Dmitri A. Tenne

Correlation between saturation magnetization, bandgap, and lattice volume of transition metal (M=Cr, Mn, Fe, Co, or Ni) doped Zn1−xMxO nanoparticles

This work reports on transition metal doped ZnO nanoparticles and compares the effects doping with different transition metal ions has on the structural, optical, and magnetic properties. Zn1−xMxO (M=Cr, Mn, Fe, Co, or Ni) nanoparticles were prepared by a chemical process for x=0.02 and 0.05 in powder form. The powders where characterized by x-ray diffraction (XRD), spectrophotometry, and magnetometry. The Zn1−xMxO samples showed a strong correlation between changes in the lattice parameters, bandgap energy, and the ferromagnetic saturation magnetization. Unit cell volume and bandgap, determined from XRD and spectrophotometry respectively, were maximized with Fe doping and decreased as the atomic number of the dopant moved away from Fe. Bandgap was generally lower at x=0.05 than x=0.02 for all dopants. The saturation magnetization reached a maximum of 6.38 memu/g for Zn0.95Fe0.05O.

Phase Transitions, Phase Coexistence, and Piezoelectric Switching Behavior in Highly Strained BiFeO 3 Films

Highly strained BiFeO3 films transition into a true tetragonal state at 430 °C but remain polar to much higher temperatures (∼800 °C). Piezoelectric switching is only possible up to 300 °C, i.e., at temperatures for which strain stabilizes the stripe-like coexistence of multiple polymorphs.

Ferroelectricity in nonstoichiometric SrTiO3 films studied by ultraviolet Raman spectroscopy

Homoepitaxial Sr1+xTiO3+δ films with −0.2≤x≤0.25 grown by reactive molecular-beam epitaxy on SrTiO3 (001) substrates have been studied by ultraviolet Raman spectroscopy. Nonstoichiometry for strontium-deficient compositions leads to the appearance of strong first-order Raman scattering at low temperatures, which decreases with increasing temperature and disappears at about 350 K. This indicates the appearance of a spontaneous polarization with a paraelectric-to-ferroelectric transition temperature above room temperature. Strontium-rich samples also show a strong first-order Raman signal, but the peaks are significantly broader and exhibit a less pronounced temperature dependence, indicating a stronger contribution of the disorder-activated mechanism in Raman scattering.

Adsorption-controlled growth of BiVO4 by molecular-beam epitaxy

Single-phase epitaxial films of the monoclinic polymorph of BiVO4 were synthesized by reactive molecular-beam epitaxy under adsorption-controlled conditions. The BiVO4 films were grown on (001) yttria-stabilized cubic zirconia (YSZ) substrates. Four-circle x-ray diffraction, scanning transmission electron microscopy (STEM), and Raman spectroscopy confirm the epitaxial growth of monoclinic BiVO4 with an atomically abrupt interface and orientation relationship (001)BiVO4 ∥ (001)YSZ with [100]BiVO4 ∥ [100]YSZ. Spectroscopic ellipsometry, STEM electron energy loss spectroscopy (STEM-EELS), and x-ray absorption spectroscopy indicate that the films have a direct band gap of 2.5 ± 0.1 eV.

Growth of nanoscale BaTiO 3 /SrTiO 3 superlattices by molecular-beam epitaxy

Abstract : Commensurate BaTiO3/SrTiO3 superlattices were grown by reactive molecular-beam epitaxy on four different substrates: TiO2-terminated (001) SrTiO3, (101) DyScO3, (101) GdScO3, and (101) SmScO3. With the aid of reflection high-energy electron diffraction (RHEED), precise single-monolayer doses of BaO, SrO, and TiO2 were deposited sequentially to create commensurate BaTiO3/SrTiO3 superlattices with a variety of periodicities. X-ray diffraction (XRD) measurements exhibit clear superlattice peaks at the expected positions. The rocking curve full width half-maximum of the superlattices was as narrow as 7 arc s (0.002 deg). High-resolution transmission electron microscopy reveals nearly atomically abrupt interfaces. Temperature-dependent ultraviolet Raman and XRD were used to reveal the paraelectric-to-ferroelectric transition temperature (TC). Our results demonstrate the importance of finite size and strain effects on the TC of BaTiO3/SrTiO3 superlattices. In addition to probing finite size and strain effects, these heterostructures may be relevant for novel phonon devices, including mirrors, filters, and cavities for coherent phonon generation and control.

Defect Induced Ferromagnetism in Undoped ZnO Nanoparticles

Undoped ZnO nanoparticles (NPs) with size ∼12 nm were produced using forced hydrolysis methods using diethylene glycol (DEG) [called ZnO-I] or denatured ethanol [called ZnO-II] as the reaction solvent; both using Zn acetate dehydrate as precursor. Both samples showed weak ferromagnetic behavior at 300 K with saturation magnetization Ms = 0.077 ± 0.002 memu/g and 0.088 ± 0.013 memu/g for ZnO-I and ZnO-II samples, respectively. Fourier transform infrared (FTIR) spectra showed that ZnO-I nanocrystals had DEG fragments linked to their surface. Photoluminescence (PL) data showed a broad emission near 500 nm for ZnO-II which is absent in the ZnO-I samples, presumably due to the blocking of surface traps by the capping molecules. Intentional oxygen vacancies created in the ZnO-I NPs by annealing at 450 °C in flowing Ar gas gradually increased Ms up to 90 min and x-ray photoelectron spectra (XPS) suggested that oxygen vacancies may have a key role in the observed changes in Ms. Finally, PL spectra of ZnO showed t...

Temperature-Dependent Raman Scattering of Multiferroic Pb(Fe 1/2 Nb 1/2 )O 3

Raman scattering measurements on multiferroic Pb(Fe(1/2)Nb(1/2))O₃ over a wide temperature range from 10 to 500 K were performed. Very broad and overlapping peaks (first-order character) and a prominent high-frequency peak at approximately 1130 cm( - 1), which we assign as a two-phonon peak, were observed. These features showed remarkable changes in their Raman scattering intensity and spectral shape at the characteristic temperature T(*) ∼ 330 K, clearly showing a structural lattice change at around T(*). The temperature dependence of some stretching vibration modes of the BO(6) units revealed an anomalous frequency shift below T(N) approxiamtely 143 K. These anomalous deviations at T(N) of the phonon frequency are associated with the spin-phonon coupling mechanism. Complementary magnetic data confirmed a weak magnetic ordering at room temperature and interestingly showed an anomaly at about T(*). These results suggest an interplay between ferroelectric, structural and magnetic degrees of freedom in PFN, starting to be significant at around T(*).

Improving the selective cancer killing ability of ZnO nanoparticles using Fe doping

Abstract This work reports a new method to improve our recent demonstration of zinc oxide (ZnO) nanoparticles (NPs) selectively killing certain human cancer cells, achieved by incorporating Fe ions into the NPs. Thoroughly characterized cationic ZnO NPs (∼6 nm) doped with Fe ions (Zn1-x Fe x O, x = 0–0.15) were used in this work, applied at a concentration of 24 μg/ml. Cytotoxicity studies using flow cytometry on Jurkat leukemic cancer cells show cell viability drops from about 43% for undoped ZnO NPs to 15% for ZnO NPs doped with 7.5% Fe. However, the trend reverses and cell viability increases with higher Fe concentrations. The non-immortalized human T cells are markedly more resistant to Fe-doped ZnO NPs than cancerous T cells, confirming that Fe-doped samples still maintain selective toxicity to cancer cells. Pure iron oxide samples displayed no appreciable toxicity. Reactive oxygen species generated with NP introduction to cells increased with increasing Fe up to 7.5% and decreased for >7.5% doping.

Magnetism of ZnO Nanoparticles: Dependence on Crystallite Size and Surfactant Coating

Many recent reports on magnetism in otherwise nonmagnetic oxides have demonstrated that nanoparticle size, surfactant coating, or doping with magnetic ions produces room-temperature ferromagnetism. Specifically, ZnO has been argued to be a room-temperature ferromagnet through all three of these methods in various experimental studies. For this reason, we have prepared a series of 1% Fe doped ZnO nanoparticle samples using a single forced hydrolysis coprecipitation synthesis method from the same precursors, while varying size (6–15 nm) and surface coating concentration to study the combined effects of these two parameters. Size was controlled by modifying the water concentration. Surfactant coating was adjusted by varying the concentration of polyacrylic acid in solution. Samples were characterized by x-ray diffraction, transmission electron microscopy, x-ray photoelectron spectroscopy, optical absorbance spectroscopy, and magnetometry. No clear systematic effect on magnetization was observed as a function...

Tuning the Properties of ZnO, Hematite, and Ag Nanoparticles by Adjusting the Surface Charge

A poly (acryl acid) (PAA) post-treatment method is performed to modify the surface charge of ZnO nanospheres, hematite nanocubes, and Ag nanoprisms from highly positive to very negative by adjusting the PAA concentration, to and greatly modify their photoluminescence, cytotoxicity, magnetism, and surface plasmon resonance. This method provides a general way to tune the nanoparticle properties for broad physicochemical and biological applications.