Vertical (La,Sr)MnO3 Nanorods from Track‐Etched Polymers Directly Buffering Substrates

A novel and general methodology for preparing vertical, complex‐oxide nanostructures from a sol–gel‐based polymer‐precursor solutions is developed using track‐etched polymers directly buffering substrates. This method is able to develop a nanostructure over the entire substrate, the dimensions and localization of the vertical nanostructures being preset by the polymeric nanotemplate. Thereby, nanostructures with lateral sizes in the range of 100 to 300 nm and up to 500 nm in height have been grown. Two examples are presented herein, the latter being the evolution of the initial, metastable nanostructure. Specifically, La_0.7Sr_0.3MnO₃ polycrystalline rods are grown at mild temperatures (800 °C); upon strong thermal activation (1000 °C) they suffer a profound transformation into vertical, single‐crystalline (La,Sr)_xO_y nanopyramids sitting on a La_0.7Sr_0.3MnO₃ epitaxial wetting layer. The driving force for this outstanding nanostructural evolution is the minimization of the total energy of the system, which is reached by reducing the grain‐boundary, total‐surface, and strain‐relaxation energies. Finally, advanced electron‐microscopy techniques are used to highlight the complex phase separation and structural transformations occurring when the metastable state is overcome.     

Investigation of the Properties of Ba-Substituted La0.7Sr0.3−x Ba x MnO3 Perovskite Manganite Films for Resistive Switching Applications

La_0.7Sr_0.3?x Ba _x MnO₃ (LSBMO: x = 0.09, 0.18, and 0.27) thin films were prepared on Pt-coated Si substrates using a radiofrequency magnetron sputtering technique at a substrate heating temperature of 450°C. The effects of varying the amount of substituted Ba²⁺ on the physical, chemical, and electrical properties of the perovskite manganite films were systematically investigated. X-Ray diffraction showed that the growth orientation and crystallinity of films were not affected by the amount of substituted Ba cations. Raman spectroscopy was used to determine the tilt of MnO₆ octahedra and the Jahn–Teller-type distortion variation of the manganite films. The change in covalent characteristics of Mn–O bonds with increasing amounts of Ba²⁺ substituent was analyzed by x-ray photoelectron spectroscopy, specifically to examine the effects of bond characteristics on the resistive switching properties of LSBMO. The resistance of the LSBMO films increased with increasing Ba²⁺ content due to an increase in the covalent nature of Mn–O bonds. The resistive switching ratio increased with increasing Ba²⁺ amount, and relationships among resistive switching, Jahn–Teller distortion, and Mn–O bond character of LSBMO films were interpreted.     

Large,Temperature‐Tunable Low‐Field Magnetoresistance in La0.7Sr0.3MnO3:NiO Nanocomposite Films Modulated by Microstructures

Magnetic properties and low‐field magnetoresistance (LFMR) in La_0.7Sr_0.3MnO₃ (LSMO):NiO nanocomposite films grown on SrTiO₃ (001) substrates, which are shown to be tunable with different microstructures, are investigated. The LSMO:NiO nanocomposite films with NiO volume ratio of 50% have a checkerboard‐like structure and show a large LFMR in a temperature range from 200 to 300 K (≈17% at 250 K with a magnetic field of 1 T). As the NiO volume ratio is increased to 70%, a nano‐columnar structure formed in the films. Their LFMR is significantly enhanced at a wide temperature range of 10–210 K. The highest value of LFMR with 41% is achieved at 10 K in a magnetic field of 1 T. The enhanced LFMR can be considered to result from the electron scattering at the ferromagnetic LSMO/NiO interfaces and magnetic tunnel junctions (MTJs) of LSMO/NiO/LSMO at the nanometer scale. These results demonstrate that large and tunable LFMR from low temperature to room temperature can be realized by controlling the microstructures in the epitaxial La_0.7Sr_0.3MnO₃:NiO nano­composite thin films, which will be expected to be applied in the devices using for a wide temperature range.     

Phase transformation and paired-plate precipitate formation in Pb0.91La0.09Zr0.65Ti0.35O3 films grown on sapphire substrates

We report on the phase transformation behavior of Pb_0.91La_0.09Zr_0.65Ti_0.35O₃ (9/65/35) PLZT films grown on r-sapphire substrates via rf-magnetron sputtering. A complex microstructure results in these films depending on deposition and annealing conditions. A random equiaxed polycrystalline grain morphology was observed after rapid thermal annealing or furnace annealing when the as-deposited films were predominantly pyrochlore. Precipitate formation (100–150 nm) was observed in PLZT films that were deposited at temperatures in excess of 490°C with a perovskite structure, after furnace annealing at 700°C. We believe that this is related to internal stresses in the films due to both the lattice mismatch and the thermal expansion mismatch between the PLZT film and the sapphire substrate.     

Thickness Dependence Study of Electron Beam Evaporated LBMO Manganite Thin Films for Bolometer Applications

La_0.7Ba_0.3MnO₃ (LBMO) thin films with different thicknesses were deposited on Si substrates using an electron beam evaporation technique for bolometer applications. To evaluate the influence of the thickness on their structural, compositional, morphological, and electrical properties, the LBMO thin films were characterized by x-ray diffraction (XRD), energy-dispersive spectroscopy, atomic force microscopy, and a four-probe method. XRD measurements showed that the crystal quality of the LBMO films improved with increasing thickness. The surface morphology revealed that the grain size and surface roughness of the films increased with increasing thickness. The resistivity increased with increasing thickness of the film. The temperature coefficient of resistance of the LBMO films decreased from 5.15%/K to 4.12%/K with increase of the film thickness from 20 nm to 100 nm.     

Effects of the incorporation of Fe on the electromagnetic and microwave absorption performance of La0.7Sr0.3MnO3±δ

The pure perovskite structure La_0.7Sr_0.3Mn_1−χFe_χO_3±δ (χ=0, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, and 0.35) powders were fabricated by the traditional solid state reaction method. Effects of the incorporation of Fe into La_0.7Sr_0.3MnO_3±δ on the permittivity and permeability were examined, and the microwave absorption performance was also investigated. The electromagnetic loss was notably enhanced, and the microwave absorption performance was improved after Fe doping. The absorbing peak shifted to the lower frequency after Fe doping. The 20 at% Fe-doped La_0.7Sr_0.3MnO_3±δ powders had the best microwave absorption property. The maximum reflection loss was −27.67 dB at 10.97 GHz, and the −6 dB absorbing bandwidth was 6.81 GHz with a matching thickness of 2 mm.     

Colossal magnetoresistance in Sol-Gel derived epitaxial thin film of Co-doped La1−xCaxMnOx

Electrical, magnetic, and magnetotransport properties of sol-gel derived epitaxial thin films of Co-doped La_1?xCa_xMnO₃ are reported. The epitaxial thin films, deposited using metal-salt routed sol-gel processing, show excellent quality of epitaxy (FWHM=0.3°). Their surface roughness is about 30Å and average grain size is 500Å. The thin films exhibit the typical behavior of colossal magnetoresistive oxide, manifesting paramagnetic semiconductor to ferromagnetic metal transition near magnetic transition. The doping of Co reduces electrical conductivity, Curie temperature (T_c) and saturation magnetization (M_s). However, the peak magnetoresistance ratio does not show a monotonous change with increasing Co content. These results are interpreted by spin-disorder scattering, magnetic inhomogeneity, and lattice distortion.     

Effect of post deposition heat treatment on microstructure parameters,optical constants and composition of thermally evaporated CdTe thin films

Thin film microstructure and its properties can be effectively altered with post deposition heat treatments. In this respect, CdTe thin films were deposited on glass substrates at a substrate temperature of 200 °C using thermal evaporation technique, followed by air annealing at different temperatures from 200 to 500 °C. Structural analysis reveals that CdTe thin films have a cubic zincblend structure with two oxide phases related to CdTe₂O₅ and CdTeO₃ at annealing temperature of 400 and 500 °C respectively. Regardless of the annealing temperature, the plane (111) was found to be the preferred orientation for all films. The crystallite size was observed to increase with annealing temperature. All films were found to display higher lattice parameters than the standard, and hence found to carry a compressive stress. Optical measurements suggest high uniformity of films both before and after post deposition heat treatment. Films annealed at 400 °C displayed superior optical properties due to its high refractive index, optical conductivity, relative density and low disorder. Furthermore, according to the compositional measurements, CdTe thin films were found to exhibit Te rich and Cd rich nature at regions near the substrate and center of the film respectively, for all annealing temperatures. However, composition of the regions near the substrate was found to become more Te rich with increasing annealing temperature. The study suggests that changing the annealing temperature as a post deposition treatment affects structural and optical properties of CdTe thin film as well as its composition. According to the observations, films annealed at 400 °C can be concluded to be the best films for photovoltaic applications due to its superior optical and structural properties.     

Faster Diffusion of Oxygen Along Dislocations in (La,Sr)MnO3+δ Is a Space-Charge Phenomenon

In displaying accelerated oxygen diffusion along extended defects, (La,Sr)MnO_3+δ is an atypical acceptor-doped perovskite-type oxide. In this study, ¹⁸O/¹⁶O diffusion experiments on epitaxial thin films of La_0.8Sr_0.2MnO_3+δ and molecular dynamics (MD) simulations are combined to elucidate the origin of this phenomenon for dislocations: Does diffusion occur along dislocation cores or along space-charge tubes? Transmission electron microscopy studies of the films revealed dislocations extending from the surface. ¹⁸O penetration profiles measured by secondary ion mass spectrometry indicated (slow) bulk diffusion and faster diffusion along dislocations. Oxygen tracer diffusivities obtained for temperatures 873 ≤ T [K] ≤ 973 were over two orders of magnitude higher for dislocations than for the bulk. The activation enthalpy of oxygen diffusion along dislocations, of (2.95 ± 0.21) eV, is surprisingly high relative to that for bulk diffusion, (2.67 ± 0.13) eV. This result militates against fast diffusion along dislocation cores. MD simulations confirmed no accelerated migration of oxide ions along dislocation cores. Faster diffusion of oxygen along dislocations in La_0.8Sr_0.2MnO_3+δ is thus concluded to occur within space-charge tubes in which oxygen vacancies are strongly accumulated. Reasons for and the consequences of space-charge zones at extended defects in manganite perovskites are discussed.     

Tunable Low‐Field Magnetoresistance in (La0.7Sr0.3MnO3)0.5:(ZnO)0.5 Self‐Assembled Vertically Aligned Nanocomposite Thin Films

Tunable and enhanced low‐field magnetoresistance (LFMR) is observed in epitaxial (La_0.7Sr_0.3MnO₃)_0.5:(ZnO)_0.5 (LSMO:ZnO) self‐assembled vertically aligned nanocomposite (VAN) thin films, which have been grown on SrTiO₃ (001) substrates by pulsed laser deposition (PLD). The enhanced LFMR properties of the VAN films reach values as high as 17.5% at 40 K and 30% at 154 K. They can be attributed to the spin‐polarized tunneling across the artificial vertical grain boundaries (GBs) introduced by the secondary ZnO nanocolumns and the enhancement of spin fluctuation depression at the spin‐disordered phase boundary regions. More interestingly, the vertical residual strain and the LFMR peak position of the VAN films can be systematically tuned by changing the deposition frequency. The tunability of the physical properties is associated with the vertical phase boundaries that change as a function of the deposition frequency. The results suggest that the tunable artificial vertical GB and spin‐disordered phase boundary in the unique VAN system with vertical ferromagnetic‐insulating‐ferromagnetic (FM‐I‐FM) structure provides a viable route to manipulate the low‐field magnetotransport properties in VAN films with favorable epitaxial quality.     

Tailoring of LaxSr1‐xCoyFe1‐yO3‐δ Nanostructure by Pulsed Laser Deposition

Pulsed Laser Deposition (PLD) was used to prepare thin films with the nominal composition La_0.58Sr_0.4Co_0.2Fe_0.8O_3‐δ (LSCF). The thin film microstructure was investigated as a function of PLD deposition parameters such as: substrate temperature, ambient gas pressure, target‐to‐substrate distance, laser fluence and frequency. It was found that the ambient gas pressure and the substrate temperature are the key PLD process parameters determining the thin film micro‐ and nanostructure. A map of the LSCF film nanostructures is presented as a function of substrate temperature (25–700 °C) and oxygen background pressure (0.013–0.4 mbar), with film structures ranging from fully dense to highly porous. Fully crystalline, dense, and crack‐free LSCF films with a thickness of 300 nm were obtained at an oxygen pressure lower than 0.13 mbar at a temperature of 600 °C. The obtained knowledge on the structure allows for tailoring of perovskite thin film nanostructure, e.g., for solid oxide fuel cell cathodes. A simple geometrical model is proposed, allowing estimation of the catalytic active surface area of the prepared thin films. It is shown that voids at columnar grain boundaries can result in an increase of the surface area by approximately 25 times, when compared to dense flat films.     

Growth-Temperature-Controlled Optical Properties of Textured MgxZn1?xO Thin Films

Pulsed laser deposition was used to grow magnesium zinc oxide thin films on amorphous fused silica substrates at several temperatures between room temperature and 750°C. In this study, the effect of growth temperature on the optical properties of textured Mg _x Zn_1−x O thin films was examined. The optical properties of the films were measured using absorption and photoluminescence spectrometry. Absorption spectra revealed that the bandgap values of textured Mg _x Zn_1−x O thin films were enhanced in films grown at higher temperatures. The absorption spectra near the absorption edge were fitted using the Urbach equation in order to investigate the effects of growth temperature on exponential band tail and bandgap. The photoluminescence spectra were measured for magnesium zinc oxide thin films deposited at 250°C, 350°C, 450°C, 550°C, and 650°C. The film grown at 350°C provided the highest excitonic peak intensity. On the other hand, the film grown at 250°C exhibited the lowest excitonic peak intensity. The excitonic peak intensity was considerably reduced in magnesium zinc oxide thin films grown at temperatures greater than 350°C. The ability to perform substrate-temperature-dependent bandgap engineering of Mg _x Zn_1−x O will enable use of this material in next-generation optical and optoelectronic devices.     

Preparation of PbTiO3 thin films by plasma enhanced MOCVD and the effect of rapid thermal annealing

Dielectric PbTiO₃-thin films were prepared on p-Si(100) substrate by plasma enhanced metalorganic chemical vapor deposition using high purity Ti(O-i-C₃H₇)₄, Pb(tmhd)₂, and oxygen. As-deposited films were post-treated by rapid thermal annealing method, and the effect of annealing was examined under various conditions. The deposition process was controlled by mixed-control scheme at temperatures lower than 350°C, but controlled by heterogeneous surface reaction at temperatures greater than 350°C. The as-deposited films showed PbO structure at 350∼400°C, but (100) and (101) PbTiO₃ orientations started to appear at 450°C. The deposition rate was increased with rf power due to the enhanced dissociation of Ti and Pb precursors. It was found that the concentration of oxygen plays an important role in crystallization of PbTiO₃ during the rapid thermal annealing. A linear relationship was obtained between the dielectric constant of PbTiO₃ films and the annealing temperature. However, the surface roughness and leakage current density increased mainly due to the defects caused by volatilization of lead and the interface layer formed during the high temperature annealing.     

Tuning the Properties of CZTS Films by Controlling the Process Parameters in Cost-Effective Non-vacuum Technique

Highly dispersive Cu₂ZnSnS₄ (CZTS) nanoparticles were successfully synthesized by a simple solvothermal route. A low cost, non-vacuum method was used to deposit CZTS nanoparticle ink on glass substrates by a doctor blade process followed by selenization in a tube furnace to form Cu₂ZnSn (S,Se)₄ (CZTSSe) layers. Different selenization conditions and particle concentrations were considered in order to improve the crystallinity and surface morphology; the annealing temperature was varied between 400°C and 550°C and the annealing time was varied between 5 min and 20 min in a selenium-nitrogen atmosphere. The influence of annealing conditions on structural, compositional, optical and electrical properties of CZTSSe thin films was studied. An improvement in the structural and surface morphology was observed with increasing of annealing temperature (up to 500°C). An enhancement in the crystallinity and surface morphology were observed for thin films annealed for 10–15 min. Absorption study revealed that the band gap energy of as-deposited CZTS thin film was approximately 1.43 eV, while for CZTSSe thin films it ranged from 1.15 eV to 1.34 eV at different annealing temperatures, and from 1.33 eV to 1.38 eV for different annealing times.     

Post-annealing Effect on Microstructures and Thermoelectric Properties of Bi0.45Sb1.55Te3 Thin Films Deposited by Co-sputtering

p-Type Bi_0.45Sb_1.55Te₃ thermoelectric (TE) thin films have been prepared at room temperature by a magnetron cosputtering process. The effect of postannealing on the microstructure and TE properties of Bi_0.45Sb_1.55Te₃ films has been investigated in the temperature range from room temperature to 350°C. x-Ray diffraction analysis shows that the annealed films have polycrystalline rhombohedral crystal structure, and the average grain size increases from 36?nm to 64?nm with increasing annealing temperature from room temperature to 350°C. Electron probe microanalysis shows that annealing above 250°C can cause Te reevaporation, which induces porous thin films and dramatically affects electrical transport properties of the thin films. TE properties of the films have been investigated at room temperature. The hole concentration shows a trend from descent to ascent and has a minimum value at the annealing temperature of 200°C, while the Seebeck coefficient shows an opposite trend and a maximum value of 245?μV?K^?1. The electrical resistivity monotonically decreases from 19.8?mΩ?cm to 1.4?mΩ?cm with increasing annealing temperature. Correspondingly, a maximum value of power factor, 27.4?μW?K^?2?cm^?1, was obtained at the annealing temperature of 250°C.     

Effects of excess Bi concentration, buffered Bi2O3 layer, and Ta doping on the orientation and ferroelectricity of chemical-solution-deposited Bi3.25La0.75Ti3O12 films

Effects of excess Bi concentration, buffered Bi₂O₃ layer, and Ta doping on the orientation and ferroelectricity of chemical-solution-deposited (CSD) Bi_3.25La_0.75Ti₃O₁₂ (BLT) films on Pt/SiO₂/Si(100) were studied. The optimum concentration of excess Bi added to the BLT films to achieve a larger remanent polarization (2Pr) was 10 mol.%. The buffered Bi₂O₃ layers could reduce the temperature for c-axis-oriented growth of BLT films from 850°C to 700°C. However, two-step annealing, i.e., first annealed at 650°C and then annealed at a temperature of 700–850°C, could effectively suppress the c-axis-oriented growth and thus improve the 2Pr of BLT films. The improvement of the 2Pr of BLT films can be explained in terms of the large polarization along the a-axis orientation and buffered Bi₂O₃ layers, which compensate the BLT films for Bi evaporation during annealing. The Ta doping can induce two contrary effects on the 2Pr of BLT films. For the (Bi_3.25La_0.75)(Ti_3−xTa_x)O₁₂ (BLTTx) films with x=0.005, the effect of a decrease of oxygen vacancies would be dominant, resulting in the improvement of 2Pr. Because the Ta concentration (x) in the BLTTx films exceeds 0.01, the effect of a decrease of grain size would become dominant, resulting in the degradation of 2Pr.     

Fabrication of metallic oxide nanowires

Micron length nanowires with varying widths were patterned in half-metallic La_2/3Sr_1/3MnO₃ (LSMO) thin films of different thicknesses, using a thin negative-tone electron beam lithography (EBL) process. Patterns were realized in the high resolution hydrogen silsesquioxane (HSQ) inorganic resist and successfully transferred to the manganite via an energetic argon ion beam etching (IBE). We have obtained wires with widths down to 65 nm and length up to 4 μm that exhibit transport properties comparable with those of unpatterned thin films.     

Effect of Rapid Thermal Annealing on Sputtered CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> Thin Films

Calcium copper titanium oxide (CaCu₃Ti₄O₁₂, abbreviated to CCTO) films were deposited on Pt/Ti/SiO₂/Si substrates at room temperature (RT) by radiofrequency magnetron sputtering. As-deposited CCTO films were treated by rapid thermal annealing (RTA) at various temperatures and in various atmospheres. X-ray diffraction patterns and scanning electron microscope (SEM) images demonstrated that the crystalline structures and surface morphologies of CCTO thin films were sensitive to the annealing temperature and ambient atmosphere. Polycrystalline CCTO films could be obtained when the annealing temperature was 700°C in air, and the grain size increased signifi- cantly with annealing in O₂. The 0.8-μm CCTO thin film that was deposited at RT for 2 h and then annealed at 700°C in O₂ exhibited a high dielectric constant (ε′) of 410, a dielectric loss (tan δ) of 0.17 (at 10 kHz), and a leakage current density (J) of 1.28 × 10⁻⁵ A/cm² (at 25 kV/cm).     

Thermo-Sensitive Ba0.64Sr0.36TiO3 Thin Film Capacitors for Dielectric Type Uncooled Infrared Sensors

Ba_0.64Sr_0.36TiO₃ (BST) thin films are prepared on Pt/Ti/SiO₂/Si₃N₄/SiO₂/Si substrates by a sol-gel method. Thermo-sensitive BST thin film capacitors with a Metal-Ferroelectrics-Metal (M-F(BST)-M) structure are fabricated as the active elements of dielectric type uncooled infrared sensors. XRD are employed to analyze the crystallographic structures of the films. AFM observations reveal a smooth and dense surface of the films with an average grain size of about 35 nm. Rapid temperature annealing (RTA) process is a very efficient way to improve crystallization quality. The preferable annealing temperature is 800°C for 1 min. The butterfly shaped C-V curves of the capacitors indicate the films have a ferroelectric nature. The dielectric constant and dielectric loss of the films at 100 kHz are 450 and 0.038, respectively. At 25°C, where the thermo-sensitive capacitors work, the temperature coefficient of dielectric constant (TCD) is about 5.9 %/°C. These results indicate that the capacitors with sol-gel derived BST thin films are promising to develop dielectric type uncooled infrared sensors.     

Effect of Temperature on Structural and Morphologic Properties of ZnO Films Annealed in Ammonia Ambient

ZnO thin films were prepared on Si(111) substrates by pulsed laser deposition (PLD). Then, the samples were annealed at different temperatures in NH₃ ambient and their properties were investigated particularly as a function of annealing temperature. The structure, morphology, and optical properties of ZnO films were studied by x-ray diffraction (XRD), Fourier transform infrared spectroscope (FTIR), scanning electron microscope (SEM), and photoluminescence (PL). The results show that the increase of annealing temperature makes for the improvement in the crystal quality and surface morphology below the temperature of 650°C. However, when the annealing temperature is above 650°C, the ZnO films will volatilize and, especially at 750°C, ZnO will volatilize completely.