Self‐Assembled Heteroepitaxial Oxide Nanocomposite Thin Film Structures: Designing Interface‐Induced Functionality in Electronic Materials

Achieving self‐assembling/self‐organizing systems is the holy grail of nanotechnology. Spontaneous organization is not unique to the physical sciences since nature has been producing such systems for millions of years. In biological systems global patterns emerge from numerous interactions among lower‐level components of the system. The same is true for physical systems. In this review, the self‐assembly mechanisms of oxide nanocomposite films, as well as the advantageous functionalities that arise from such ordered structures, are explored.     

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.     

Effect of substrate smoothness on the microstructure of YBa9n2Cu3O7−x/Y2O3/YBa2Cu3O7−x trilayers

Transmission electron microscopy was used to analyze the microstructure of YBa₂Cu₃O_7−x/Y₂O₃/YBa₂Cu₃O_7−x trilayer structures deposited by off-axis sputtering on MgO substrates with varying degrees of roughness. Substrate surface hillocks with a peak-to-valley height of about 4.5 nm were found to contribute to strain that extended through the film and disrupted the smoothness of the Y₂O₃ layer. In some cases, these hillocks served as nucleation sites for yttria precipitates. Such defects may seriously jeopardize the realization of weak-link Josephson junctions.     

A Three Component Self‐Assembled Epitaxial Nanocomposite Thin Film

A self‐assembled three phase epitaxial nanocomposite film is grown consisting of ≈3 nm diameter fcc metallic Cu nanorods within square prismatic SrO rocksalt nanopillars in a Sr(Ti,Cu)O_3‐δ perovskite matrix. Each phase has an epitaxial relation to the others. The core–shell‐matrix structures are grown on SrTiO₃ substrates and can also be integrated onto Si using a thin SrTiO₃ buffer. The structure is made by pulsed laser deposition in vacuum from a SrTi_0.75Cu_0.25O₃ target, and formed as a result of the limited solubility of Cu in the perovskite matrix. Wet etching removes the 3 nm diameter Cu nanowires leaving porous SrO pillars. The three‐phase nanocomposite film is used as a substrate for growing a second epitaxial nanocomposite consisting of CoFe₂O₄ spinel pillars in a BiFeO₃ perovskite matrix, producing dramatic effects on the structure and magnetic properties of the CoFe₂O₄. This three‐phase vertical nanocomposite provides a complement to the well‐known two‐phase nanocomposites, and may offer a combination of properties of three different materials as well as additional avenues for strain‐mediated coupling within a single film.     

Preparation of 3 Inch Double-Sided YBa2Cu3O7-X High Temperature Superconducting Thin Films

Owing to its excellent electrical property,YBCO thin film is much better than metal in the application for microwave devices. It makes the devices smaller, lighter, and with higher quality factor and lower insertion loss. YBCO thin film has attracted attentions for many years. Aiming at the uniformity and property of 3-inch double-sided YBCO thin film, the following aspects is considered in this dissertation:     

Properties of Flame Sprayed Ce0.8Gd0.2O1.9‐δ Electrolyte Thin Films

Thin films of Ce_0.8Gd_0.2O_1.9‐δ (CGO) are deposited by flame spray deposition with a deposition rate of about 30 nm min^?1. The films (deposited at 200 °C) are dense, smooth, and particle‐free and show a biphasic amorphous/nanocrystalline microstructure. Isothermal grain growth and microstrain are determined as a function of dwell time and temperature and correlated to the electrical conductivity. CGO films annealed for 10 h at 600 °C present the best electrical conductivity of 0.46 S m^?1 measured at 550 °C. Reasons for the superior performance of films annealed at low temperature over higher‐temperature‐treated samples are discussed and include grain‐size evolution, microstrain relaxation, and chemical decomposition. Nanoindentation measurements are conducted on the CGO thin films as a function of annealing temperature to determine the hardness and elastic modulus of the films for potential application as free‐standing electrolyte membranes in low‐temperature micro‐SOFCs (solid oxide fuel cells).     

Interfacial properties of YBa2Cu3O7−x thin films on AI2O3 substrates prepared by pulsed laser deposition

The interfaces of YBa₂Cu₃O_7−x (YBCO) superconducting thin films grown on (1 102) r-plane A1₂O₃ by pulsed laser deposition have been investigated by a transmission electron microscopy and an Auger electron spectroscopy depth profile. We used the PrBa₂Cu₃O_7−x (PBCO) buffer layer to prevent the interdiffusion and compared the interfaces of YBCO/A1₂O₃ and YBCO/PBCO/A1₂O₃. The intermediate layer in the YBCO film deposited on bare sapphire is visible between the film and the substrate but no boundary layer in the film grown on PBCO buffered sapphire was observed directly by the cross-section image of TEM. The thickness of the intermediate layer in the film on bare sapphire is about 30 nm. This result of TEM observation is consistent with that of AES depth profile.     

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.     

Systematic Control of Nucleation Density in Poly(3‐Hexylthiophene) Thin Films

While molecular ordering via crystallization is responsible for many of the impressive optoelectronic properties of thin‐film semiconducting polymer devices, crystalline morphology and its crucial influence on performance remains poorly controlled and is usually studied as a passive result of the conditions imposed by film deposition parameters. A method for systematic control over crystalline morphology in conjugated polymer thin films by very precise control of nucleation density and crystal growth conditions is presented. A precast poly(3‐hexylthiophene) film is first swollen into a solution‐like state in well‐defined vapor pressures of a good solvent, while the physical state of the polymer chains is monitored using in situ UV–vis spectroscopy and ellipsometry. Nucleation density is selected by a controlled deswelling of the film or by a self‐seeding approach using undissolved crystalline aggregates that remain in the swollen film. Nucleation densities ranging successively over many orders of magnitude are achieved, extending into the regime of spherulitic domains 10 to 100 μm in diameter, a length scale highly relevant for typical probes of macroscopic charge transport such as field‐effect transistors. This method is presented as a tool for future systematic study of the structure‐function relation in semicrystalline semiconducting polymers in a broad range of applications.     

Voltage‐Controlled Nonstoichiometry in Oxide Thin Films: Pr0.1Ce0.9O2−δ Case Study

While the properties of functional oxide thin films often depend strongly on oxygen stoichiometry, there have been few means available for its control in a reliable and in situ fashion. This work describes the use of DC bias as a means of systematically controlling the stoichiometry of oxide thin films deposited onto yttria‐stabilized zirconia substrates. Impedance spectroscopy is performed on the electrochemical cell Pr_0.1Ce_0.9O_2?δ (PCO)/YSZ/Ag for conditions: T = 550 to 700 °C, pO ₂ = 10^?4 to 1 atm, and ΔE = ‐100 to 100 mV. The DC bias ΔE is used to control the effective pO ₂ or oxygen activity at the PCO/YSZ interface. The non‐stoichiometry (δ) of the PCO films is calculated from the measured chemical capacitance (C_chem ). These δ values, when plotted isothermally as a function of effective pO ₂, established, either by the surrounding gas composition alone, or in combination with applied bias, agree well with each other and to predictions based on a previously determined defect model. These results confirm the suitability of using bias to precisely control δ of thin films in an in situ fashion and simultaneously monitor these changes by measurement of C_chem . Of further interest is the ability to reach effective pO ₂s as high as 280 atm.     

Integration of Self‐Assembled Epitaxial BiFeO3–CoFe2O4 Multiferroic Nanocomposites on Silicon Substrates

Perovskite‐spinel epitaxial nanocomposite thin films are commonly grown on single crystal perovskite substrates, but integration onto a Si substrate can greatly increase their usefulness in devices. Epitaxial BiFeO₃–CoFe₂O₄ nanocomposites consisting of CoFe₂O₄ pillars in a BiFeO₃ matrix are grown on (001) Si with two types of buffer layers: molecular beam epitaxy (MBE)‐grown SrTiO₃‐coated Si and pulsed‐laser‐deposited (PLD) Sr(Ti_0.65Fe_0.35)O₃/CeO₂/yttria‐stabilized ZrO₂/Si. The nanocomposite grows with the same crystallographic orientation and morphology as that observed on single crystal SrTiO₃ when the buffered Si substrates are smooth, but roughness of the Sr(Ti_0.65Fe_0.35)O₃ promoted additional CoFe₂O₄ pillar orientations with 45° rotation. The nanocomposites on MBE‐buffered Si show very high magnetic anisotropy resulting from magnetoelastic effects, whereas the hysteresis of nanocomposites on PLD‐buffered Si can be understood as a combination of the hysteresis of the Sr(Ti_0.65Fe_0.35)O₃ film and the CoFe₂O₄ pillars.     

Metal organic chemical vapor deposition of superconducting YBa2Cu3O7-x thin films

The discovery of YBCO superconductors has stimulated a great deal of scientific and technological research into thin films of these materials. Because the MOCVD technique is known to produce high quality films in the III/V and II/VI material groups, our approach has been to apply the method to superconducting thin films. Thin films were grown in a vertical high speed (0–2000 rpm) rotating disk reactor. The source materials were metalβ-diketonates kept at temperatures in excess of 100° in order to obtain growth rates of 0.3 to 0.5μm/hr. The precursors were transported to the chamber with a nitrogen carrier and injected separately in order to avoid any gas phase reactions. The chamber pressure was maintained at 76 Torr with an oxygen partial pressure of 38 Torr. A resistance heater was used to keep the substrate temperature at 500° YBa₂Cu₃O_7-x films were deposited simultaneously on a variety of substrates such as (100) MgO, (1-102) sapphire, (100) SrTiO₃ and (100) YSZ. Full XPS spectra were collected for the binary oxides. The scans demonstrate the existence of Y₂O₃, BaO, and CuO with the correct valence state for the metallic species. Energy dispersive analysis of x-ray (EDAX) was used to determine film compositions by comparing EDAX spectral intensity to a known superconducting standard. Appropriate changes were made in the precursor flows to correct the stoichiometry. The as-grown films were dark brown and semi-transparent. Cross-sectional SEM photomicrographs revealed an ordered columnar structure. After annealing at 950–980° however, the films on (100) SrTiO₃ appeared dull black and opaque. The surface morphology exhibited smooth large plate-like grains. X-ray data clearly display an orthorhombic phase, with c-axis perpendicular to the substrate surface. Four point resistance measurements for films on (100) SrTiO₃ show the onset of superconductivity at 90 K with a complete loss of resistance at 88 K. This sharp (≤2K) transition shows the high quality of these MOCVD grown YBCO films and are the first reported results from a large area (2 × 50 mm substrates) commercial reactor.     

Facile Single‐Precursor Synthesis and Surface Modification of Hafnium Oxide Nanoparticles for Nanocomposite γ‐Ray Scintillators

Inorganic nanoparticles/polymer nanocomposites provide a low cost, high performance alternative for gamma scintillation. However, inorganic nanoparticles used thus far suffer from either moderate atomic numbers or low band gaps, limiting the gamma stopping power and photoelectron production in these systems. Here, a highly efficient, facile single‐precursor synthesis protocol is reported for hafnium oxide nanoparticles with an average diameter of 5 nm. The nanoparticle surface is further functionalized for the fabrication of highly transparent bulk‐size nanocomposite monoliths (2 mm thick, transmittance at 550 nm >75%) with nanoparticle loadings up to 40 wt% (net hafnium wt% up to 28.5%). Using poly(vinyltoluene) as the matrix, 2‐(4‐tert‐butylphenyl)‐5‐(4‐biphenylyl)‐1,3,4‐oxadiazole and 1,4‐bis(5‐phenyl‐2‐oxazolyl)benzene as the cascade fluors, and hafnium oxide nanoparticles as the gamma sensitizer, the nanocomposite monolith of 1 cm diameter and 2 mm thickness is fabricated capable of producing a full energy photopeak for 662 keV gamma rays, with the best deconvoluted photopeak energy resolution <8%.     

Nanostructured Crystalline Comb Polymer of Perylenebisimide by Directed Self‐Assembly: Poly(4‐vinylpyridine)‐pentadecylphenol Perylenebisimide

Well defined nanostructured polymeric supramolecular assemblies are formed when an asymmetric perylenebisimide substituted with ethylhexyl chains on one end and functionalized with 3‐pentadecylphenol at the other termini ( PDP‐UPBI ) is complexed with poly(4‐vinylpyridine) (P4VP) via a non‐covalent specific interaction such as hydrogen‐bonding. The resulting P4VP(PDP‐UPBI) _n complexes are fully solution processable. The bulk structure and morphologies of the supramolecular film studied using small angle and wide angle X‐ray scattering reveals highly crystalline nature of the complex. Thin film morphology of the 1:1 complex analyzed using transmission electron microscopy shows uniform lamellar structures in the domain range of 5–10 nm. A clear trend of improved electrical parameters in P4VP(PDP‐UPBI) system compared to pristine ( PDP‐UPBI ) is observed from space charge limited current measurements. In short, a simple and facile method to obtain spatially defined organization of n‐type semiconductor perylenebisimide molecules using hydrogen bonding interactions with P4VP as the structural motif is showcased herein.     

Interactive Growth Effects of Rare‐Earth Nanoparticles on Nanorod Formation in YBa2Cu3Ox Thin Films

The controlled growth of self‐assembled second‐phase nanostructures has been shown to be an essential tool for enhancing properties of several composite oxide thin film systems. Here, the role of Y₂O₃ nanoparticles on the growth of BaZrO₃ (BZO) nanorods is investigated in order to understand the mechanisms governing their self‐assembly in YBa₂Cu₃O_7–x (YBCO) thin films and to more fully control the resulting defect landscape. By examining the microstructure and current‐carrying capacity of BZO‐doped YBCO films, it is shown that the nanorod growth dynamics are significantly enhanced when compared to films double‐doped with BZO and Y₂O₃ nanoparticles. The average nanorod length and associated critical current densities are found to increase at a significantly higher rate in the absence of Y₂O₃ nanoparticles when the growth temperature is increased. Using microstructural data from transmission electron microscopy studies and the response in critical current density, the interactive effects of multiple dopants that must be considered to fully control the defect landscape in oxide thin films are shown.     

Steering the Growth of Metal Ad‐particles via Interface Interactions Between a MgO Thin Film and a Mo Support

The coincidence lattice formed between a crystalline MgO film and a Mo(001) support is found to be an ideal template to produce long‐range ordered ensembles of Fe and Cr particles for electronic, magnetic and chemical applications. The structural and electronic properties of this super‐lattice are analyzed by means of scanning tunnelling microscopy and density functional theory. The different registers of atoms at the interface induce periodic changes in the MgO lattice parameter, in the metal‐oxide binding length, and the workfunction. These variations modulate the adsorption landscape for Cr and Fe atoms and give rise to the observed ordering phenomena. Preferred nucleation and growth is revealed in those regions of the coincidence lattice that have a small lattice mismatch with the ad‐particles and enable electron‐transfer processes with the support.