Plant-Assisted Green Synthesis of MgO Nanoparticles as a Sustainable Material for Bone Regeneration: Spectroscopic Properties.

This work is devoted to magnesium oxide (MgO) nanoparticles (NPs) for their use as additives for bone implants. Extracts from four different widely used plants, including Aloe vera, Echeveria elegans, Sansevieria trifasciata, and Sedum morganianum, were evaluated for their ability to facilitate the "green synthesis" of MgO nanoparticles. The thermal stability and decomposition behavior of the MgONPs were analyzed by thermogravimetric analysis (TGA). Structure characterization was performed by X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS), ultraviolet-visible spectroscopy (UV-Vis), dynamic light scattering (DLS), and Raman scattering spectroscopy (RS). Morphology was studied by scanning electron microscopy (SEM). The photocatalytic activity of MgO nanoparticles was investigated based on the degradation of methyl orange (MeO) using UV-Vis spectroscopy. Surface-enhanced Raman scattering spectroscopy (SERS) was used to monitor the adsorption of L-phenylalanine (L-Phe) on the surface of MgONPs. The calculated enhancement factor (EF) is up to 102 orders of magnitude for MgO. This is the first work showing the SERS spectra of a chemical compound immobilized on the surface of MgO nanoparticles.

Nitrogen Dioxide Sensing Using Multilayer Structure of Reduced Graphene Oxide and α-Fe2O3.

Multilayers consisting of graphene oxide (GO) and α-Fe2O3 thin layers were deposited on the ceramic substrates by the spray LbL (layer by layer) coating technique. Graphene oxide was prepared from graphite using the modified Hummers method. Obtained GO flakes reached up to 6 nanometers in thickness and 10 micrometers in lateral size. Iron oxide Fe2O3 was obtained by the wet chemical method from FeCl3 and NH4OH solution. Manufactured samples were deposited as 3 LbL (GO and Fe2O3 layers deposited sequentially) and 6 LbL structures with GO as a bottom layer. Electrical measurements show the decrease of multilayer resistance after the introduction of the oxidizing NO2 gas to the ambient air atmosphere. The concentration of NO2 was changed from 1 ppm to 20 ppm. The samples changed their resistance even at temperatures close to room temperature, however, the sensitivity increased with temperature. Fe2O3 is known as an n-type semiconductor, but the rGO/Fe2O3 hybrid structure behaved similarly to rGO, which is p-type. Both chemisorbed O2 and NO2 act as electron traps decreasing the concentration of electrons and increasing the effective multilayer conductivity. An explanation of the observed variations of multilayer structure resistance also the possibility of heterojunctions formation was taken into account.

Cobalt-platinum nanomotors for local gas generation.

Bimetallic Co-Pt nanorods exhibit an enhanced capacity for the production of gas from liquid-phase chemicals. Based on the systematic structural and magnetic characterization we discuss potential applications of these hybrid nanostructures for localized fuel generation in microdevices. Experimental proof of the feasibility for controlling the rate of catalytic reaction via external magnetic stimuli is shown. This unique functionality makes these hybrids promising candidates for optimizing the energy conversion rate in microfluidics fuel cells.

Gas-Sensing Performance of M-Doped CuO-Based Thin Films Working at Different Temperatures upon Exposure to Propane.

Cupric oxide (CuO) thin films are promising materials in gas sensor applications. The CuO-based gas sensors behaved as p-type semiconductors and can be used as part of an e-nose or smart sensor array for breath analysis. The authors present the investigation results on M-doped CuO-based (M = Ag, Au, Cr, Pd, Pt, Sb, Si) sensors working at various temperatures upon exposure to a low concentration of C3H8, which can be found in exhaled human breath, and it can be considered as a one of the biomarkers of several diseases. The films have been deposited in magnetron sputtering technology on low temperature cofired ceramics substrates. The results of the gas sensors' response are also presented and discussed. The Cr:CuO-based structure, annealed at 400 °C for 4 h in air, showed the highest sensor response, of the order of 2.7 at an operation temperature of 250 °C. The response and recovery time(s) were 10 s and 24 s, respectively. The results show that the addition of M-dopants in the cupric oxide films effectively act as catalysts in propane sensors and improve the gas sensing properties. The films' phase composition, microstructure and surface topography have been assessed by the X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX) methods.

Graphene removal by water-assisted focused electron-beam-induced etching - unveiling the dose and dwell time impact on the etch profile and topographical changes in SiO2 substrates.

Graphene is one of the most extensively studied 2D materials, exhibiting extraordinary mechanical and electronic properties. Although many years have passed since its discovery, manipulating single graphene layers is still challenging using standard resist-based lithography techniques. Recently, it has been shown that it is possible to etch graphene directly in water-assisted processes using the so-called focused electron-beam-induced etching (FEBIE), with a spatial resolution of ten nanometers. Nanopatterning graphene with such a method in one single step and without using a physical mask or resist is a very appealing approach. During the process, on top of graphene nanopatterning, we have found significant morphological changes induced in the SiO2 substrate even at low electron dose values (<8 nC/µm2). We demonstrate that graphene etching and topographical changes in SiO2 substrates can be controlled via electron beam parameters such as dwell time and dose.

Determination of the surface diffusion coefficient and the residence time of adsorbates via local focused electron beam induced chemical vapour deposition.

In this paper we present a model for local gas assisted focused electron beam induced deposition which allows estimating the surface diffusion coefficient and the residence time of volatile precursor adsorbates. Elaborating the existing continuum model for one adsorbate species and using a novel set of parameters we simplified the differential equation describing the dynamics of this process. We will show that stationary exposure experiments do not allow for a unique determination of the parameters residence time, surface diffusion coefficient, and net cross-section. Rather an estimation of parameter windows is possible by assuming meaningful values for the electron dissociation cross section. The model was applied to the experimental results for Cu(hfac)2 as a gas precursor.

Ions-free electrochemically synthetized in aqueous media flake-like CuO nanostructures as SERS reproducible substrates for the detection of neurotransmitters.

The process of catalytic destruction of tumor cells can be strengthened by introducing copper(II) oxide nanostructures (CuONSs) with receptor's agonists/antagonists immobilized on their surface. Here we show a simple and reliable electrochemical method for the fabrication ions-free flake-like CuO nanostructures in a surfactant/ions free aqueous environment. For the determination of the metal surface plasmon, size, rheology, and structure of the fabricated nanostructures ultraviolet-visible (UV-Vis), Fourier-transform infrared (FT-IR), Raman, and X-ray photoelectron (XPS) spectroscopies as well as scanning electron microscope (SEM), high-resolution transmission electron microscopy with energy dispersive X-ray (HDTEM-EDS), X-ray powder diffraction (XRD), and dynamic light scattering (DLS) analysis were used. The fabricated nanostructures were used as highly sensitive, uniform, and reproducible sensors of a natural ligand (bombesin) of some types of metabotropic seven transmembrane G protein-coupled superfamily receptors (GPCRs), which are over-express on the surface of many malignant tumors. Surface-enhanced Raman scattering (SERS) was used to monitor the geometry of adsorbate, separate, enrich, and detect various bombesin C-terminal fragments. It has been shown that the type of used substrate, surface development, and ions present in the solution have little effect on the mode of adsorption.

Comparative study of post-growth annealing of Cu(hfac)2, Co2(CO)8 and Me2Au(acac) metal precursors deposited by FEBID.

Non-noble metals, such as Cu and Co, as well as noble metals, such as Au, can be used in a number modern technological applications, which include advanced scanning-probe systems, magnetic memory and storage, ferroelectric tunnel junction memristors, metal interconnects for high performance integrated circuits in microelectronics and nano-optics applications, especially in the areas of plasmonics and metamaterials. Focused-electron-beam-induced deposition (FEBID) is a maskless direct-write tool capable of defining 3-dimensional metal deposits at nanometre scale for above applications. However, codeposition of organic ligands when using organometallic precursors is a typical problem that limits FEBID of pure metal nanostructures. In this work, we present a comparative study using a post-growth annealing protocol at 100, 200, and 300 °C under high vacuum on deposits obtained from Co2(CO)8, Cu(II)(hfac)2, and Me2Au(acac) to study improvements on composition and electrical conductivity. Although the as-deposited material was similar for all precursors, metal grains embedded in a carbonaceous matrix, the post-growth annealing results differed. Cu-containing deposits showed the formation of pure Cu nanocrystals at the outer surface of the initial deposit for temperatures above 100 °C, due to the migration of Cu atoms from the carbonaceous matrix containing carbon, oxygen, and fluorine atoms. The average size of the Cu crystals doubles between 100 and 300 °C of annealing temperature, while the composition remains constant. In contrast, for Co-containing deposits oxygen release was observed upon annealing, while the carbon content remained approximately constant; the cobalt atoms coalesced to form a metallic film. The as-deposited Au-containing material shows subnanometric grains that coalesce at 100 °C, maintaining the same average size at annealing temperatures up to 300 °C. Raman analysis suggests that the amorphous carbonaceous matrix of the as-written Co, Cu and Au deposits turned into nanocrystalline graphite with comparable crystal sizes of 12-14 nm at 300 °C annealing temperature. However, we observed a more effective formation of graphite clusters in Co- than in Cu- and Au-containing deposits. The graphitisation has a minor influence on the electrical conductivity improvements of Co-C deposits, which is attributed to the high as-deposited Co content and the related metal grain percolation. On the contrary, electrical conductivity improvements by factors of 30 and 12 for, respectively, Cu-C and Au-C deposits with low metal content are mainly attributed to the graphitisation. This relatively simple vacuum-based post-growth annealing protocol may be useful for other precursors as it proved to be efficient in reliably tuning the electrical properties of as-deposited FEBID materials. Finally, a H2-assisted gold purification protocol is demonstrated at temperatures around 300 °C by fully removing the carbon matrix and drastically reducing the electrical resistance of the deposit.

Interaction of bombesin and its fragments with gold nanoparticles analyzed using surface-enhanced Raman spectroscopy.

This work demonstrates the application of commercially available stable surface composed of gold nanograins with diameters ranging from 70 to 226nm deposited onto silicon wafer for surface-enhanced Raman scattering investigations of biologically active compounds, such as bombesin (BN) and its fragments. BN is an important neurotransmitter involved in a complex signaling pathways and biological responses; for instance, hypertensive action, contractive on uterus, colon or ileum, locomotor activity, stimulation of gastric and insulin secretion as well as growth promotion of various tumor cell lines, including: lung, prostate, stomach, colon, and breast. It has also been shown that 8-14 BN C-terminal fragment partially retains the biological activity of BN. The SERS results for BN and its fragment demonstrated that (1) three amino acids from these peptides sequence; i.e., l-histidine, l-methionine, and l-tryptophan, are involved in the interaction with gold coated silicon wafer and (2) the strength of these interactions depends upon the aforementioned amino acids position in the peptide sequence.

Continuum models of focused electron beam induced processing.

Focused electron beam induced processing (FEBIP) is a suite of direct-write, high resolution techniques that enable fabrication and editing of nanostructured materials inside scanning electron microscopes and other focused electron beam (FEB) systems. Here we detail continuum techniques that are used to model FEBIP, and release software that can be used to simulate a wide range of processes reported in the FEBIP literature. These include: (i) etching and deposition performed using precursors that interact with a surface through physisorption and activated chemisorption, (ii) gas mixtures used to perform simultaneous focused electron beam induced etching and deposition (FEBIE and FEBID), and (iii) etch processes that proceed through multiple reaction pathways and generate a number of reaction products at the substrate surface. We also review and release software for Monte Carlo modeling of the precursor gas flux which is needed as an input parameter for continuum FEBIP models.

Toward ultraflat surface morphologies during focused electron beam induced nanosynthesis: disruption origins and compensation.

Emerging applications for nanoscale materials demand precise deposit shape retention from design to deposition. This study investigates the effects that disrupt high-fidelity shapes during focused electron beam induced nanosynthesis. It is shown that process parameters, patterning strategies and deposit topography can impose lateral precursor coverage gradients during growth resulting in unwanted topographic artifacts. The study classifies the evolving surface shapes into four general types and explains the formation and transition from a fundamental point of view. Continuum model calculations and simulations expand the experimental results to provide a comprehensive insight into understand the disruption mechanism. The findings demonstrate that the well-established concept of growth regimes has to be expanded by its lateral gradients as they strongly influence final shape fidelities. Finally, the study is complemented by a compensation strategy that improves the edge fidelity on the lower nanoscale to further push this technique toward the intrinsic limitations.

Correction: Formation of pure Cu nanocrystals upon post-growth annealing of Cu-C material obtained from focused electron beam induced deposition: comparison of different methods.

[This corrects the article DOI: 10.3762/bjnano.6.156.].

Formation of pure Cu nanocrystals upon post-growth annealing of Cu-C material obtained from focused electron beam induced deposition: comparison of different methods.

In this paper we study in detail the post-growth annealing of a copper-containing material deposited with focused electron beam induced deposition (FEBID). The organometallic precursor Cu(II)(hfac)2 was used for deposition and the results were compared to that of compared to earlier experiments with (hfac)Cu(I)(VTMS) and (hfac)Cu(I)(DMB). Transmission electron microscopy revealed the deposition of amorphous material from Cu(II)(hfac)2. In contrast, as-deposited material from (hfac)Cu(I)(VTMS) and (hfac)Cu(I)(DMB) was nano-composite with Cu nanocrystals dispersed in a carbonaceous matrix. After annealing at around 150-200 °C all deposits showed the formation of pure Cu nanocrystals at the outer surface of the initial deposit due to the migration of Cu atoms from the carbonaceous matrix containing the elements carbon, oxygen, and fluorine. Post-irradiation of deposits with 200 keV electrons in a transmission electron microscope favored the formation of Cu nanocrystals within the carbonaceous matrix of freestanding rods and suppressed the formation on their surface. Electrical four-point measurements on FEBID lines from Cu(hfac)2 showed five orders of magnitude improvement in conductivity when being annealed conventionally and by laser-induced heating in the scanning electron microscope chamber.

The nanoscale implications of a molecular gas beam during electron beam induced deposition.

The gas flux direction in focused electron beam induced processes can strongly destabilize the morphology on the nanometer scale. We demonstrate how pattern parameters such as position relative to the gas nozzle, axial rotation, scanning direction, and patterning sequence result in different growth modes for identical structures. This is mainly caused by nanoscale geometric shadowing, particularly when shadowing distances are comparable to surface diffusion lengths of (CH3)3-Pt-CpCH3 adsorbates. Furthermore, two different adsorbate replenishment mechanisms exist and are governed by either surface diffusion or directional gas flux adsorption. The experimental study is complemented by calculations and dynamic growth simulations which successfully emulate the observed morphology instabilities and support the proposed growth model.