Jordan Chess

Cytotoxicity of ZnO Nanoparticles Can Be Tailored by Modifying Their Surface Structure: A Green Chemistry Approach for Safer Nanomaterials

ZnO nanoparticles (NP) are extensively used in numerous nanotechnology applications; however, they also happen to be one of the most toxic nanomaterials. This raises significant environmental and health concerns and calls for the need to develop new synthetic approaches to produce safer ZnO NP, while preserving their attractive optical, electronic, and structural properties. In this work, we demonstrate that the cytotoxicity of ZnO NP can be tailored by modifying their surface-bound chemical groups, while maintaining the core ZnO structure and related properties. Two equally sized (9.26 ± 0.11 nm) ZnO NP samples were synthesized from the same zinc acetate precursor using a forced hydrolysis process, and their surface chemical structures were modified by using different reaction solvents. X-ray diffraction and optical studies showed that the lattice parameters, optical properties, and band gap (3.44 eV) of the two ZnO NP samples were similar. However, FTIR spectroscopy showed significant differences in the surface structures and surface-bound chemical groups. This led to major differences in the zeta potential, hydrodynamic size, photocatalytic rate constant, and more importantly, their cytotoxic effects on Hut-78 cancer cells. The ZnO NP sample with the higher zeta potential and catalytic activity displayed a 1.5-fold stronger cytotoxic effect on cancer cells. These results suggest that by modifying the synthesis parameters/conditions and the surface chemical structures of the nanocrystals, their surface charge density, catalytic activity, and cytotoxicity can be tailored. This provides a green chemistry approach to produce safer ZnO NP.

Efficient linear phase contrast in scanning transmission electron microscopy with matched illumination and detector interferometry

The ability to image light elements in soft matter at atomic resolution enables unprecedented insight into the structure and properties of molecular heterostructures and beam-sensitive nanomaterials. In this study, we introduce a scanning transmission electron microscopy technique combining a pre-specimen phase plate designed to produce a probe with structured phase with a high-speed direct electron detector to generate nearly linear contrast images with high efficiency. We demonstrate this method by using both experiment and simulation to simultaneously image the atomic-scale structure of weakly scattering amorphous carbon and strongly scattering gold nanoparticles. Our method demonstrates strong contrast for both materials, making it a promising candidate for structural determination of heterogeneous soft/hard matter samples even at low electron doses comparable to traditional phase-contrast transmission electron microscopy. Simulated images demonstrate the extension of this technique to the challenging problem of structural determination of biological material at the surface of inorganic crystals.

Tailoring magnetic energies to form dipole skyrmions and skyrmion lattices

Author(s): Montoya, SA; Couture, S; Chess, JJ; Lee, JCT; Kent, N; Henze, D; Sinha, SK; Im, MY; Kevan, SD; Fischer, P; McMorran, BJ; Lomakin, V; Roy, S; Fullerton, EE | Abstract:

Synthesizing skyrmion bound pairs in Fe-Gd thin films

We show that properly engineered amorphous Fe-Gd alloy thin films with perpendicular magnetic anisotropy exhibit bound pairs of like-polarity, opposite helicity skyrmions at room temperature. Magnetic mirror symmetry planes present in the stripe phase, instead of chiral exchange, determine the internal skyrmion structure and the net achirality of the skyrmion phase. Our study shows that stripe domain engineering in amorphous alloy thin films may enable the creation of skyrmion phases with technologically desirable properties.

Role of oxygen defects on the magnetic properties of ultra-small Sn1−xFexO2 nanoparticles

Although the role of oxygen defects in the magnetism of metal oxide semiconductors has been widely discussed, it is been difficult to directly measure the oxygen defect concentration of samples to verify this. This work demonstrates a direct correlation between the photocatalytic activity of Sn1−xFexO2 nanoparticles and their magnetic properties. For this, a series of ∼2.6 nm sized, well characterized, single-phase Sn1−xFexO2 crystallites with x = 0−0.20 were synthesized using tin acetate, urea, and appropriate amounts of iron acetate. X-ray photoelectron spectroscopy confirmed the concentration and 3+ oxidation state of the doped Fe ions. The maximum magnetic moment/Fe ion, μ, of 1.6 × 10−4 μB observed for the 0.1% Fe doped sample is smaller than the expected spin-only contribution from either high or low spin Fe3+ ions, and μ decreases with increasing Fe concentration. This behavior cannot be explained by the existing models of magnetic exchange. Photocatalytic studies of pure and Fe-doped SnO2 were used to understand the roles of doped Fe3+ ions and of the oxygen vacancies and defects. The photocatalytic rate constant k also showed an increase when SnO2 nanoparticles were doped with low concentrations of Fe3+, reaching a maximum at 0.1% Fe, followed by a rapid decrease of k for further increase in Fe%. Fe doping presumably increases the concentration of oxygen vacancies, and both Fe3+ ions and oxygen vacancies act as electron acceptors to reduce e−-h+ recombination and promote transfer of electrons (and/or holes) to the nanoparticle surface, where they participate in redox reactions. This electron transfer from the Fe3+ ions to local defect density of states at the nanoparticle surface could develop a magnetic moment at the surface states and leads to spontaneous ferromagnetic ordering of the surface shell under favorable conditions. However, at higher doping levels, the same Fe3+ ions might act as recombination centers causing a decrease of both k and magnetic moment μ.

Dopant spin states and magnetism of Sn1−xFexO2 nanoparticles

This work reports detailed investigations of a series of ∼2.6 nm sized, Sn1−xFexO2 crystallites with x = 0–0.10 using Mossbauer spectroscopy, x-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance spectroscopy (EPR), and magnetometry to determine the oxidation state of Fe dopants and their role in the observed magnetic properties. The magnetic moment per Fe ion μ was the largest ∼6.48 × 10−3 μB for the sample with the lowest (0.001%) Fe doping, and it showed a rapid downward trend with increasing Fe doping. Majority of the Fe ions are in 3+ oxidation state occupying octahedral sites. Another significant fraction of Fe dopant ions is in 4+ oxidation state and a still smaller fraction might be existing as Fe2+ ions, both occupying distorted sites, presumably in the surface regions of the nanocrystals, near oxygen vacancies. These studies also suggest that the observed magnetism is not due to exchange coupling between Fe3+ spins. A more probable role for the multi-valent Fe ions may be to act as charge reservoirs, leading to charge transfer ferromagnetism.

Correlation between magnetism and electronic structure of Zn1−xCoxO nanoparticles

Zn1−xCoxO nanoparticles (∼9 nm) were produced with x ranging from 0 to 0.2 using a forced hydrolysis method. X-ray diffraction measurements confirm the samples to be single phase, and reveal a systematic change in the lattice parameters upon cobalt doping. The unit cell volume V decreases up to x = 0.025 after which it stays roughly constant. The band gap energy (Eg), determined from the photoluminescence spectra gradually increases from x = 0 to 0.025 and then remains nearly constant for x > 0.025. Room temperature hysteresis loops, obtained using vibrating sample magnetometry, show a similar trend in the saturation magnetization (Ms). Undoped ZnO nanoparticles show a weak magnetic hysteresis; doping causes an increase in Ms up to x = 0.025 and then decreases to lower values for x > 0.025. The magnetic moment per Co ion μ decreases rapidly with x nearly following μ(x) ∝ 1/x, indicating that the moments from the Co ions have little impact on the observed magnetic properties. Electron paramagnetic resonanc...

Streamlined approach to mapping the magnetic induction of skyrmionic materials

Recently, Lorentz transmission electron microscopy (LTEM) has helped researchers advance the emerging field of magnetic skyrmions. These magnetic quasi-particles, composed of topologically non-trivial magnetization textures, have a large potential for application as information carriers in low-power memory and logic devices. LTEM is one of a very few techniques for direct, real-space imaging of magnetic features at the nanoscale. For Fresnel-contrast LTEM, the transport of intensity equation (TIE) is the tool of choice for quantitative reconstruction of the local magnetic induction through the sample thickness. Typically, this analysis requires collection of at least three images. Here, we show that for uniform, thin, magnetic films, which includes many skyrmionic samples, the magnetic induction can be quantitatively determined from a single defocused image using a simplified TIE approach.

Resonant properties of dipole skyrmions in amorphous Fe/Gd multilayers

Author(s): Montoya, SA; Couture, S; Chess, JJ; Lee, JCT; Kent, N; Im, MY; Kevan, SD; Fischer, P; McMorran, BJ; Roy, S; Lomakin, V; Fullerton, EE | Abstract:

Development of STEM-Holography

Low-atomic number materials play a crucial role in life sciences, medicine, and the carbon energy cycle. However, our ability to image these materials at the atomic length scale is limited because they do not scatter electrons at high-angles in the same way a crystalline or high atomic number material does. Additionally, these materials are easily damaged under electron beam illumination. To get around these issues, bold efforts have been made in the fields of electron holography [2] and ptychography [3, 4], leading to myriad techniques that can potentially achieve sub-nanometer resolution. Additionally, offaxis electron holography has been developed and applied in many research groups [5 8], pushing the boundaries of electron microscopy with unprecedented feats such as the atomic resolution electrostatic potential mapping of graphene sheets [9].