Probing Ag nanoparticle surface oxidation in contact with (in)organics: an X‐ray scattering and fluorescence yield approach

Characterizing interfacial reactions is a crucial part of understanding the behavior of nanoparticles in nature and for unlocking their functional potential. Here, an advanced nanostructure characterization approach to study the corrosion processes of silver nanoparticles (Ag‐Nps), currently the most highly produced nanoparticle for nanotechnology, is presented. Corrosion of Ag‐Nps under aqueous conditions, in particular in the presence of organic matter and halide species common to many natural environments, is of particular importance because the release of toxic Ag⁺ from oxidation/dissolution of Ag‐Nps may strongly impact ecosystems. In this context, Ag‐Nps capped with polyvinolpyrrolidone (PVP) in contact with a simple proxy of organic matter in natural waters [polyacrylic acid (PAA) and Cl^? in solution] has been investigated. A combination of synchrotron‐based X‐ray standing‐wave fluorescence yield‐ and X‐ray diffraction‐based experiments on a sample consisting of an approximately single‐particle layer of Ag‐Nps deposited on a silicon substrate and coated by a thin film of PAA containing Cl revealed the formation of a stable AgCl corrosion product despite the presence of potential surface stabilizers (PVP and PAA). Diffusion and precipitation processes at the Ag‐Nps–PAA interface were characterized with a high spatial resolution using this new approach.     

Investigations of magnetic and dielectric properties of cupric oxide nanoparticles

Cupric oxide nanoparticles of ∼8-10 nm width and 40-45 nm length self assembled as large particles ∼1-1.5 μm have been investigated, in the 10-325 K temperature range, using magnetic and dielectric measurements. In magnetic measurements a single broad peak at ∼230 K in a zero field cooled sample has been observed. Coercivity, in magnetization measurements at 10 K, suggests that the nanoparticles are core-shell type particles with an antiferromagnetic core and a ferromagnetic shell. Dielectric measurements, at various frequencies from 3.7 Hz to 949 kHz, exhibit a sharp peak at 284 K followed by weak anomalies around 213 and 230 K.     

The effect of surface morphology on the response of Fe2O3-loaded vanadium oxide nanotubes gas sensor

The effect of surface morphology on the response of an ethanol sensor based on vanadium nanotubes surface loaded with Fe₂O₃ nanoparticles (Fe₂O₃/VONTs) was investigated in this work. The particle size of Fe₂O₃ loaded on VONTs was varied by using novel citric acid-assisted hydrothermal method. In the synthesis progress, citric acid was used as a surfactant and chelate agent, which ensured the growth of a uniform Fe₂O₃ loading on the nanotubes surface. The ethanol sensing properties was then measured for these Fe₂O₃/VONTs at 230-300 °C. The results showed that the sensor response increased with the particles size and the loading amount of Fe₂O₃. It appears that the load of Fe₂O₃ on the VONTs surface increases the concentration of oxygen vacancies and decreases the concentration of free electrons. The effects of morphology on the sensor resistance were interpreted in terms of the Debye length and the difference in the number of active sites.     

Superhydrophobicity of silica nanoparticles modified with polystyrene

Polystyrene/silica nanoparticles were prepared by radical polymerization of silica nanoparticles possessing vinyl groups and styrene with benzoyl peroxide. The resulting vinyl silica nanoparticles, polystyrene/silica nanoparticles were characterized by means of Fourier transformation infrared spectroscopy, scanning electron microscopy and UV-vis absorption spectroscopy. The results indicated that polystyrene had been successfully grafted onto vinyl silica nanoparticles via covalent bond. The morphological structure of polystyrene/silica nanoparticles film, investigated by scanning electron microscopy, showed a characteristic rough structure. Surface wetting properties of the polystyrene/silica nanoparticles film were evaluated by measuring water contact angle and the sliding angle using a contact angle goniometer, which were measured to be 159° and 2°, respectively. The excellent superhydrophobic property enlarges potential applications of the superhydrophobic surfaces.     

Synthesis of silver nanoparticle in imidazolium and pyrolidium based ionic liquid reverse micelles: A step forward in nanostructure inorganic material in room temperature ionic liquid field

Two silver salts, silver tetrafluoroborate and silver trifluoromethanesulfonate were dissolved in two different room temperature ionic liquids (RTILs), 1-Butyl-3 methyl imidazolium tetrafluoroborate ([Bmim][BF₄]) and 1-Butyl-1 methyl pyrrolidinium trifluoromethanesulfonate ([Bmpy][Tfms]). Triton x-100 (TX-100) surfactant and cyclohexane as nonpolar medium are used to dissolve these RTILs to create reverse micellar system. Pure reverse micellar system is characterized by dynamic light scattering (DLS) measurement. These pure RTIL reverse micellar systems are used to prepare stable silver nanoparticle solution without using any other auxiliary solvent in the whole process.     

Quantitative nanoscopic impedance measurements on silver-ion conducting glasses using atomic force microscopy combined with impedance spectroscopy

Nanoscopic impedance measurements were carried out on silver ion conducting glasses by coupling an impedance spectrometer with an atomic force microscope. When ac voltages were applied to a conducting AFM tip being in contact with the glass surface, silver nanoparticles were formed during the cathodic half cycle, which were not completely reoxidized in the anodic half cycle. We describe two protocols allowing for a controlled particle growth. The electrochemical oxidation/reduction processes led to low tip/sample interfacial impedances, and the formed silver particles acted as nanoelectrodes sensing the spreading resistance of the glass below the particles. We made a quantitative check of the spreading resistance formula under the assumption that spreading of the electric field is governed by the lateral diameter of the particles and found good agreement between the mean value of the local conductivities obtained at different tip positions and the macroscopic conductivity.     

Influence of adhesion of silica and ceria abrasive nanoparticles on Chemical-Mechanical Planarization of silica surfaces

We report on a direct measurement of adhesion between abrasive nanoparticles of irregular shape, which are used in semiconductor industry in the process of Chemical-Mechanical Planarization (CMP), and silica surface. The adhesion of ceria and silica nanoparticles to silica surface is measured in multiple chemistries of different CMP slurries using a specially developed atomic force microscopy (AFM) method. Using this method, we study the influence of adhesion on the main parameters of CMP, removal rate and defectivity, scratches. While being plausible to expect correlation between these parameters and adhesion, it has not been systematically studied as of yet. We observed direct correlation between adhesion and removal rate. Comparing the measured defectivity and adhesion, we observe the presence of some correlation between these parameters. We conclude that both adhesion and shape of abrasive particles influence defectivity, micro-scratches. Direct measurements of the adhesion between abrasive nano-particles and surface can be used in the screening of new slurries as well as various modeling related to wearing of the surfaces.     

Modifications in silver-doped silicate glasses induced by ns laser beams

Glass layers for planar light waveguides prepared by Ag-Na ion exchange of different silicate glasses in molten salt baths are annealed and/or irradiated with a laser beam in the UV region, with different energy density values and total pulse numbers. The samples are mainly characterized by optical absorption spectroscopy, luminescence spectroscopy, and Rutherford backscattering spectrometry, in order to determine the role of irradiation parameters and of the host matrix structure in the aggregation phenomena. Photoluminescence spectroscopy gave information regarding the presence of Ag multimeric aggregates, the primal seeds for the growing (nano)crystals. The appearance of the plasmon resonance band in the optical absorption spectra proved the formation of Ag clusters and allowed the evolution steps of the clusterization process to be followed as a function of the energy deposited during the laser irradiation.     

Surface modification of gold nanoparticles and their monolayer behavior at the air/water interface

Gold nanoparticles were prepared by two different methods. The first method was chemically grafting the particles with different lengths of alkylthiol (C₆SH, C₁₂SH and C₁₈SH). For the second method, the Au particles were surface modified first by mercaptosuccinic acid (MSA) to render a surface with carboxylic acid groups which play a role to physically adsorb cationic surfactant in chloroform. This method was termed physical/chemical method. In the first method, the effects of alkyl chain length and dispersion solvent on the monolayer behavior of surface modified gold nanoparticles was evaluated. The gold nanoparticles prepared by 1-hexanthiol demonstrated the narrowest size distribution. Most of them showed narrower particle size distributions in chloroform than in hexane. For the physical/chemical method, the particles can spread more uniformly on the water surface which is attributed to the amphiphilic character of the particles at the air/water interface. However, the particles cannot pack closely due to the relatively weak particle-particle interaction. The effect of alkyl chain length was also assessed for the second method.     

Peptide-induced patterning of gold nanoparticle thin films

In this work, the use of patterned proteins and peptides for the deposition of gold nanoparticles on several substrates with different surface chemistries is presented. The patterned biomolecule on the surface acts as a catalyst to precipitate gold nanoparticles from a precursor solution of HAuCl₄ onto the substrate. The peptide patterning on the surfaces was accomplished by physical adsorption or covalent attachment. It was shown that by using covalent attachment with a linker molecule, the influence of the surface properties from the different substrates on the biomolecule adsorption and subsequent nanoparticle deposition could be avoided. By adjusting the reaction conditions such as pH or HAuCl₄ concentration, the sizes and morphologies of deposited gold nanoparticle agglomerates could be controlled. Two biomolecules were used for this experiment, 3XFLAG peptide and bovine serum albumin (BSA). A micro-transfer molding technique was used to pattern the peptides on the substrates, in which a pre-patterned poly(dimethylsiloxane) (PDMS) mold was used to deposit a lift-off pattern of polypropylmethacrylate (PPMA) on the various substrates. The proteins were either physically adsorbed or covalently attached to the substrates, and an aqueous HAuCl₄ solution was applied on the substrates with the protein micropatterns, causing the precipitation of gold nanoparticles onto the patterns. SEM, AFM, and Electron Beam Induced Current (EBIC) were used for characterization.