Sample Preparation Route Research Articles

Understanding and Controlling the Crystallization Process in Reconfigurable Plasmonic Superlattices

The crystallization of nanomaterials is a primary source of solid-state, photonic structures. Thus, a detailed understanding of this process is of paramount importance for the successful application of photonic nanomaterials in emerging optoelectronic technologies. While colloidal crystallization has been thoroughly studied, for example, with advanced in situ electron microscopy methods, the noncolloidal crystallization (freezing) of nanoparticles (NPs) remains so far unexplored. To fill this gap, in this work, we present proof-of-principle experiments decoding a crystallization of reconfigurable assemblies of NPs at a solid state. The chosen material corresponds to an excellent testing bed, as it enables both in situ and ex situ investigation using X-ray diffraction (XRD), transmission electron microscopy (TEM), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), atomic force microscopy (AFM), and optical spectroscopy in visible and ultraviolet range (UV–vis) techniques. In particular, ensemble measurements with small-angle XRD highlighted the dependence of the correlation length in the NPs assemblies on the number of heating/cooling cycles and the rate of cooling. Ex situ TEM imaging further supported these results by revealing a dependence of domain size and structure on the sample preparation route and by showing we can control the domain size over 2 orders of magnitude. The application of HAADF-STEM tomography, combined with in situ thermal control, provided three-dimensional single-particle level information on the positional order evolution within assemblies. This combination of real and reciprocal space provides insightful information on the anisotropic, reversibly reconfigurable assemblies of NPs. TEM measurements also highlighted the importance of interfaces in the polydomain structure of nanoparticle solids, allowing us to understand experimentally observed differences in UV–vis extinction spectra of the differently prepared crystallites. Overall, the obtained results show that the combination of in situ heating HAADF-STEM tomography with XRD and ex situ TEM techniques is a powerful approach to study nanoparticle freezing processes and to reveal the crucial impact of disorder in the solid-state aggregates of NPs on their plasmonic properties.

Comparing Xe+ pFIB and Ga+ FIB for TEM sample preparation of Al alloys: Minimising FIB-induced artefacts.

Recently, the dual beam Xe+ plasma focused ion beam (Xe+pFIB) instrument has attracted increasing interest for site‐specific transmission electron microscopy (TEM) sample preparation for a local region of interest as it shows several potential benefits compared to conventional Ga+FIB milling. Nevertheless, challenges and questions remain especially in terms of FIB‐induced artefacts, which hinder reliable S/TEM microstructural and compositional analysis. Here we examine the efficacy of using Xe+ pFIB as compared with conventional Ga+ FIB for TEM sample preparation of Al alloys. Three potential source of specimen preparation artefacts were examined, namely: (1) implantation‐induced defects such as amophisation, dislocations, or ‘bubble’ formation in the near‐surface region resulting from ion bombardment of the sample by the incident beam; (2) compositional artefacts due to implantation of the source ions and (3) material redeposition due to the milling process. It is shown that Xe+pFIB milling is able to produce improved STEM/TEM samples compared to those produced by Ga+ milling, and is therefore the preferred specimen preparation route. Strategies for minimising the artefacts induced by Xe+pFIB and Ga+FIB are also proposed.Lay Description FIB (focused ion beam) instruments have become one of the most important systems in the preparation of site‐specific TEM specimens, which are typically 50‐100 nm in thickness. TEM specimen preparation of Al alloys is particularly challenging, as convention Ga‐ion FIB produces artefacts in these materials that make microstructural analysis difficult or impossible. Recently, the use of noble gas ion sources, such as Xe, has markedly improved milling speeds and is being used for the preparation of various materials. Hence, it is necessary to investigate the structural defects formed during FIB milling and assess the ion‐induced chemical contamination in these TEM samples. Here we explore the feasibility and efficiency of using Xe+PFIB as a TEM sample preparation route for Al alloys in comparison with the conventional Ga+FIB.

Ultrasound Assisted Ferrofluid Dispersive Liquid Phase Microextraction Coupled with Flame Atomic Absorption Spectroscopy for the Determination of Cobalt in Environmental Samples

This study proposes a novel deep eutectic solvent based-ferrofluid to develop a dispersive liquid phase microextraction method. The efficiency of the protocol was evaluated by determining the trace levels of Co (II) from environmental water samples by flame atomic absorption spectroscopy. Ultrasound was employed to enhance the sorbent dispersion with enhanced extraction recovery. The experimental variables with a significant impact on the cobalt extraction efficiency were also examined. Using the optimal conditions, the limit of detection and enrichment factor were 0.7 and 50 µg/L, respectively. The relative standard deviation was 2.6%. The proposed method successfully determined cobalt in water samples with recovery and relative standard deviation values from 96.4 to 99.0% and 2.4 to 3.9%, respectively. This promising method is an environmentally friendly, feasible, and efficient sample preparation route.

Atomic Force Microscopy Study of Cross-Sections of Perovskite Layers

Improvement of methods for imaging of the volume structure of photoactive layers is one of the important directions towards development of highly efficient solar cells. In particular, volume structure of photoactive layer has critical influence on perovskite solar cell performance and life time. In this study, a perovskite photoactive layer cross-section was prepared by using Focused Ion Beam (FIB) and imaged by Atomic Force Microscopy (AFM) methods. The proposed approach allows using advances of AFM for imaging structure of perovskites in volume. Two different types of perovskite layers was investigated: FAPbBr3 and MAPbBr3. The heterogeneous structure inside film, which consist of large crystals penetrating the film as well as small particles with sizes of several tens nanometers, is typical for FAPbBr3. The ordered nanocrystalline structure with nanocrystals oriented at 45 degree to film surface is observed in MAPbBr3. An optimized sample preparation route, which includes FIB surface polishing by low energy Ga ions at the angles around 10 degree to surface plane, is described and optimal parameters of surface treatment are discussed. Use of AFM phase contrast method provides high contrast imaging of perovskite structure due to strong dependence of phase shift of oscillating probe on materials properties. The described method of imaging can be used for controllable tuning of perovskite structure by changes of the sample preparation routes.

Reactivity-driven cleanup of 2-Aminobenzamide derivatized oligosaccharides

N-glycan profiling is commonly accomplished by the derivatization of the enzymatically released oligosaccharides with a fluorophore, thereby facilitating their analysis by hydrophilic-interaction liquid chromatography (HILIC). These fluorescent dyes are often present in large excess during derivatization reactions, and their removal is typically required to minimize chromatographic interference. Herein, we report a reactivity-driven 2-phase extraction protocol with the aldehyde reagent octanal, which demonstrated efficient 2-aminobenzamide cleanup as well as high derivatized N-glycan recovery. This cleanup method can be performed within minutes, and therefore provides an alternative sample preparation route for N-glycan profiling with improved time efficiency and operational simplicity.

Tuning Charge Carrier Dynamics and Surface Passivation in Organolead Halide Perovskites with Capping Ligands and Metal Oxide Interfaces

AbstractOrganolead halide perovskites have emerged as exciting optoelectronic materials but a complete understanding of their photophysical properties is still lacking. Here, a morphological series of methylammonium lead bromide (MAPbBr3) perovskites are studied by transient optical spectroscopies over eight orders of magnitude in timescale to investigate the effect of nanostructuring and surface states on the charge carrier dynamics. The sample preparation route and corresponding morphology changes influence the position of the optical features, recombination dynamics, excitation fluence dependence, and dramatically impact surface trap passivation. Growth of the perovskite layer in the presence of capping ligands or within mesoporous alumina increases the photoluminescence efficiency by multiple orders of magnitude, indicating that interfacing with metal oxides can lead to the passivation of surface nonradiative recombination centers. Nanoparticles (NPs) dispersed in solution show mixed behavior since they consist of NPs on nanoplatelets, while isolated NPs could be grown within mesoporous alumina with the addition of capping ligands. Investigation on the microsecond timescale suggests that an exponential distribution of states below the band edges results in long‐lived charges. The investigations of the relationship between sample architecture and charge carrier dynamics will help in the appropriate choice of perovskite morphology for use in optoelectronic devices.

Electronic paper from facile, two-step deposition of CuS

A method is proposed to impregnate regular cellulosic paper with semi-conductive particles of copper sulfide. The method consists of a simple two-step procedure: first, metal (Cu) ions in solution are applied to the paper, and second, the aqueous application of a source of sulfide ions, which leads to the spontaneous formation of metal sulfides in the pores of the paper matrix, as evidenced by a color change. This methodology is easy to implement and involves very low-cost and easily available chemical agents, leading to the production of low-price semiconductor devices. In this work, the microscopic morphology and crystalline structures of films were studied, as well as their optical and electrical properties. The proposed sample preparation route could potentially be implemented in further research using different metals in order to obtain tunable physical properties, such as band gap, conductivity and conductivity carrier types.

Effect of Sample Preparation Route on the Thermal Diffusivity of Nd2O3 - A Laser Induced Photoacoustic Study

Effect of Sample Preparation Route on the Thermal Diffusivity of Nd2O3 - A Laser Induced Photoacoustic Study

Relaxor Ferroelectric Behavior in Barium Strontium Titanate

The development of barium strontium titanate‐based tunable dielectrics is currently hindered by high losses in the paraelectric phase. Barium strontium titanate (BST) thin films and ceramics show a range of ferroelectric transition behavior, from normal, diffuse, and relaxor‐like ferroelectric responses, depending on the sample preparation route. Rayleigh analysis, the temperature‐dependent dielectric response, and the optical second harmonic generation were used to characterize the ferroelectric response of bulk and thin film BST. Ferroelectricity is observed to persist in BST for 30°C above the global phase transition temperature in ceramics and over 50°C in thin films. Piezoresponse force microscopy on BST ceramics with extensive residual ferroelectricity reveals the coexistence of nanoscale polar regions, typical of relaxor ferroelectrics, as well as micrometer scale domain structures. The nature of the phase transition was probed using electron energy loss spectroscopy and found to correlated with the nanoscale A‐site chemical inhomogeneity in the samples.

Critical magnetic behavior and large magnetocaloric effect in Pr0.67Ba0.33MnO3 perovskite manganite

We report results of critical magnetic behavior and magnetocaloric investigations of the perovskite manganite Pr0.67Ba0.33MnO3. The compound exhibits a paramagnetic (PM) to ferromagnetic (FM) transition at the Curie temperature TC, and significant negative magnetoresistance in a wide temperature range. To probe the magnetic interactions responsible for the magnetic transitions, we performed a critical exponent analysis in the vicinity of the FM–PM transition region. Magnetic entropy change ΔSM was estimated from isothermal magnetization data. We have found a remarkable large value of |ΔSM| around TC’s, of about 5.50J/kgK for μ0ΔH=4T and a large relative cooling power (~225J/kg). The analysis was done by using the modified Arrot plot (MAP) method. The values of the obtained critical exponents associated with this transition, β=0.366, γ=1.375 and δ=4.743 are close to those expected for the short range 3D Heisenberg model. The model was also confirmed by using |ΔSM|∝(μ0H)n, the field dependence of magnetic entropy change method. The large measured magnetocaloric effect is presumed to arise as a consequence of the sample preparation route.

Assessment of DFG-S19 method for the determination of common endocrine disruptor pesticides in wine samples with an estimation of the uncertainty of the analytical results

A gas chromatographic method for the determination of endocrine disruptor pesticides (Chlorpyrifos, Penconazole, Procymidone, Iprodione, Bromopropylate and Lambda-Cyhalothrin) in wine samples is described. A general DFG-S19 method for residual pesticide determination in all kind of food stuff was investigated to simplify and adopt for wine samples in this work. Alternative sample preparation routes were elucidated and compared according to their recovery values. Four different separation techniques were tested and the method employing florosil column after a LLE procedure was applied for wine samples with satisfactory recovery ratios (72–97%). The pesticides were extracted from the sample by cyclohexane–ethyl acetate mixture (1:1 v/v) and cleaned up by florosil column. The regression coefficients were at least 0.99 and relative standard deviations were no higher than 16%. Detection limits were in the range of 0.6–2.9ng/mL and the relative expanded measurement uncertainties were calculated in the 7–22% range.

The detection of high‐mass aliphatics in petroleum by matrix‐assisted laser desorption/ionisation mass spectrometry

The development of simplified procedures for isolating high-mass alkanes present in crude oils is described. The new procedures, which bypass the sample recovery step with hot toluene in the conventional alkane-isolation procedure, also provide an effective sample preparation route, prior to analysis by matrix-assisted laser desorption/ionisation mass spectrometry (MALDI-MS). Urea-alkane adducts are formed by mixing sample and urea solutions on chromatographic paper or silica-coated plates. Unreacted hydrocarbons are removed by developing the plates with chloroform. In a second development with water, adducts are broken up in situ and the liberated urea removed, leaving bands of isolated alkanes behind. For MALDI-MS, strips of paper/plates, carrying the isolated alkanes, are fixed on metal target plates. The samples are treated with matrix (AgNO(3)) and analysed by MALDI-MS. The observed signal represents silver ion adducts of the isolated alkanes. Silver appears to work without much fragmentation and to generate whole silver adduct ions. Much improved MALDI-MS detection sensitivity and a wider range of masses was observed when samples were ablated from paper/plate surfaces, than by ablation from bulk samples spread over a smooth surface--the conventional method. Chromatographic paper gave better resolution and a broader range of masses than silica-coated plates. The analytical sequences have been confirmed using standard alkanes (C(20)-C(60)) and Polywax. The proposed procedures enhanced the sensitivity and detection range of the MS analysis. The method was useful in detecting n-alkanes to m/z 1500 (C(100)) and required relatively small quantities of sample and reagents. It provides a promising qualitative analysis route for the rapid isolation and reliable determination of alkanes in crude oils.

On sample preparation and dielectric breakdown in nanostructured epoxy resins

There are many methods available to achieve a good dispersion of fillers within a polymeric matrix. This investigation considered several methods of dispersing three chosen fillers within an epoxy resin; the same processes were also performed on unfilled materials to investigate any effects they may have on the host material. For this investigation, the epoxy system (EP) was combined with sodium montmorillonite (MMT), micrometric silicon dioxide (SD) or nanometric silicon dioxide (NSD) as fillers. The effect of the different sample preparation routes on breakdown behaviour was then evaluated. While more thorough mixing protocols were found to lead to improved breakdown behaviour in the case of the various filled systems, surprisingly, an entirely equivalent form of behaviour was also seen in the unfilled epoxy. The influence of changes in sample geometry on the breakdown strength was established.

Carboxylated core–shell particles: II. Experimental and theoretical comparison of salt-induced swelling

In a previous work [1] we showed that the swelling behavior of carboxylated core-shell particles (PS-PC) can be modified using a specific sample preparation route or favoring the hydrophobic attractive interaction by other way, i.e. controlling the temperature. In that paper, we found that the swelling was promoted in those particles which were initially in a highly swollen state (pH⩾10) while it was hindered for those particles which were not previously in this trigger pH. In this work, we present a discussion of the salt-induced swelling of the same carboxylated core-shell system (PS-PC) with two tuned swelling behaviors: the former, called A-2, exhibits promoted swelling while in the latter, called B-1, the swelling is greatly suppressed because of a compact conformation of the polymer shell is induced [1]. Good agreement between experimental, numerical and theoretical results at all pH values is obtained for promoted particles (A-2). On the other hand, the salt-induced swelling behaviors shown by hindered particles (B-1) corroborate that polymer restructuring includes assembly among ionic groups which affect their ionization degree and also the electrosteric interaction between particles. Finally, the salt-induced swelling behavior shown by the B-1 system at pH 8.6 resembles the Pincus regime predicted by scaling theory.

Microstructure and Properties of the Ni-CGO Composite Anodes Prepared by the Electrostatic-Assisted Ultrasonic Spray Pyrolysis Method

Composite NiO–CGO (Ce0.9Gd0.1O1.95) films were deposited on CGO substrates using the electrostatic-assisted ultrasonic spray pyrolysis (EAUSP) method. Deposition parameters were varied systematically to investigate their effects on film microstructure and electrochemical performance. The X-ray diffraction patterns indicate that the desired crystalline phases of NiO and CGO were obtained in the deposited and then the calcined films. The NiO phase was further converted into a crystalline Ni phase after a reduction treatment. Scanning electron microscope examination revealed that the deposition temperature and electric field strength were dominant factors determining the morphology and microstructure of the deposited films. A deposition temperature of 450°C and an electrostatic field introduced by an applied voltage of 12 kV were identified to yield a cauliflower-like structure with high porosity. A film thus deposited with a NiO:CGO mole ratio of 6:4 performed best as a solid oxide fuel cell anode, as revealed by the ac impedance measurement of Ni–CGO//CGO//Ni–CGO cells in an atmosphere of humidified H2. The representative area-specific resistance value was 0.09 Ω·cm2 at 550°C, which was considerably smaller than that obtained by conventional sample preparation routes. In view of the simplicity, efficiency, and economy of film deposition and the sound electrochemical characteristics of the films obtained found in the current work, it is concluded that the EAUSP method is a promising method for the preparation of Ni–CGO composite anode films.

Microstructure and Properties of the La0.6Sr0.4Co0.2Fe0.8O3 Cathodes Prepared by Electrostatic-Assisted Ultrasonic Spray Pyrolysis Method

Deposition of (LSCF) oxide films on Gd-doped ceria (CGO) substrates by an electrostatic-assisted ultrasonic spray pyrolysis (EAUSP) method was demonstrated for the first time in this work. The electrostatic field employed for directing the aerosol stream toward the substrate was shown to be indispensable for film deposition. The X-ray diffraction result indicates that a single phase of cubic perovskite was obtained in the calcined films. Scanning electron microscopy examination reveals that the electric field strength had a profound effect on film porosity with weaker field, resulting in higher porosity. The results of impedance measurement on LSCF//CGO//LSCF cells indicate that the area specific resistance values of current LSCF films and their activation energies are comparable to that obtained by conventional sample preparation routes. In view of the simplicity, efficiency, and economy of film deposition, and the sound electrochemical characteristics of the obtained films manifested in current work, it is concluded that the EAUSP method is a promising method for preparation of SOFC electrode films.

A Salt-Free Zero-Charged Aqueous Onion-Phase Enhances the Solubility of Fullerene C60 in Water

An onion-phase (multilamellar vesicular phase or Lalpha-phase) was prepared from salt-free zero-charged cationic and anionic (catanionic) surfactant mixtures of tetradecyltrimethylammonium hydroxide (TTAOH)/lauric acid (LA)/H2O. The H+ and OH- counterions form water (TTAOH + LA --> TTAL + H2O), leaving the solution salt free. The onion-phase solution has novel properties including low conductivity, low osmotic pressure and unscreened electrostatic repulsions between cationic and anionic surfactants because of the absence of salt. The spherical multilamellar vesicles have an average 250 nm radius as measured by freeze-fracture transmission electron microscopy (FF-TEM) and the maximum interlayer distance, i.e., the thickness of the hydrophobic bilayer and the water layer, was calculated to be around 52 nm by small-angle X-ray scattering (SAXS). Extremely hydrophobic C60 fullerene can be solubilized in this salt-free zero-charged aqueous onion-phase. As a typical result, 0.588 mg.mL(-1) (approximately 0.82 mmol.L(-1)) C60 has been successfully solubilized into a 50 mmol.L(-1) catanionic surfactant onion-phase aqueous solution. The weight ratio of fullerene to TTAL is calculated to be around 1:40. Solubilization of C60 in the salt-free catanionic onion-phase solution was investigated by using different sample preparation routes, and a variety of techniques were used to characterize these vesicular systems with or without encapsulated C60. The onion-phase solution changed color from slightly bluish to yellow or brown after C60 was solubilized. 1H and 13C NMR measurements indicated that the C60 molecules are located in the hydrophobic layers, i.e., in the central positions [omega-CH3 and delta-(CH2)x] of the hydrophobic layers of the TTAL onion-phase. Salt-free zero-charged catanionic vesicular aqueous solutions are good candidates for enhancing the solubility of C60 in aqueous solutions and may broaden the functionality of fullerenes to new potential applications in biology, medicine, and materials. Hopefully, our method can also be extended to solubilize functionalized carbon nanotubes in aqueous solutions.

Examination of surface films on aluminium and its alloys by low-voltage scanning and scanning transmission electron microscopy

The potential of low-voltage, high-resolution scanning and scanning transmission electron microscopy (SEM/STEM) for morphological characterization of various surface insulating films on aluminium and its alloys has been assessed by examination of porous anodic films, barrier anodic films and corrosion product layers. The characterization shows clearly the value of the approaches, particularly the ability to image directly fine details of appropriately-prepared aluminium surfaces that have usually required examination by transmission electron microscopy (TEM). Such ready characterization assists mechanistic understanding of the contributions of the macroscopic surface and flaws or second phase to the filming and corrosion processes. Further, the approaches are applicable to other materials where such understanding was limited by the sample preparation routes available for TEM.

Tunneling barrier in nanoparticle junctions of La2/3(Ca,Sr)1/3MnO3: Nonlinear current–voltage characteristics

We study the nonlinear current–voltage (I–V) characteristics and analyze the voltage-dependent tunneling conductance in nanoparticles of La2/3A1/3MnO3 (A=Ca, Sr). The powders were prepared by different wet-chemical routes and low calcination temperatures were used to obtain an average particle size D≈30 nm. The data are comprehensively explained in terms of the tunneling picture, which allows one to estimate the height of the grain boundary insulating barrier (φ) for each sample. For constant D, our results show that the sample preparation route is mainly responsible for the value of φ in nanoparticles, while the Coulomb gap in the Coulomb blockade regime is ∼3 times higher for Sr- than for Ca-doping. We also show that a small fraction of the barriers contribute to the nonlinear transport, and the current is mainly carried through low-resistive percolated paths. In addition, despite the different barrier strengths, the low-field magnetoresistance (LFMR) is similar for all samples, implying that φ is not the fundamental parameter determining the LFMR.

The use of the focused ion beam technique to prepare cross-sectional transmission electron microscopy specimen of polymer solar cells deposited on glass

The use of the focused ion beam (FIB) technique for cross-sectional transmission electron microscopy (TEM) specimen preparation of polymer solar cells deposited on glass substrates is described. Ultra-thin sections were prepared using the ‘lift-out’ technique. Electron microscopy investigations of these specimen resulted in detailed morphological information of the devices (e.g. thickness and interface roughness of the layers). In comparison with standard sample preparation routes for TEM investigations the used technique is well suited for precise sectioning of hybrid structures.