of ∼2 at. %) through the concomitant ablation of both SnO₂ target and Pt strips. Conventional and high-resolution transmission electron microscopy (HRTEM) observations have revealed that the microstructure of the PLD SnO₂ films is highly sensitive to their deposition temperature. Indeed, its changes from a porous granular structure with extremely fine equiaxed grains (∼4 nm diameter), at T_d=20 °C to a very compact and textured columnar structure characterized by SnO₂ columns (∼25 nm diameter) composed of grains of ∼12 nm of diameter, at T_d=600 °C. In addition, the PLD SnO₂ films were found to exhibit the highest nanoporosity at T_d=300 °C which also coincides with the granular-to-columnar microstructural transition. On the other hand, the microstructure of the Pt-doped SnO₂ films, deposited at 300 °C, was found to contain a high density of defects, such as twin boundaries and edge dislocations. By combining HRTEM and EDS microanalysis, we were able to show that the Pt-dopant self-organizes into spherical nanoparticles (1-2 nm diameter) randomly distributed at the SnO₂ grain boundaries. Finally, doping the films with such platinum nanoclusters is found to affect the SnO₂ nanostructure by particularly reducing the SnO₂ mean grain size (from ∼10 nm when undoped to ∼6 nm for the doped films).     

Fluorinated Eu‐Doped SnO2 Nanostructures with Simultaneous Phase and Shape Control and Improved Photoluminescence

Fluorinated Eu‐doped SnO₂ nanostructures with tunable morphology (shuttle‐like and ring‐like) are prepared by a hydrothermal method, using NaF as the morphology controlling agent. X‐ray diffraction, field‐emission scanning electron microscopy, high‐resolution transmission electron microscopy, X‐ray photoelectron spectroscopy, and energy dispersive spectroscopy are used to characterize their phase, shape, lattice structure, composition, and element distribution. The data suggest that Eu³⁺ ions are uniformly embedded into SnO₂ nanocrystallites either through substitution of Sn⁴⁺ ions or through formation of Eu‐F bonds, allowing for high‐level Eu³⁺ doping. Photoluminescence features such as transition intensity ratios and Stark splitting indicate diverse localization of Eu³⁺ ions in the SnO₂ nanoparticles, either in the crystalline lattice or in the grain boundaries. Due to formation of Eu‐F and Sn‐F bonds, the fluorinated surface of SnO₂ nanocrystallites efficiently inhibits the hydroxyl quenching effect, which accounts for their improved photoluminescence intensity.     

Grain size effect on the universality of AC conductivity in SnO2

Nanocrystalline tin oxide (SnO₂) material with different grain sizes was synthesized by using a chemical precipitation method. This material was characterized by using the X-ray diffraction and transmission electron microscopy. The electrical properties of compressed nanocrystalline SnO₂ were studied by using impedance spectroscopy. AC conductivity data for SnO₂ material having grain sizes between 9 and 34 nm were analyzed using a power law. The exponent n is found to be 0.5 for bulk (34 nm) and unity for material with grain size below 18 nm. The results show a universal behavior for very low average grain sizes and the non-universal behavior for larger grain sizes even at room temperature.     

Pulsed Laser Ablation for Tin Dioxide: Nucleation,Growth, and Microstructures

Pulsed-laser ablation approaches are being developed for the growth of oxide thin films as versatile platform for advanced applications. Semiconducting SnO ₂ thin film is of fundamental importance in the advancement of microdevices. In this review, SnO ₂ thin films of various microstructures have been made using the pulsed-laser deposition method. The microstructural aspects include tetragonal, porous, and orthorhombic structure characteristics. The quantum-dots and dynamic simulations of SnO ₂ nanocrystals have blossomed into a submonolayer regime devoted to the nucleation and growth for these functional films. SnO ₂ thin films with some of the microstructural features may have great implications for the development of novel prototype gas sensors and transparent conduction electrodes.     

Laser induced modification of surface structures

The results on surface modification of materials of different structures; morphology, grain sizes, density and porosity by exposure to nanosecond laser light are given. Laser induced changes in their surface characteristics are presented. Surface layers of Si₃N₄, SiC dense ceramics and BN graphite and turbostratic pressed powders are studied by scanning electron microscopy to reveal the new nanostructures (nanowires or nanotubes) and new morphologies. A pronounced evolution in structure and grain size of BN graphite powders was demonstrated in laser processing layers.     

Synthesis and characterization of single crystalline SnO<Subscript>2</Subscript> nanorods by high-pressure pulsed laser deposition

Tin oxide (SnO₂) nanorods were grown by high-pressure pulsed laser deposition (PLD). The nanorods were grown without the use of a catalyst but required high background pressure growth in order to realize small grain columnar growth and nanorod formation, with nanorod formation most favored on non-epitaxial substrates. The structures and morphology were characterized by field emission scanning electron microscopy (FESEM) and high resolution transmission electron microscopy (HRTEM). X-ray diffraction and HRTEM analysis indicate that the as-grown SnO₂ nanorods are single crystals with a rutile structure. The nanorods are approximately 50–90 nm in diameters and 1.5 μm in length. This method provides an approach for large area synthesis of one dimensional SnO₂ nanostructure materials. PACS 81.16.Mk; 61.46.-w; 81.07.-b     

Synthesis and Optical Properties of Eu3+ Ion Doped Nanocrystalline Hydroxyapatites

The Ca₁₀(PO₄)₆(OH)₂ hydroxyapatite (HA) nanopowders doped with Eu³⁺ ions were prepared using a wet synthesis method. Their structure and morphology were investigated. The XRD analysis has proven a single-phase of HA nanocrystallites. The average sizes of HA nanocrystallites calcinated at 400°C and 700°C were determined to be about 20 nm and 30 nm, respectively. The emission and excitation spectra as well as the fluorescence decay rates of Eu³⁺ ion doped HA nanocrystallites were measured. Particular attention was given to the spectroscopic properties of Eu³⁺ ions as a luminescent probe of nanocrystalline HA structure as a result of varying annealing temperature and dopant concentration. The Judd-Ofelt analysis of f-f transitions of Eu³⁺:HA nanocrystallites was performed. The effect of calcination temperatures on grain sizes and luminescence properties is noted and discussed.     

High Pressure effects on electrical resistivity and dielectric properties of nanocrystalline SnO2

Nanocrystalline tin oxide (SnO₂) was prepared by chemical precipitation method with different grain sizes. The X-ray diffraction studies showed the structural stability of nanocrystalline SnO₂ under high-pressure. Electrical and dielectric properties were studied on these samples using complex impedance spectroscopy under different hydrostatic pressures. Electrical resistivity and dielectric studies showed a transition in nanocrystalline SnO₂ when it was subjected to high-pressure. The transition pressures obtained from both the resistivity and dielectric measurements agree with each other. The transition pressures were found to increase considerably with the decrease in grain size. Dielectric constant was found to decrease with the reduction of grain size. In order to find whether the transition with pressure is structure- related or not, Raman spectroscopy was done at normal temperature and pressure (NTP) and as a function of pressure at room temperature. Raman modes at NTP showed lines which correspond to tetragonal rutile structure of SnO₂. In situ high-pressure Raman measurements were carried out up to 3.38 GPa. No structural change was found with pressure.     

Structural and spectral properties of SnO2 nanocrystal prepared by microemulsion technique

Extrafine SnO₂ nanocrystals as small as 2.4 nm were synthesized by the microemulsion method. The grain sizes and crystallization process were measured and investigated by X-ray diffraction. Two growth processes were proposed, and the activation energies of 4.3 and 23 KJ/mol were obtained for respective low-and fast-growth processes. TEM micrographs and the selected-area diffraction recorded their morphology and crystallization, well crystallized at about 773 K. All the IR modes measured by FT-IR spectrometer were assigned. The 616 cm^-1 mode after annealing at 673 K showed fine crystallization. The temperature dependence of the Raman spectra shows that increase in intensity and decrease in linewidth of the 636 cm^-1 mode with the increasing grain size indicate a phonon confinement effect. A new 330 cm^-1 Raman mode originally inactive in bulk, was observed in the SnO₂ nanocrystal by size effect. A low frequency mode at 76 cm^-1 shifts to 38 cm^-1 as the temperature goes up 873 K, which can be characterized to determine the SnO₂ grain sizes. PACS 61.46.+w; 61.10.-i; 78.30.-j; 81.20.-n     

Microstructural and electrical characterizations of tungsten-doped La2Mo2O9 prepared by spray pyrolysis

La₂Mo_{2 ? x} W _x O₉ (x?=?0, 0.5, 1.0, and 1.3) nanocrystalline powders were synthesized by spray pyrolysis (SP) assisted by an ultrasonic atomizer. Microstructure, sinterability and thermal stability of the prepared powders were investigated. Spherical particles of 430 to 530 nm in diameter and crystallite sizes in the 30–44 nm range were obtained. Additionally, the fine microstructure has allowed the reduction of sintering temperatures with respect to that usually reported for a solid-state reaction (SSR) method. Pellets with a variety of average grain sizes and morphologies were obtained by applying different sintering programs starting from La₂Mo_{2 ? x} W _x O₉ powders (x?=?0 and 1.3) obtained by SP and SSR processes. The electrical properties of these ionic conductors were analyzed by Electrochemical Impedance Spectroscopy (EIS) and correlated with microstructural observations. No significant variation of the electrical properties of these ionic conductors was found as compared to conventional ceramics with remarkable microstructural differences.     

Impedance spectroscopy analysis of Li<Subscript>2</Subscript>SnO<Subscript>3</Subscript>

In this work, Li₂SnO₃ has been synthesized by the sol–gel method using acetates of lithium and tin. Thermogravimetric analysis (TGA) has been applied to the precursor of Li₂SnO₃ to determine the suitable calcination temperature. The formation of the compound calcined at 800 °C for 9 h has been confirmed by X-ray diffraction (XRD) analysis. The Li₂SnO₃ is then pelletized and electrically characterized by using electrochemical impedance spectroscopy (EIS) in the frequency range from 50 Hz to 1 MHz. The complex impedance spectra clearly show the dominating presence of the grain boundary effect on electrical properties whereas the complex modulus plots reveal two semicircles which are due to the grain (bulk) and grain boundary. The spectra of imaginary parts of both impedance and modulus versus frequency show the existence of peaks with the modulus plots exhibiting two peaks that are ascribed to the grain and grain boundary of the material. The peak maximum shifts to higher frequency with an increase in temperature and the broad nature of the peaks indicates the non-Debye nature of Li₂SnO₃. The activation energy associated with the dielectric relaxation obtained from the electrical impedance spectra is 0.67 eV. From the electric modulus spectra, the activation energies related to conductivity relaxation in the grain and grain boundary of Li₂SnO₃ are 0.59 and 0.69 eV, respectively. The conductivity–temperature relationship is thermally assisted and obeys the Arrhenius rule with the activation energy of 0.66 eV. The conduction mechanism of Li₂SnO₃ is via hopping.     

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.     

Effect of microstructural characteristics on the magnetic properties of sol-gel synthesized ZnMnO

In this paper we report the effect of microstructural characteristics on the magnetic properties of sol-gel synthesized Mn-doped ZnO. The microstructural characteristics of the samples (e.g., grain sizes and their distribution) have been varied by changing the sintering temperature (T_S) and sintering duration (T_H). Weak room temperature ferromagnetism (RTFM) has been observed in the samples sintered for ∼8 h at 500, 600, 700, 800 and 900 °C. The ferromagnetic fraction and the saturation magnetization, however, first increase as T_S increases from 500 to 600 °C and after that both start decreasing. On the other hand, the samples sintered for ∼12 h at the same temperatures show paramagnetic behavior at room temperature. Field emission scanning electron microscope (FESEM) results show enhancement in the grain sizes with the increase in both T_S and T_H. Energy dispersive X-ray (EDAX) results show increase in the oxygen content in the sample with increase in both T_S and T_H. X-ray diffractometer (XRD) measurements reveal that the basic crystal structure of all the samples corresponds to the wurtzite structure of pure ZnO together with some minor impurities. The correlation between the observed magnetic properties and the microstructural characteristics of the samples has been discussed in this paper.     

Scattering mechanisms of charge carriers in transparent conducting oxide films

Scattering mechanisms of charge carriers in Transparent Conducting Oxide (TCO) films have been analyzed theoretically. For the degenerate polycrystalline TCO films with relatively large crystallite sizes and high carrier concentrations (higher than 5 × 10¹⁸ cm^–3), the depletion layers between crystallites are very thin compared to the crystallite sizes, and the grain boundary scattering on electrical carriers makes a small contribution to limit the mobility of the films. Instead of thermionic emission current, a tunneling current dominates the electron transport over grain boundaries. The Petritz model which is based on thermionic emission and extensively quoted in literature should not be applicable. The main scattering mechanisms for the TCO films are ionized impurity scattering in the low-temperature range and lattice vibration scattering in the high-temperature range. The ionized impurity scattering mobility is independent of temperature and the mobility due to thermal lattice vibration scattering is inversely proportional to the temperature. The results obtained from Hall measurements on our ZnO, ITO, SnO₂ and SnO₂:F films prepared with various methods supports the analysis.     

Thermoreflectance studies in CdNiTe nanocrystalline films

CdNiTe ternary semiconductor thin films were deposited using the cathodic erosion by radiofrequency technique (r.f. sputtering), on 7059 Corning glass substrates. Cd_1−xNi_xTe targets with different Ni compositions in the range 0<x<0.15 were used. Structural analysis in these samples using SEM and X-ray diffraction have shown that films are polycrystalline with grain sizes between 26 and 35 nm; for higher Ni-content, films have smaller grain sizes. As-grown samples and thermal-annealed films in an inert atmosphere at temperatures of 300 and 400 °C were studied using the thermoreflectance spectroscopy (TR) at room temperature. From these measurements the bandgap energy variation as a function of the nanocrystallite size and the annealing temperatures was obtained. From the TR spectra a systematic shift to higher energies of the E₀-point as the grain size decreases has been measured, and we have interpreted this result as due to the CdTe–Ni alloying process added to a quantum-size effect in which the nanocrystallites act as quantum dots. We discuss the TR lineshapes and their evolution with thermal annealing.     

纳米板钛矿基二氧化钛中的晶格畸变

借助精确的Ｘ射线衍射测量,结合独立衍射峰对不同晶粒度纳米板钛矿基二氧化钛样品中板钛矿和金红石相的微结构参量进行了较细致的研究,给出了标明物相、晶面指数（ｈｋｌ）和晶面间距ｄｈｋｌ值详细分析结果的系列ＸＲＤ谱,并得到了晶面间距、晶格常数、轴比、晶胞体积等参数数值及其相对常规粗晶的变化情况,从而初步揭示出其晶粒微结构的尺寸效应。首次发现,纳米板钛矿基二氧化钛样品中板钛矿和金红石相晶粒均存在着非单调的各     

The infrared vibration characteristics of SnO2 nanoparticles

The infrared vibration characteristics of SnO₂ nanoparticles with different sizes were studied using the infrared spectra. The Fröhlich modes were observed in experiments and compared with the theoretical values. The influence of phonon localization resulting from quantum size effects on the infrared spectra of SnO₂ nanoparticles is discussed.     

Mössbauer study of SnO<Subscript>2</Subscript> powders doped with dilute <Superscript>57</Superscript>Fe prepared by a sol-gel method

SnO₂ powders, doped with various ⁵⁷Fe contents were prepared by a sol-gel method, and annealed finally at 500 °C and 650 °C. These samples were characterized by Mössbauer spectroscopy, vibrating sample magnetometer (VSM), scanning electron microscopy (SEM), and X-ray diffraction (XRD) to investigate the relationship of magnetic properties, grain sizes, annealing temperatures and Mössbauer parameters. The particle sizes of SnO₂ powders reduced to less than 100 nm with the increase of Fe contents up to 5%. Rutile SnO₂ was the only phase obtained for all samples. Room temperature Mössbauer spectra suggest the presence of two different paramagnetic iron sites for all samples and one magnetically relaxed species for those samples with the lowest iron concentrations. The magnetization increased with the Fe content, but was reduced for the samples annealed at 650 °C perhaps due to a segregation of α-Fe₂O₃ doped with tin.     

Co-doping effect of SnO2 and ZnO in In2O3 ceramics: Change in solubility limit and electrical properties

In this study, SnO₂ and ZnO were co-doped in In₂O₃, and the phase development and electrical characteristics were examined. When Zn²⁺ was added to 20 at.% Sn⁴⁺ contained In₂O₃, in which a large amount of In₄Sn₃O₁₂ second phase exists, the amount of the second phase decreased as the content of Zn²⁺ increased, which promoted grain growth and increased carrier mobility. In the case of a simultaneous substitution of Sn⁴⁺ and Zn²⁺ into In₂O₃ with almost the same atomic ratio, a large grain size without second phase was observed, while small grain sizes with many second phases were developed when Sn⁴⁺ and Zn²⁺ were added with different atomic ratios. The electrical characteristics analyzed by Hall effect measurement showed that the electron mobility and conductivity showed a close relationship with the microstructure, while the carrier concentration was almost constant regardless of the Zn²⁺ content.     

Structural,electrical and magnetic properties of (Fe,Co) co-doped SnO2 diluted magnetic semiconductor nanostructures

Nanostructures (NSs) of basic composition Sn_1−xFe_x/2Co_x/2O₂ with x=0.00, 0.04, 0.06, 0.08 and 0.1 were synthesized by citrate-gel route and characterized to understand their structural, electrical and magnetic properties. X-ray diffraction and Raman spectroscopy were used to confirm the formation of single phase rutile type tetragonal structure. The crystallite sizes calculated by using Williamson Hall were found to decrease with increasing doping level. In addition to the fundamental Raman peaks of rutile SnO₂, the other three weak Raman peaks at about 505, 537 and 688 cm⁻¹ were also observed. Field emission scanning electron microscopy studies showed the emergence of structural transformation. Electric properties such as dc electrical resistivity as a function of temperature and ac conductivity as a function of frequency were also studied. The variation of dielectric properties with frequency reveals that the dispersion is due to Maxwell–Wagner type of interfacial polarization in general. Hysteresis loops were clearly observed in M–H curves of Fe and Co co-doped SnO₂ NSs. However, pure SnO₂ nanoparticles (NPs) showed paramagnetic behaviour which vanished at higher values of magnetic field. The grain and grain boundary contribution in the conduction process is estimated through complex impedance plot fitted with non-linear least square (NLLS) approach which shows that the role of grain boundaries increases rapidly as compared to the grain volume with the increase of Fe and Co ions in to system.