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P.P. and C.W. acknowledge partial support by Swiss National Science Foundation Division II grant 200021_178782. L.R.D. acknowledges support from the US National Science Foundation under grant DMR‐1708615. L.W.M. acknowledges support from the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division under Contract No. DE‐AC02‐05‐CH11231 (Materials Project program KC23MP) for the growth and study of defect structures in ferroic materials. A.B.N. gratefully acknowledges support from the Engineering and Physics Sciences Research Council (EPSRC) through grants EP/R023751/1 and EP/L017008/1. Deterministic control of the intrinsic polarization state of ferroelectric thin films is essential for device applications. Independently of the well-established role of electrostatic boundary conditions and epitaxial strain, the importance of growth temperature as a tool to stabilize a target polarization state during thin film growth is shown here. Full control of the intrinsic polarization orientation of PbTiO3 thin films is demonstrated-from monodomain up, through polydomain, to monodomain down as imaged by piezoresponse force microscopy-using changes in the film growth temperature. X-ray diffraction and scanning transmission electron microscopy reveal a variation of c-axis related to out-of-plane strain gradients. These measurements, supported by Ginzburg-Landau-Devonshire free energy calculations and Rutherford backscattering spectroscopy, point to a defect mediated polarization gradient initiated by a temperature dependent effective built-in field during growth, allowing polarization control not only under specific growth conditions, but ex-situ, for subsequent processing and device applications. Publisher PDF

Complex-oxide materials tuned to be near phase boundaries via chemistry/composition, temperature, pressure, etc. are known to exhibit large susceptibilities. Here, we observe a strain-driven nanoscale phase competition in epitaxially constrained Bi0.7La0.3FeO3 thin films near the antipolar-nonpolar phase boundary and explore the evolution of the structural, dielectric, (anti)ferroelectric, and magnetic properties with strain. We find that compressive and tensile strains can stabilize an antipolar PbZrO3-like Pbam phase and a nonpolar Pnma orthorhombic phase, respectively. Heterostructures grown with little to no strain exhibit a self-assembled nanoscale mixture of the two orthorhombic phases, wherein the relative fraction of each phase can be modified with film thickness. Subsequent investigation of the dielectric and (anti)ferroelectric properties reveals an electric-field-driven phase transformation from the nonpolar phase to the antipolar phase. X-ray linear dichroism reveals that the antiferromagnetic-spin axes can be effectively modified by the strain-induced phase transition. This evolution of antiferromagnetic-spin axes can be leveraged in exchange coupling between the antiferromagnetic Bi0.7La0.3FeO3 and a ferromagnetic Co0.9Fe0.1 layer to tune the ferromagnetic easy axis of the Co0.9Fe0.1. These results demonstrate that besides chemical alloying, epitaxial strain is an alternative and effective way to modify subtle phase relations and tune physical properties in rare earth-alloyed BiFeO3. Furthermore, the observation of antiferroelectric-antiferromagnetic properties in the Pbam Bi0.7La0.3FeO3 phase could be of significant scientific interest and great potential in magnetoelectric devices because of its dual antiferroic nature.

In this work, thermochromic Cr2O3/VO2/SiO2 (CVS) sandwich structures on glass substrates were designed and fabricated by magnetron sputtering method. Optical design and calculation were employed to optimize the structure using a optimization program. The bottom Cr2O3 layer provides a structural template for improving the crystallinity of VO2 and increasing the luminous transmittance of the structure. Then, the VO2 layer with a monoclinic (M) phase at low temperature undergoes a reversible phase-transition to rutile (R) phase at high temperature for solar modulation. The top SiO2 layer not only acts as an antireflection layer but also greatly enhances the environmental stability of the multilayer structures as well as providing a self-cleaning layer for versatility of smart coatings. According to optical measurements, the fabricated CVS multilayer structure exhibits excellent optical performance with ultrahigh solar modulation ability ( Δ T sol = 16.1%) and an improved luminous transmittance ( T lum , lt = 54.0%), which is nearly the maximum simulation value for VO2-based multilayer thin coatings. Meanwhile, stability and deterioration as well as relative mechanisms of the VO2 coatings were also investigated by monitoring the valence change of the vanadium element. The proposed structure shows remarkable environmental stability due to the dual-protection from the Cr2O3 and the SiO2 layer, which shows negligible deterioration even after accelerated aging of 103 h and 4*103 fatigue cycles, while VO2-single layer samples almost become invalid. Finally, energy-efficient effect was successfully demonstrated using CVS coated glass as the roof of a “winter garden”.

The effects of growth conditions on the chemistry, structure, electrical leakage, dielectric response, and ferroelectric behavior of Ba1−xTiOy thin films are explored. Although single-phase, coherently-strained films are produced in all cases, small variations in the laser fluence during pulsed-laser deposition growth result in films with chemistries ranging from BaTiO3 to Ba0.93TiO2.87. As the laser fluence increases, the films become more barium deficient and the out-of-plane lattice parameter expands (as much as 5.4% beyond the expected value for Ba0.93TiO2.87 films). Stoichiometric BaTiO3 films are found to be three orders of magnitude more conducting than Ba0.93TiO2.87 films and the barium-deficient films exhibit smaller low-field permittivity, lower loss tangents, and higher dielectric maximum temperatures. Although large polarization is observed in all cases, large built-in potentials (shifted loops) and hysteresis-loop pinching are present in barium-deficient films – suggesting the presence of defect dipoles. The effects of these defect dipoles on ferroelectric hysteresis are studied using first-order reversal curves. Temperature-dependent current–voltage and deep-level transient spectroscopy studies reveal at least two defect states, which grow in concentration with increasing deficiency of both barium and oxygen, at ∼0.4 eV and ∼1.2 eV above the valence band edge, which are attributed to defect–dipole complexes and defect states, respectively. The defect states can also be removed via ex post facto processing. Such work to understand and control defects in this important material could provide a pathway to enable better control over its properties and highlight new avenues to manipulate functions in these complex materials.

A strain-driven orthorhombic (O) to rhombohedral (R) phase transition is reported in La-doped BiFeO3 thin films on silicon substrates. Biaxial compressive epitaxial strain is found to stabilize the rhombohedral phase at La concentrations beyond the morphotropic phase boundary (MPB). By tailoring the residual strain with film thickness, we demonstrate a mixed O/R phase structure consisting of O phase domains measuring tens of nanometers wide within a predominant R phase matrix. A combination of piezoresponse force microscopy (PFM), transmission electron microscopy (TEM), polarization–electric field hysteresis loop (P–E loop), and polarization maps reveal that the O-R structural change is an antiferroelectric to ferroelectric (AFE-FE) phase transition. Using scanning transmission electron microscopy (STEM), an atomically sharp O/R MPB is observed. Moreover, X-ray absorption spectra (XAS) and X-ray linear dichroism (XLD) measurements reveal a change in the antiferromagnetic axis orientation from out of plane...

Antiferroelectric PbZrO3 is being considered for a wide range of applications where the competition between centrosymmetric and noncentrosymmetric phases is important to the response. Here, we focus on the epitaxial growth of PbZrO3 thin films and understanding the chemistry–structure coupling in Pb1+δZrO3 (δ = 0, 0.1, 0.2). High-quality, single-phase Pb1+δZrO3 films are synthesized via pulsed-laser deposition. Although no significant lattice parameter change is observed in X-ray studies, electrical characterization reveals that while the PbZrO3 and Pb1.1ZrO3 heterostructures remain intrinsically antiferroelectric, the Pb1.2ZrO3 heterostructures exhibit a hysteresis loop indicative of ferroelectric response. Further X-ray scattering studies reveal strong quarter-order diffraction peaks in PbZrO3 and Pb1.1ZrO3 heterostructures indicative of antiferroelectricity, while no such peaks are observed for Pb1.2ZrO3 heterostructures. Density functional theory calculations suggest the large cation nonstoichiometry ...

A range of modern applications require large and tunable dielectric, piezoelectric or pyroelectric response of ferroelectrics. Such effects are intimately connected to the nature of polarization and how it responds to externally applied stimuli. Ferroelectric susceptibilities are, in general, strongly temperature dependent, diminishing rapidly as one transitions away from the ferroelectric phase transition (TC). In turn, researchers seek new routes to manipulate polarization to simultaneously enhance susceptibilities and broaden operational temperature ranges. Here, we demonstrate such a capability by creating composition and strain gradients in Ba1−xSrxTiO3 films which result in spatial polarization gradients as large as 35 μC cm−2 across a 150 nm thick film. These polarization gradients allow for large dielectric permittivity with low loss (ɛr≈775, tan δ, Future technologies based on ferroelectric materials will require new routes to control the nature of polar order. Through a combined experimental and theoretical study of compositionally and strain-graded Ba1-xSrxTiO3 heterostructures, Damodaran et al. demonstrate the ability to engineer large polarization gradients and temperature-stable susceptibilities.

In this communication, we report the successful growth of high-quality Aurivillius oxide thin films with m = 8 (where m denotes the number of pseudo-perovskite blocks) using pulsed laser deposition. Both the ferroelectric and magnetic properties of the layer-structure epitaxial Bi9Ti3Fe5O27 films were investigated. Surprisingly, the optimized thin films exhibit in-plane ferroelectric polarization switching and ferromagnetism even at room temperature, though the bulk material is antiferromagnetic. In addition, dielectric measurements indicate that such thin films exhibit potential for high-frequency device applications. This work therefore demonstrates a new pathway to developing single-phase multiferroic materials where ferroelectricity and ferromagnetism coexist with great potential for low energy device applications.

A novel approach to on-demand improvement of electronic properties in complex-oxide ferroelectrics is demonstrated whereby ion bombardment - commonly used in classic semiconductor materials - is applied to the PbTiO3 system. The result is deterministic reduction in leakage currents by 5 orders of magnitude, improved ferroelectric switching, and unprecedented insights into the nature of defects and intergap state evolution in these materials.

We explore the effect of growth conditions on the cation and anion chemistry, electrical leakage, conduction mechanisms, and ferroelectric and dielectric behavior of BiFeO3. Although it is possible to produce single-phase, coherently strained films in all cases, small variations in the pulsed-laser deposition growth process, specifically the laser repetition rate and target composition, result in films with chemistries ranging from 10% Bi-deficiency to 4% Bi-excess and films possessing Bi gradients as large a 6% across the film thickness. Corresponding variations and gradients in the O chemistry are also observed. As a result of the varying film chemistry, marked differences in surface and domain morphology are observed wherein Bi-deficiency stabilizes atomically smooth surfaces and ordered stripe domains. Subsequent investigation of the current–voltage response reveals large differences in leakage current density arising from changes in both the overall stoichiometry and gradients. In turn, the film stoi...

Ferroelectric domain walls are of great interest as elementary building blocks for future electronic devices due to their intrinsic few-nanometre width, multifunctional properties and field-controlled topology. To realize the electronic functions, domain walls are required to be electrically conducting and addressable non-destructively. However, these properties have been elusive because conducting walls have to be electrically charged, which makes them unstable and uncommon in ferroelectric materials. Here we reveal that spontaneous and recorded domain walls in thin films of lead zirconate and bismuth ferrite exhibit large conductance at microwave frequencies despite being insulating at d.c. We explain this effect by morphological roughening of the walls and local charges induced by disorder with the overall charge neutrality. a.c. conduction is immune to large contact resistance enabling completely non-destructive walls read-out. This demonstrates a technological potential for harnessing a.c. conduction for oxide electronics and other materials with poor d.c. conduction, particularly at the nanoscale., Conducting charged ferroelectric domain walls, as potential building blocks for future electronic devices, are unstable and uncommon in ferroelectric materials. Here, Tselev et al. show that neutral insulating domain walls in PbZrO3 and BiFeO3 thin films are conductive under microwave excitation, allowing for non-destructive read-out.

Domains and domain walls are critical in determining the response of ferroelectrics, and the ability to controllably create, annihilate, or move domains is essential to enable a range of next-generation devices. Whereas electric-field control has been demonstrated for ferroelectric 180° domain walls, similar control of ferroelastic domains has not been achieved. Here, using controlled composition and strain gradients, we demonstrate deterministic control of ferroelastic domains that are rendered highly mobile in a controlled and reversible manner. Through a combination of thin-film growth, transmission-electron-microscopy-based nanobeam diffraction and nanoscale band-excitation switching spectroscopy, we show that strain gradients in compositionally graded PbZr1-xTixO3 heterostructures stabilize needle-like ferroelastic domains that terminate inside the film. These needle-like domains are highly labile in the out-of-plane direction under applied electric fields, producing a locally enhanced piezoresponse. This work demonstrates the efficacy of novel modes of epitaxy in providing new modalities of domain engineering and potential for as-yet-unrealized nanoscale functional devices.

Author(s): Chen, A; Zhang, W; Dedon, LR; Chen, D; Khatkhatay, F; MacManus-Driscoll, JL; Wang, H; Yarotski, D; Chen, J; Gao, X; Martin, LW; Roelofs, A; Jia, Q | Abstract: Memristors with excellent scalability have the potential to revolutionize not only the field of information storage but also neuromorphic computing. Conventional metal oxides are widely used as resistive switching materials in memristors. Interface-type memristors based on ferroelectric materials are emerging as alternatives in the development of high-performance memory devices. A clear understanding of the switching mechanisms in this type of memristors, however, is still in its early stages. By comparing the bipolar switching in different systems, it is found that the switchable diode effect in ferroelectric memristors is controlled by polarization modulated Schottky barrier height and polarization coupled interfacial deep states trapping/detrapping. Using semiconductor theories with consideration of polarization effects, a phenomenological theory is developed to explain the current–voltage behavior at the metal/ferroelectric interface. These findings reveal the critical role of the interaction among polarization charges, interfacial defects, and Schottky interface in controlling ferroelectric resistive switching and offer the guidance to design ferroelectric memristors with enhanced performance.

Electric-field control of magnetism requires deterministic control of the magnetic order and understanding of the magnetoelectric coupling in multiferroics like BiFeO3 and EuTiO3. Despite this critical need, there are few studies on the strain evolution of magnetic order in BiFeO3 films. Here, in (110)-oriented BiFeO3 films, we reveal that while the polarization structure remains relatively unaffected, strain can continuously tune the orientation of the antiferromagnetic-spin axis across a wide angular space, resulting in an unexpected deviation of the classical perpendicular relationship between the antiferromagnetic axis and the polarization. Calculations suggest that this evolution arises from a competition between the Dzyaloshinskii–Moriya interaction and single-ion anisotropy wherein the former dominates at small strains and the two are comparable at large strains. Finally, strong coupling between the BiFeO3 and the ferromagnet Co0.9Fe0.1 exists such that the magnetic anisotropy of the ferromagnet can be effectively controlled by engineering the orientation of the antiferromagnetic-spin axis.

Complex-oxide materials tuned to be near phase boundaries via chemistry/composition, temperature, pressure, etc. are known to exhibit large susceptibilities. Here, we observe a strain-driven nanoscale phase competition in epitaxially constrained Bi

Electric-field control of magnetism requires deterministic control of the magnetic order and understanding of the magnetoelectric coupling in multiferroics like BiFeO

Emergent phenomena at polar-nonpolar oxide interfaces have been studied intensely in pursuit of next-generation oxide electronics and spintronics. Here we report the disentanglement of critical thicknesses for electron reconstruction and the emergence of ferromagnetism in polar-mismatched LaMnO_{3}/SrTiO_{3} (001) heterostructures. Using a combination of element-specific x-ray absorption spectroscopy and dichroism, and first-principles calculations, interfacial electron accumulation, and ferromagnetism have been observed within the polar, antiferromagnetic insulator LaMnO_{3}. Our results show that the critical thickness for the onset of electron accumulation is as thin as 2 unit cells (UC), significantly thinner than the observed critical thickness for ferromagnetism of 5 UC. The absence of ferromagnetism below 5 UC is likely induced by electron overaccumulation. In turn, by controlling the doping of the LaMnO_{3}, we are able to neutralize the excessive electrons from the polar mismatch in ultrathin LaMnO_{3} films and thus enable ferromagnetism in films as thin as 3 UC, extending the limits of our ability to synthesize and tailor emergent phenomena at interfaces and demonstrating manipulation of the electronic and magnetic structures of materials at the shortest length scales.

A strain-driven orthorhombic (O) to rhombohedral (R) phase transition is reported in La-doped BiFeO

In the pursuit of energy efficient materials, vanadium dioxide (VO

Leveraging competition between energetically degenerate states to achieve large field-driven responses is a hallmark of functional materials, but routes to such competition are limited. Here, a new route to such effects involving domain-structure competition is demonstrated, which arises from strain-induced spontaneous partitioning of PbTiO

Three new lead oxide benzoates have been prepared solvothermally. In two polymorphs, 1 and 2, of Pb2O(C6H5COO)2, distorted Pb4O tetrahedra share edges to form helical ∞1[Pb2O] chains. Unprecedented among Pb4O-based structures, these motifs may be viewed as double helices of lead atoms surrounding the central oxygen atoms. Both right- and left-handed helices are included in each structure. Formation of the polymorphs was controlled through variation in synthetic conditions. Polymorph 1 crystallizes in the achiral, polar space group Fdd2. Polymorph 2, in P21, is a rare example of a kryptoracemate in which crystallographically independent chains of both chiralities occur in the asymmetric unit. This second polymorph is both chiral and polar, and the pseudosymmetric relationship between the helices has been examined. In Pb4O(C6H5COO)6 (3), discrete Pb4O tetrahedra are bridged by benzoate ligands to form a one-dimensional hybrid structure. The compounds have been further characterized via IR spectroscopy, elem...

Solid-oxide fuel/electrolyzer cells are limited by a dearth of electrolyte materials with low ohmic loss and an incomplete understanding of the structure-property relationships that would enable the rational design of better materials. Here, using epitaxial thin-film growth, synchrotron radiation, impedance spectroscopy, and density-functional theory, the impact of structural parameters (i.e., unit-cell volume and octahedral rotations) on ionic conductivity is delineated in La0.9 Sr0.1 Ga0.95 Mg0.05 O3- δ . As compared to the zero-strain state, compressive strain reduces the unit-cell volume while maintaining large octahedral rotations, resulting in a strong reduction of ionic conductivity, while tensile strain increases the unit-cell volume while quenching octahedral rotations, resulting in a negligible effect on the ionic conductivity. Calculations reveal that larger unit-cell volumes and octahedral rotations decrease migration barriers and create low-energy migration pathways, respectively. The desired combination of large unit-cell volume and octahedral rotations is normally contraindicated, but through the creation of superlattice structures both expanded unit-cell volume and large octahedral rotations are experimentally realized, which result in an enhancement of the ionic conductivity. All told, the potential to tune ionic conductivity with structure alone by a factor of ≈2.5 at around 600 °C is observed, which sheds new light on the rational design of ion-conducting perovskite electrolytes.

Single-crystalline thin films of complex oxides show a rich variety of functional properties such as ferroelectricity, piezoelectricity, ferro and antiferromagnetism and so on that have the potential for completely new electronic applications. Direct synthesis of such oxides on silicon remains challenging because of the fundamental crystal chemistry and mechanical incompatibility of dissimilar interfaces. Here we report integration of thin (down to one unit cell) single crystalline, complex oxide films onto silicon substrates, by epitaxial transfer at room temperature. In a field-effect transistor using a transferred lead zirconate titanate layer as the gate insulator, we demonstrate direct reversible control of the semiconductor channel charge with polarization state. These results represent the realization of long pursued but yet to be demonstrated single-crystal functional oxides on-demand on silicon., Synthesis of single-crystal complex-oxide films directly on silicon is difficult due to differing interfacial chemistry. Here, the authors demonstrate room-temperature integration of single-crystal lead zirconate titanate on to silicon to act as a gate insulator in a field-effect transistor.

The complex interplay of spin, charge, orbital and lattice degrees of freedom provides a plethora of exotic phases and physical phenomena. In recent years, complex spin topologies have emerged as a consequence of the electronic band structure and the interplay between spin and spin-orbit coupling in materials. Here we produce complex topologies of electrical polarization--namely, nanometre-scale vortex-antivortex (that is, clockwise-anticlockwise) arrays that are reminiscent of rotational spin topologies--by making use of the competition between charge, orbital and lattice degrees of freedom in superlattices of alternating lead titanate and strontium titanate layers. Atomic-scale mapping of the polar atomic displacements by scanning transmission electron microscopy reveals the presence of long-range ordered vortex-antivortex arrays that exhibit nearly continuous polarization rotation. Phase-field modelling confirms that the vortex array is the low-energy state for a range of superlattice periods. Within this range, the large gradient energy from the vortex structure is counterbalanced by the corresponding large reduction in overall electrostatic energy (which would otherwise arise from polar discontinuities at the lead titanate/strontium titanate interfaces) and the elastic energy associated with epitaxial constraints and domain formation. These observations have implications for the creation of new states of matter (such as dipolar skyrmions, hedgehog states) and associated phenomena in ferroic materials, such as electrically controllable chirality.

Author(s): Saremi, S; Xu, R; Dedon, LR; Gao, R; Ghosh, A; Dasgupta, A; Martin, LW | Abstract: Despite continued interest in the multiferroic BiFeO3 for a diverse range of applications, use of this material is limited by its poor electrical leakage. This work demonstrates some of the most resistive BiFeO3 thin films reported to date via defect engineering achieved via high-energy ion bombardment. High leakage in as-grown BiFeO3 thin films is shown to be due to the presence of moderately shallow isolated trap states, which form during growth. Ion bombardment is shown to be an effective way to reduce this free carrier transport (by up to ≈4 orders of magnitude) by trapping the charge carriers in bombardment-induced, deep-lying defect complexes and clusters. The ion bombardment is also found to give rise to an increased resistance to switching as a result of an increase in defect concentration. This study demonstrates a systematic ion-dose-dependent increase in the coercivity, extension of the defect-related creep regime, increase in the pinning activation energy, decrease in the switching speed, and broadening of the field distribution of switching. Ultimately, the use of such defect-engineering routes to control materials will require identification of an optimum range of ion dosage to achieve maximum enhancement in resistivity with minimum impact on ferroelectric switching.

Leveraging competition between energetically degenerate states to achieve large field-driven responses is a hallmark of functional materials, but routes to such competition are limited. Here, a new route to such effects involving domain-structure competition is demonstrated, which arises from strain-induced spontaneous partitioning of PbTiO3 thin films into nearly energetically degenerate, hierarchical domain architectures of coexisting c/a and a1 /a2 domain structures. Using band-excitation piezoresponse force microscopy, this study manipulates and acoustically detects a facile interconversion of different ferroelastic variants via a two-step, three-state ferroelastic switching process (out-of-plane polarized c+ → in-plane polarized a → out-of-plane polarized c- state), which is concomitant with large nonvolatile electromechanical strains (≈1.25%) and tunability of the local piezoresponse and elastic modulus (>23%). It is further demonstrated that deterministic, nonvolatile writing/erasure of large-area patterns of this electromechanical response is possible, thus showing a new pathway to improved function and properties.

Requisite to growing stoichiometric perovskite thin films of the solid-solution A′1-xAxBO3 by hybrid molecular beam epitaxy is understanding how the growth conditions interpolate between the end members A'BO3 and ABO3, which can be grown in a self-regulated fashion, but under different conditions. Using the example of La1-xSrxVO3, the two-dimensional growth parameter space that is spanned by the flux of the metal-organic precursor vanadium oxytriisopropoxide and composition, x, was mapped out. The evolution of the adsorption-controlled growth window was obtained using a combination of X-ray diffraction, atomic force microscopy, reflection high-energy electron-diffraction (RHEED), and Rutherford backscattering spectroscopy. It is found that the stoichiometric growth conditions can be mapped out quickly with a single calibration sample using RHEED. Once stoichiometric conditions have been identified, the out-of-plane lattice parameter can be utilized to precisely determine the composition x. This strategy e...

Ferroelectrics, with their spontaneous switchable electric polarization and strong coupling between their electrical, mechanical, thermal, and optical responses, provide functionalities crucial for a diverse range of applications. Over the past decade, there has been significant progress in epitaxial strain engineering of oxide ferroelectric thin films to control and enhance the nature of ferroelectric order, alter ferroelectric susceptibilities, and to create new modes of response which can be harnessed for various applications. This review aims to cover some of the most important discoveries in strain engineering over the past decade and highlight some of the new and emerging approaches for strain control of ferroelectrics. We discuss how these new approaches to strain engineering provide promising routes to control and decouple ferroelectric susceptibilities and create new modes of response not possible in the confines of conventional strain engineering. To conclude, we will provide an overview and prospectus of these new and interesting modalities of strain engineering helping to accelerate their widespread development and implementation in future functional devices.

Nature 530, 198–201 (2016); doi: 10.1038/nature16463 In this Letter, the surname of author Christian M. Schleputz was incorrectly spelled “Schlepuetz”. This has been corrected in the online versions of the paper.

LaVO3 thin films were grown on SrTiO3 (001) by hybrid molecular beam epitaxy. A volatile metalorganic precursor, vanadium oxytriisopropoxide (VTIP), and elemental La were co-supplied in the presence of a molecular oxygen flux. By keeping the La flux fixed and varying the VTIP flux, stoichiometric LaVO3 films were obtained for a range of cation flux ratios, indicating the presence of a self-regulated growth window. Films grown under stoichiometric conditions were found to have the largest lattice parameter, which decreased monotonically with increasing amounts of excess La or V. Energy dispersive X-ray spectroscopy and Rutherford backscattering measurements were carried out to confirm film compositions. Stoichiometric growth of complex vanadate thin films independent of cation flux ratios expands upon the previously reported self-regulated growth of perovskite titanates using hybrid molecular beam epitaxy, thus demonstrating the general applicability of this growth approach to other complex oxide materials, where a precise control over film stoichiometry is demanded by the application.

Small-angle neutron scattering with polarization analysis reveals that Fe3O4 nanoparticles with 90 A diameters have ferrimagnetic moments significantly reduced from that of bulk Fe3O4 at 10 K, nominal saturation. Combined with previous results for an equivalent applied field at 200 K, a core-disordered shell picture of a spatially reduced ferrimagnetic core emerges, even well below the bulk blocking temperature. Zero-field cooling suggests that this magnetic morphology may be intrinsic to the nanoparticle, rather than field induced, at 10 K.