Room temperature ferroelectric and magnetic investigations and detailed phase analysis of Aurivillius phase Bi 5Ti 3Fe 0.7Co 0.3O 15 thin films

Aurivillius phase Bi 5Ti 3Fe 0.7Co 0.3O 15 (BTF7C3O) thin films on α-quartz substrates were fabricated by a chemical solution deposition method and the room temperature ferroelectric and magnetic properties of this candidate multiferroic were compared with those of thin films of Mn 3 substituted, Bi 5Ti 3Fe 0.7Mn 0.3O 15 (BTF7M3O). Vertical and lateral piezoresponse force microscopy (PFM) measurements of the films conclusively demonstrate that BTF7C3O and BTF7M3O thin films are piezoelectric and ferroelectric at room temperature, with the major polarization vector in the lateral plane of the films. No net magnetization was observed for the in-plane superconducting quantum interference device (SQUID) magnetometry measurements of BTF7M3O thin films. In contrast, SQUID measurements of the BTF7C3O films clearly demonstrated ferromagnetic behavior, with a remanent magnetization, B r, of 6.37 emu/cm 3 (or 804 memu/g), remanent moment 4.99 × 10 -5 emu. The BTF7C3O films were scrutinized by x-ray diffraction, high resolution transmission electron microscopy, scanning transmission electron microscopy, and energy dispersive x-ray analysis mapping to assess the prospect of the observed multiferroic properties being intrinsic to the main phase. The results of extensive micro-structural phase analysis demonstrated that the BTF7C3O films comprised of a 3.95 Fe/Co-rich spinel phase, likely CoFe 2 - xTi xO 4, which would account for the observed magnetic moment in the films. Additionally, x-ray magnetic circular dichroism photoemission electron microscopy (XMCD-PEEM) imaging confirmed that the majority of magnetic response arises from the Fe sites of Fe/Co-rich spinel phase inclusions. While the magnetic contribution from the main phase could not be determined by the XMCD-PEEM images, these data however imply that the Bi 5Ti 3Fe 0.7Co 0.3O 15 thin films are likely not single phase multiferroics at room temperature. The PFM results presented demonstrate that the naturally 2D nanostructured Bi 5Ti 3Fe 0.7Co 0.3O 15 phase is a novel ferroelectric and has potential commercial applications in high temperature piezoelectric and ferroelectric memory technologies. The implications for the conclusive demonstration of ferroelectric and ferromagnetic properties in single-phase materials of this type are discussed.

Room temperature electromechanical and magnetic investigations of ferroelectric Aurivillius phase Bi5Ti3(FexMn1−x)O15 (x = 1 and 0.7) chemical solution deposited thin films

Aurivillius phase thin films of Bi5Ti3(FexMn1−x)O15 with x = 1 (Bi5Ti3FeO15) and 0.7 (Bi5Ti3Fe0.7Mn0.3O15) on SiO2-Si(100) and Pt/Ti/SiO2-Si substrates were fabricated by chemical solution deposition. The method was optimized in order to suppress formation of pyrochlore phase Bi2Ti2O7 and improve crystallinity. The structuralproperties of the films were examined by x-ray diffraction, scanning electron microscopy, and atomic force microscopy. Optimum crystallinity and pyrochlore phase suppression was achieved by the addition of 15 to 25 mol. % excess bismuth to the sols. Based on this study, 17.5 mol. % excess bismuth was used in the preparation of Bi2Ti2O7-free films of Bi5Ti3FeO15 on SrTiO3(100) and NdGaO3(001) substrates, confirming the suppression of pyrochlore phase using this excess of bismuth. Thirty percent of the Fe3+ ions in Bi5Ti3FeO15 was substituted with Mn3+ ions to form Bi2Ti2O7-free thin films of Bi5Ti3Fe0.7Mn0.3O15 on Pt/Ti/SiO2-Si, SiO2-Si(100), SrTiO3(100), and NdGaO3(001) substrates. Bi5Ti3FeO15 and Bi5Ti3Fe0.7Mn0.3O15thin films on Pt/Ti/SiO2-Si and SiO2-Si(100) substrates were achieved with a higher degree of a-axis orientation compared with the films on SrTiO3(100) and NdGaO3(001) substrates. Room temperature electromechanical and magnetic properties of the thin films were investigated in order to assess the potential of these materials for piezoelectric,ferroelectric, and multiferroic applications. Vertical piezoresponse force microscopy measurements of the films demonstrate that Bi5Ti3FeO15 and Bi5Ti3Fe0.7Mn0.3O15thin films are piezoelectric at room temperature. Room temperature switching spectroscopy-piezoresponse force microscopy measurements in the presence and absence of an applied bias demonstrate local ferroelectric switching behaviour (180°) in the films. Superconducting quantum interference device magnetometry measurements do not show any room temperature ferromagnetic hysteresis down to an upper detection limit of 2.53 × 10−3 emu; and it is concluded, therefore, that such films are not mutiferroic at room temperature. Piezoresponse force microscopy lithography images of Bi5Ti3Fe0.7Mn0.3O15thin films are presented.

Magnetic field-induced ferroelectric switching in multiferroic aurivillius phase thin films at room temperature

Single-phase multiferroic materials are of considerable interest for future memory and sensing applications. Thin films of Aurivillius phase Bi 7Ti3Fe3O21 and Bi6Ti 2.8Fe1.52Mn0.68O18 (possessing six and five perovskite units per half-cell, respectively) have been prepared by chemical solution deposition on c-plane sapphire. Superconducting quantum interference device magnetometry reveal Bi7Ti3Fe 3O21 to be antiferromagnetic (TN = 190 K) and weakly ferromagnetic below 35 K, however, Bi6Ti2.8Fe 1.52Mn0.68O18 gives a distinct room-temperature in-plane ferromagnetic signature (Ms = 0.74 emu/g, μ0Hc =7 mT). Microstructural analysis, coupled with the use of a statistical analysis of the data, allows us to conclude that ferromagnetism does not originate from second phase inclusions, with a confidence level of 99.5%. Piezoresponse force microscopy (PFM) demonstrates room-temperature ferroelectricity in both films, whereas PFM observations on Bi6Ti2.8Fe1.52Mn0.68O18 show Aurivillius grains undergo ferroelectric domain polarization switching induced by an applied magnetic field. Here, we show for the first time that Bi6Ti2.8Fe1.52Mn0.68O18 thin films are both ferroelectric and ferromagnetic and, demonstrate magnetic field-induced switching of ferroelectric polarization in individual Aurivillius phase grains at room temperature.

Large magnetoelectric coupling in nanoscale BiFeO3 from direct electrical measurements

We report the results of direct measurement of remanent hysteresis loops on nanochains of BiFeO3 at room temperature under zero and ∼20 kOe magnetic field. We noticed a suppression of remanent polarization by nearly ∼40% under the magnetic field. The powder neutron diffraction data reveal significant ion displacements under a magnetic field which seems to be the origin of the suppression of polarization. The isolated nanoparticles, comprising the chains, exhibit evolution of ferroelectric domains under dc electric field and complete 180 switching in switching-spectroscopy piezoresponse force microscopy. They also exhibit stronger ferromagnetism with nearly an order of magnitude higher saturation magnetization than that of the bulk sample. These results show that the nanoscale BiFeO3 exhibits coexistence of ferroelectric and ferromagnetic order and a strong magnetoelectric multiferroic coupling at room temperature comparable to what some of the type-II multiferroics show at a very low temperature.

Direct visualization of magnetic-field-induced magnetoelectric switching in multiferroic Aurivillius phase thin films

Multiferroic materials displaying coupled ferroelectric and ferromagnetic order parameters could provide a means for data storage whereby bits could be written electrically and read magnetically, or vice versa. Thin films of Aurivillius phase Bi6Ti2.8Fe1.52Mn0.68O18, previously prepared by a chemical solution deposition (CSD) technique, are multiferroics demonstrating magnetoelectric coupling at room temperature. Here, we demonstrate the growth of a similar composition, Bi6Ti2.99Fe1.46Mn0.55O18, via the liquid injection chemical vapor deposition technique. High-resolution magnetic measurements reveal a considerably higher in-plane ferromagnetic signature than CSD grown films (MS = 24.25 emu/g (215 emu/cm3), MR = 9.916 emu/g (81.5 emu/cm3), HC = 170 Oe). A statistical analysis of the results from a thorough microstructural examination of the samples, allows us to conclude that the ferromagnetic signature can be attributed to the Aurivillius phase, with a confidence level of 99.95%. In addition, we report the direct piezoresponse force microscopy visualization of ferroelectric switching while going through a full in-plane magnetic field cycle, where increased volumes (8.6 to 14% compared with 4 to 7% for the CSD-grown films) of the film engage in magnetoelectric coupling and demonstrate both irreversible and reversible magnetoelectric domain switching.

Nanostructured copper oxides and phosphates from a new solid-state route

Nanostructured copper containing materials of CuO, Cu3(PO4)3 and Cu2P2O7 have been prepared by solid-state pyrolysis of molecular CuCl2·NC5H4OH (I), CuCl2·CNCH2C6H4OH (II), oligomeric [Cu(PPh3)Cl]4 (III), N3P3[OC6H4CH2CN·CuCl]6[PF6] (IV), N3P3[OC6H5]5[OC5H4N·Cu][PF6] (V), polymeric chitosan·(CuCl2)n (VI) and polystyrene-co-4-vinylpyridine PS-b-4-PVP·(CuCl2) (VII) precursors. The products strongly depend on the precursor used. The pyrolytic products from phosphorus-containing precursors (III), (IV) and (V) are Cu phosphates or pyrophosphates, while non-phosphorous-containing precursors (VI) and (VII), result in mainly CuO. The use of chitosan as a solid-state template/stabilizer induces the formation of CuO and Cu2O nanoparticles. Copper pyrophosphate (Cu2P2O7) deposited on Si using (IV) as the precursor exhibits single-crystal dots of average diameter 100 nm and heights equivalent to twice the unit cell b-axis (1.5–1.7 nm) and an areal density of 5.1–7.7 Gigadots/in.2. Cu2P2O7 deposited from precursor (VI) exhibits unique labyrinthine high surface area deposits. The morphology of CuO deposited on Si from pyrolysis of (VI) depends on the polymer/Cu meta ratio. Magnetic measurements performed using SQUID on CuO nanoparticle networks suggest superparamagnetic behavior. The results give insights into compositional, shape and morphological control of the as-formed nanostructures through the structure of the precursors.

Effect of reaction mechanism on precursor exposure time in atomic layer deposition of silicon oxide and silicon nitride

Atomic layer deposition (ALD) of highly conformal, silicon-based dielectric thin films has become necessary because of the continuing decrease in feature size in microelectronic devices. The ALD of oxides and nitrides is usually thought to be mechanistically similar, but plasma-enhanced ALD of silicon nitride is found to be problematic, while that of silicon oxide is straightforward. To find why, the ALD of silicon nitride and silicon oxide dielectric films was studied by applying ab initio methods to theoretical models for proposed surface reaction mechanisms. The thermodynamic energies for the elimination of functional groups from different silicon precursors reacting with simple model molecules were calculated using density functional theory (DFT), explaining the lower reactivity of precursors toward the deposition of silicon nitride relative to silicon oxide seen in experiments, but not explaining the trends between precursors. Using more realistic cluster models of amine and hydroxyl covered surfaces, the structures and energies were calculated of reaction pathways for chemisorption of different silicon precursors via functional group elimination, with more success. DFT calculations identified the initial physisorption step as crucial toward deposition and this step was thus used to predict the ALD reactivity of a range of amino-silane precursors, yielding good agreement with experiment. The retention of hydrogen within silicon nitride films but not in silicon oxide observed in FTIR spectra was accounted for by the theoretical calculations and helped verify the application of the model.

Tetraspanin 3: A central endocytic membrane component regulating the expression of ADAM10, presenilin and the amyloid precursor protein

Despite existing knowledge about the role of the A Disintegrin and Metalloproteinase 10 (ADAM10) as the α-secretase involved in the non-amyloidogenic processing of the amyloid precursor protein (APP) and Notch signalling we have only limited information about its regulation. In this study, we have identified ADAM10 interactors using a split ubiquitin yeast two hybrid approach. Tetraspanin 3 (Tspan3), which is highly expressed in the murine brain and elevated in brains of Alzheimer's disease (AD) patients, was identified and confirmed to bind ADAM10 by co-immunoprecipitation experiments in mammalian cells in complex with APP and the γ-secretase protease presenilin. Tspan3 expression increased the cell surface levels of its interacting partners and was mainly localized in early and late endosomes. In contrast to the previously described ADAM10-binding tetraspanins, Tspan3 did not affect the endoplasmic reticulum to plasma membrane transport of ADAM10. Heterologous Tspan3 expression significantly increased the appearance of carboxy-terminal cleavage products of ADAM10 and APP, whereas N-cadherin ectodomain shedding appeared unaffected. Inhibiting the endocytosis of Tspan3 by mutating a critical cytoplasmic tyrosine-based internalization motif led to increased surface expression of APP and ADAM10. After its downregulation in neuroblastoma cells and in brains of Tspan3-deficient mice, ADAM10 and APP levels appeared unaltered possibly due to a compensatory increase in the expression of Tspans 5 and 7, respectively. In conclusion, our data suggest that Tspan3 acts in concert with other tetraspanins as a stabilizing factor of active ADAM10, APP and the γ-secretase complex at the plasma membrane and within the endocytic pathway.