Controlling the Magneto-Optical Response in Ultrathin Films of EuO1-x via Interface Engineering with Ferroelectric BaTi2O5.

Utilizing pulsed laser deposition, a film of EuO1-x was deposited onto a Si(001) substrate with MgO buffer and compared to the same heterostructure with an additional BaTi2O5 thin film on top of the EuO1-x surface. X-ray diffraction (XRD) indicates the films crystallize into a preferred EuO(111) orientation; it also reveals the clear presence of EuSi2, which suggests Si or Eu diffuses across the MgO buffer layer. EuO1-x films exhibit a ferromagnetic (FM) signature and temperature-dependent exchange bias, indicated by MOKE measurements, suggesting the presence of a magnetic order well above the EuO Curie temperature with possible origins in charge carrier density near the interface. In comparison, an antiferromagnetic character persists well above the EuO Curie temperature of 69 K and the enhanced Curie temperature of 150 K for BaTi2O5 films grown on the EuO1-x films. The antiferromagnetic behavior is not seen in thicker EuO1-x thin films when integrated with other ferroelectric (FE) phases of the BaO-TiO2 system, suggesting an origin in the perturbed charge population at the BaTi2O5/EuO1-x interface.

Chiral photocurrent in a Quasi-1D TiS3(001) phototransistor.

The presence of in-plane chiral effects, hence spin-orbit coupling, is evident in the changes in the photocurrent produced in a TiS3(001) field-effect phototransistor with left versus right circularly polarized light. The direction of the photocurrent is protected by the presence of strong spin-orbit coupling and the anisotropy of the band structure as indicated in NanoARPES measurements. Dark electronic transport measurements indicate that TiS3is n-type and has an electron mobility in the range of 1-6 cm2V-1s-1.I-Vmeasurements under laser illumination indicate the photocurrent exhibits a bias directionality dependence, reminiscent of bipolar spin diode behavior. Because the TiS3contains no heavy elements, the presence of spin-orbit coupling must be attributed to the observed loss of inversion symmetry at the TiS3(001) surface.

Surface Versus Bulk State Transitions in Inkjet-Printed All-Inorganic Perovskite Quantum Dot Films.

The anion exchange of the halides, Br and I, is demonstrated through the direct mixing of two pure perovskite quantum dot solutions, CsPbBr3 and CsPbI3, and is shown to be both facile and result in a completely alloyed single phase mixed halide perovskite. Anion exchange is also observed in an interlayer printing method utilizing the pure, unalloyed perovskite solutions and a commercial inkjet printer. The halide exchange was confirmed by optical absorption spectroscopy, photoluminescent spectroscopy, X-ray diffraction, and X-ray photoemission spectroscopy characterization and indicates that alloying is thermodynamically favorable, while the formation of a clustered alloy is not favored. Additionally, a surface-to-bulk photoemission core level transition is observed for the Cs 4d photoemission feature, which indicates that the electronic structure of the surface is different from the bulk. Time resolved photoluminescence spectroscopy indicates the presence of multiple excitonic decay features, which is argued to originate from states residing at surface and bulk environments.

Effect of Band Symmetry on Photocurrent Production in Quasi-One-Dimensional Transition-Metal Trichalcogenides.

Photocurrent production in quasi-one-dimensional (1D) transition-metal trichalcogenides, TiS3(001) and ZrS3(001), was examined using polarization-dependent scanning photocurrent microscopy. The photocurrent intensity was the strongest when the excitation source was polarized along the 1D chains with dichroic ratios of 4:1 and 1.2:1 for ZrS3 and TiS3, respectively. This behavior is explained by symmetry selection rules applicable to both valence and conduction band states. Symmetry selection rules are seen to be applicable to the experimental band structure, as is observed in polarization-dependent nanospot angle-resolved photoemission spectroscopy. Based on these band symmetry assignments, it is expected that the dichroic ratios for both materials will be maximized using excitation energies within 1 eV of their band gaps, providing versatile polarization sensitive photodetection across the visible spectrum and into the near-infrared.

Tunable spin-state bistability in a spin crossover molecular complex.

The spin crossover (SCO) transitions at both the surface and over the entire volume of the [Fe{H2B(pz)2}2(bipy)] polycrystalline films on Al2O3 substrates have been studied, where pz = pyrazol-1-yl and bipy = 2,2'-bipyridine. For [Fe{H2B(pz)2}2(bipy)] films of hundreds of nm thick, magnetometry and x-ray absorption spectroscopy measurements show thermal hysteresis in the SCO transition with temperature, although the transition in bulk [Fe{H2B(pz)2}2(bipy)] occurs in a non-hysteretic fashion at 157 K. While the size of the crystallites in those films are similar, the hysteresis becomes more prominent in thinner films, indicating a significant effect of the [Fe{H2B(pz)2}2(bipy)]/Al2O3 interface. Bistability of spin states, which can be inferred from the thermal hysteresis, was directly observed using temperature-dependent x-ray diffraction; the crystallites behave as spin-state domains that coexist during the transition. The difference between the spin state of molecules at the surface of the [Fe{H2B(pz)2}2(bipy)] films and that of the molecules within the films, during the thermal cycle, indicates that both cooperative (intermolecular) effects and coordination are implicated in perturbations to the SCO transition.

Inkjet Printing All Inorganic Halide Perovskite Inks for Photovoltaic Applications.

A method for synthesizing photoactive inorganic perovskite quantum dot inks and an inkjet printer deposition method, using the synthesized inks, are demonstrated. The ink synthesis is based on a simple wet chemical reaction and the inkjet printing protocol is a facile step by step method. The inkjet printed thin films have been characterized by X-ray diffraction, optical absorption spectroscopy, photoluminescent spectroscopy, and electronic transport measurements. X-ray diffraction of the printed quantum dot films indicates a crystal structure consistent with an orthorhombic room temperature phase with (001) orientation. In conjunction with other characterization methods, the X-ray diffraction measurements show high quality films can be obtained through the inkjet printing method.

Composition-Dependent Charge Transport in Boron Carbides Alloyed with Aromatics: Plasma Enhanced Chemical Vapor Deposition Aniline/Orthocarborane Films.

Boron carbide films, alloyed with aniline moieties, were deposited by plasma enhanced chemical vapor deposition (PECVD) from aniline and orthocarborane precursors and were found to exhibit composition-dependent drift carrier lifetimes as derived from I( V) and C( V)) measurements. For a film with an aniline/carborane ratio of 5:1, the effective drift carrier lifetimes are ∼80 µs at low bias voltage but quickly drop to a few microseconds with increasing bias. A film with a 10:1 aniline/carborane ratio, however, exhibited lifetimes of ∼6 µs, or less, at 1 kHz, and much smaller values at 10 kHz. These lifetimes are orders of magnitude longer than those in polyaniline films and comparable to those in PECVD carborane films without aromatic content. X-ray photoelectron spectroscopy (XPS), FTIR, and ellipsometry, combined with density functional theory (DFT)-based cluster calculations, indicate that aniline and orthocarborane moieties are largely intact within the films. Bonding occurs primarily between aniline C sites and carborane B sites, and the aniline coordination number per carborane icosahedron is ∼2 as the aniline/carborane ratio is increased from 3:1 to 10:1. This aniline/carborane coordination ratio independent of aniline/orthocarborane stoichiometry is consistent with the dependence of charge transport properties on aniline film content at high bias voltage.

Coexistence of Two Electronic Nano-Phases on a CH3NH3PbI3-xClx Surface Observed in STM Measurements.

Scanning tunneling microscopy is utilized to investigate the local density of states of a CH3NH3PbI3-xClx perovskite in cross-sectional geometry. Two electronic phases, 10-20 nm in size, with different electronic properties inside the CH3NH3PbI3-xClx perovskite layer are observed by the dI/dV mapping and point spectra. A power law dependence of the dI/dV point spectra is revealed. In addition, the distinct electronic phases are found to have preferential orientations close to the normal direction of the film surface. Density functional theory calculations indicate that the observed electronic phases are associated with local deviation of I/Cl ratio, rather than different orientations of the electric dipole moments in the ferroelectric phases. By comparing the calculated results with experimental data we conclude that phase A (lower contrast in dI/dV mapping at -2.0 V bias) contains a lower I/Cl ratio than that in phase B (higher contrast in dI/dV).

Built-in Electric Field Induced Mechanical Property Change at the Lanthanum Nickelate/Nb-doped Strontium Titanate Interfaces.

The interactions between electric field and the mechanical properties of materials are important for the applications of microelectromechanical and nanoelectromechanical systems, but relatively unexplored for nanoscale materials. Here, we observe an apparent correlation between the change of the fractured topography of Nb-doped SrTiO3 (Nb:STO) within the presence of a built-in electric field resulting from the Schottky contact at the interface of a metallic LaNiO3 thin film utilizing cross-sectional scanning tunneling microscopy and spectroscopy. The change of the inter-atomic bond length mechanism is argued to be the most plausible origin. This picture is supported by the strong-electric-field-dependent permittivity in STO and the existence of the dielectric dead layer at the interfaces of STO with metallic films. These results provided direct evidence and a possible mechanism for the interplay between the electric field and the mechanical properties on the nanoscale for perovskite materials.