Magnetic properties of copper hexadecaphthalocyanine (F16CuPc) thin films and powders

The structural and magnetic properties of F16CuPc thin films and powder, including x-ray diffraction (XRD), superconducting quantum interference device (SQUID) magnetometry, and theoretical modelling of exchange interactions are reported. Analysis of XRD from films, with thickness ranging between 100 and 160 nm, deposited onto Kapton and a perylene-3,4,9,10-tetracarboxylic-3,4,9,10-dianhydride (PTCDA) interlayer shows that the stacking angle (defined in the text) of the film is independent of the thickness, but that the texture is modified by both film thickness and substrate chemistry. The SQUID measurements suggest that all samples are paramagnetic, a result that is confirmed by our theoretical modelling including density functional theory calculations of one-dimensional molecular chains and Green's function perturbation theory calculations for a molecular dimer. By investigating theoretically a range of different geometries, we predict that the maximum possible exchange interaction between F16CuPc molecules is twice as large as that in unfluorinated copper-phthalocyanine (CuPc). This difference arises from the smaller intermolecular spacing in F16CuPc. Our density functional theory calculation for isolated F16CuPc molecule also shows that the energy levels of Kohn-Sham orbitals are rigidly shifted similar to 1 eV lower in F16CuPc compared to CuPc without a significant modification of the intramolecular spin physics, and that therefore the two molecules provide a suitable platform for independently varying magnetism and charge transport. 

Ferroelectricity in Strain-Free SrTiO3 Thin Films

Biaxial strain is known to induce ferroelectricity in thin films of nominally nonferroelectric materials such as SrTiO3. By a direct comparison of the strained and strain-free SrTiO3 films using dielectric, ferroelectric, Raman, nonlinear optical and nanoscale piezoelectric property measurements, we conclude that all SrTiO3 films and bulk crystals are relaxor ferroelectrics, and the role of strain is to stabilize longerrange correlation of preexisting nanopolar regions, likely originating from minute amounts of unintentional Sr deficiency in nominally stoichiometric samples. These findings highlight the sensitive role of stoichiometry when exploring strain and epitaxy-induced electronic phenomena in oxide films, heterostructures, and interfaces.

Substrate Clamping Effects on Irreversible Domain Wall Dynamics in Lead Zirconate Titanate Thin Films

The role of long-range strain interactions on domain wall dynamics is explored through macroscopic and local measurements of nonlinear behavior in mechanically clamped and released polycrystalline lead zirconate-titanate (PZT) films. Released films show a dramatic change in the global dielectric nonlinearity and its frequency dependence as a function of mechanical clamping. Furthermore, we observe a transition from strong clustering of the nonlinear response for the clamped case to almost uniform nonlinearity for the released film. This behavior is ascribed to increased mobility of domain walls. These results suggest the dominant role of collective strain interactions mediated by the local and global mechanical boundary conditions on the domain wall dynamics. The work presented in this Letter demonstrates that measurements on clamped films may considerably underestimate the piezoelectric coefficients and coupling constants of released structures used in microelectromechanical systems, energy harvesting systems, and microrobots.

Nanoscale Origins of Nonlinear Behavior in Ferroic Thin Films

The nonlinear response of a ferroic to an applied field has been studied through the phenomenological Rayleigh Law for over a hundred years. Yet, despite this, the fundamental physical mechanisms at the nanoscale that lead to macroscopic Rayleigh behavior have remained largely elusive, and experimental evidence at small length scales is limited. Here, it is shown using a combination of scanning probe techniques and phase field modeling, that nanoscale piezoelectric response in prototypical Pb(Zr,Ti)O3 films appears to follow a distinctly non-Rayleigh regime. Through statistical analysis, it is found that an averaging of local responses can lead directly to Rayleigh-like behavior of the strain on a macroscale. Phase-field modeling confirms the twist of the ferroelastic interface is key in enhancing piezoelectric response. The studies shed light on the nanoscale origins of nonlinear behavior in disordered ferroics.

Stripe domain structure in epitaxial (001) BiFeO3 thin films on orthorhombic TbScO3 substrate

We have analyzed the ferroelastic and ferroelectric domain structure of high crystalline quality (001) BiFeO3 films on orthorhombic (110) TbScO3 substrates. Two domains were present in stripes separated by (010) vertical boundaries, with spontaneous polarizations in adjacent domains rotated by 109 degrees. The striped morphology was caused by nucleation of only two ferroelastic domains on the low symmetry GdFeO3-type substrate. Domain engineering through substrate symmetry is an important finding for rhombohedral ferroelectric epitaxial thin films. The stripe pattern with vertical walls may be useful for extracting domain wall contributions to magnetism and electrical transport properties of BiFeO3 materials.

Nanoscale switching characteristics of nearly tetragonal BiFeO3 thin films

We have investigated the nanoscale switching properties of strain-engineered BiFeO(3) thin films deposited on LaAlO(3) substrates using a combination of scanning probe techniques. Polarized Raman spectral analysis indicates that the nearly tetragonal films have monoclinic (Cc) rather than P4mm tetragonal symmetry. Through local switching-spectroscopy measurements and piezoresponse force microscopy, we provide clear evidence of ferroelectric switching of the tetragonal phase, but the polarization direction, and therefore its switching, deviates strongly from the expected (001) tetragonal axis. We also demonstrate a large and reversible, electrically driven structural phase transition from the tetragonal to the rhombohedral polymorph in this material, which is promising for a plethora of applications.

Inorganic species of arsenic in soil solution determined by microcartridges and ferrihydrite-based diffusive gradient in thin films

The bioavailability of soil arsenic (As) is determined by its speciation in soil solution, i.e., arsenite [As(III)] or arsenate [As(V)]. Soil bioavailability studies require suitable methods to cope with small volumes of soil solution that can be speciated directly after sampling, and thereby minimise any As speciation change during sample collection. In this study, we tested a self-made microcartridge to separate both As species and compared it to a commercially available cartridge. In addition, the diffusive gradient in thin films technique (DGT), in combination with the microcartridges, was applied to synthetic solutions and to a soil spiked with As. This combination was used to improve the assessment of available inorganic As species with ferrihydrite(FH)-DGT, in order to validate the technique for environmental analysis, mainly in soils. The self-made microcartridge was effective in separating As(III) from As(V) in solution with detection by inductively coupled plasma optical emission spectrometry (ICP-OES) in volumes of only 3 ml. The DGT study also showed that the FH-based binding gels are effective for As(III) and As(V) assessment, in solutions with As and P concentrations and ionic strength commonly found in soils. The FH-DGT was tested on flooded and unflooded As spiked soils and recoveries of As(III) and As(V) were 85–104% of the total dissolved As. This study shows that the DGT with FH-based binding gel is robust for assessing inorganic species of As in soils.

Strain dependent microstructural modifications of BiCrO3 epitaxial thin films

Strain-dependent microstructural modifications were observed in epitaxial BiCrO3 (BCO) thin films fabricated on single crystalline substrates, utilizing pulsed laser deposition. The following conditions were employed to modify the epitaxial-strain: (i) in-plane tensile strain, BCOSTO [BCO grown on buffered SrTiO3 (001)] and in-plane compressive strain, BCONGO [BCO grown on buffered NdGaO3 (110)] and (ii) varying BCO film thickness. A combination of techniques like X-ray diffraction, X-ray photoelectron spectroscopy (XPS) and high resolution transmission electron microscopy (TEM) was used to analyse the epitaxial growth quality and the microstructure of BCO. Our studies revealed that in the case of BCOSTO, a coherent interface with homogeneous orthorhombic phase is obtained only for BCO film with thicknesses, d < 50 nm. All the BCOSTO films with d = 50 nm were found to be strain-relaxed with an orthorhombic phase showing 1/2 <100> and 1/4 <101> satellite reflections, the latter oriented at 45° from orthorhombic diffraction spots. High angle annular dark field scanning TEM of these films strongly suggested that the satellite reflections, 1/2 <100> and 1/4 <101>, originate from the atomic stacking sequence changes (or “modulated structure”) as reported for polytypes, without altering the chemical composition. The unaltered stoichiometry was confirmed by estimating both valency of Bi and Cr cations by surface and in-depth XPS analysis as well as the stoichiometric ratio (1 Bi:1 Cr) using scanning TEM–energy dispersive X-ray analysis. In contrast, compressively strained BCONGO films exhibited monoclinic symmetry without any structural modulations or interfacial defects, up to d ~ 200 nm. Our results indicate that both the substrate-induced in-plane epitaxial strain and the BCO film thickness are the crucial parameters to stabilise a homogeneous BCO phase in an epitaxially grown film.

Nanoscale mapping of oxygen vacancy kinetics in nanocrystalline Samarium doped ceria thin films

The position-dependent oxygen vacancy dynamics induced by a biased scanning probe microscopy tip in Samarium doped ceria thin films grown on MgO (100) substrates is investigated. The granularity of the samples gives rise to spatially dependent local electrochemical activity, as explored by electrochemical strain microscopy. The kinetics of the oxygen vacancy relaxation process is investigated separately for grain boundaries and grains. Higher oxygen vacancy concentration variation and slower diffusion are observed in the grain boundary regions as compared to the grains.

Ferroelectric nanostructures fabricated by focused-ion-beam milling in epitaxial BiFeO3 thin films

We studied a suitable route to fabricate ferroelectric islands by focused-ion-beam milling in bismuth ferrite epitaxial thin films. Piezoresponse force microscopy shows that the damage induced by the milling process is extended to 1 mu m away from the edge of the focused-ion-beam patterned islands. After a combined vacuum and oxygen atmosphere annealing procedure, ferroelectricity is fully recovered in structures with sizes down to 500 nm, while for 250 nm islands the defects at the interfaces induce polarization direction pinning.

Piezoelectric properties of PbTiO(3) thin films characterized with piezoresponse force and high resolution transmission electron microscopy

In this paper we investigate the piezoelectric properties of PbTiO(3) thin films grown by pulsed laser deposition with piezoresponse force microscopy and transmission electron microscopy. The as-grown films exhibit an upward polarization, inhomogeneous distribution of piezoelectric characteristics concerning local coercive fields, and piezoelectric coefficient. In fact, the data obtained reveal imprints during piezoresponse force microscopy measurements, nonlinearity in the piezoelectric deformation, and limited polarization reversal. Moreover, transmission electron microscopy shows the presence of defects near the film/substrate interface, which can be associated with the variations of piezoelectric properties.

Monodomain strained ferroelectric PbTiO(3) thin films: Phase transition and critical thickness study

This work demonstrates that instead of paraelectric PbTiO(3), completely c-oriented ferroelectric PbTiO(3) thin films were directly grown on (001)-SrTiO(3) substrates by pulsed-laser deposition with thickness up to 340 nm at a temperature well above the Curie temperature of bulk PbTiO(3). The influence of laser-pulse frequency, substrate-surface termination on growth, and functional properties were studied using x-ray diffraction, transmission electron microscopy, and piezoresponse force microscopy. At low growth rates (frequency 8 Hz) a domains were formed for film thickness above 20-100 nm. Due to coherency strains the Curie temperature (T(c)) of the monodomain films was increased approximately by 350 degrees C with respect to the T(c) of bulk PbTiO(3) even for 280-nm-thick films. Nonetheless, up to now this type of growth mode has been considered unlikely to occur since the Matthews-Blakeslee (MB) model already predicts strain relaxation for films having a thickness of only similar to 10 nm. However, the present work disputes the applicability of the MB model. It clarifies the physical reasons for the large increase in T(c) for thick films, and it is shown that the experimental results are in good agreement with the predictions based on the monodomain model of Pertsev et al. [Phys. Rev. Lett. 80, 1988 (1998)].