Implications of size dispersion on X-ray scattering of crystalline nanoparticles: CeO2 as a case study.

Controlling the shape and size dispersivity and crystallinity of nanoparticles (NPs) has been a challenge in identifying these parameters' role in the physical and chemical properties of NPs. The need for reliable quantitative tools for analyzing the dispersivity and crystallinity of NPs is a considerable problem in optimizing scalable synthesis routes capable of controlling NP properties. The most common tools are electron microscopy (EM) and X-ray scattering techniques. However, each technique has different susceptibility to these parameters, implying that more than one technique is necessary to characterize NP systems with maximum reliability. Wide-angle X-ray scattering (WAXS) is mandatory to access information on crystallinity. In contrast, EM or small-angle X-ray scattering (SAXS) is required to access information on whole NP sizes. EM provides average values on relatively small ensembles in contrast to the bulk values accessed by X-ray techniques. Besides the fact that the SAXS and WAXS techniques have different susceptibilities to size distributions, SAXS is easily affected by NP-NP interaction distances. Because of all the variables involved, there have yet to be proposed methodologies for cross-analyzing data from two techniques that can provide reliable quantitative results of dispersivity and crystallinity. In this work, a SAXS/WAXS-based methodology is proposed for simultaneously quantifying size distribution and degree of crystallinity of NPs. The most reliable easy-to-access size result for each technique is demonstrated by computer simulation. Strategies on how to compare these results and how to identify NP-NP interaction effects underneath the SAXS intensity curve are presented. Experimental results are shown for cubic-like CeO2 NPs. WAXS size results from two analytical procedures are compared, line-profile fitting of individual diffraction peaks in opposition to whole pattern fitting. The impact of shape dispersivity is also evaluated. Extension of the proposed methodology for cross-analyzing EM and WAXS data is possible.

Carbon nanotube-cellulose ink for rapid solvent identification.

In this work, a conductive ink based on microfibrillated cellulose (MFC) and multiwalled carbon nanotubes (MWCNTs) was used to produce transducers for rapid liquid identification. The transducers are simple resistive devices that can be easily fabricated by scalable printing techniques. We monitored the electrical response due to the interaction between a given liquid with the carbon nanotube-cellulose film over time. Using principal component analysis of the electrical response, we were able to extract robust data to differentiate between the liquids. We show that the proposed liquid sensor can classify different liquids, including organic solvents (acetone, chloroform, and different alcohols) and is also able to differentiate low concentrations of glycerin in water (10-100 ppm). We have also investigated the influence of two important properties of the liquids, namely dielectric constant and vapor pressure, on the transduction of the MFC-MWCNT sensors. These results were corroborated by independent heat flow measurements (thermogravimetric analysis). The proposed MFC-MWCNT sensor platform may help paving the way to rapid, inexpensive, and robust liquid analysis and identification.

Aerosol-Printed MoS2 Ink as a High Sensitivity Humidity Sensor.

Molybdenum disulfide (MoS2) is attractive for use in next-generation nanoelectronic devices and exhibits great potential for humidity sensing applications. Herein, MoS2 ink was successfully prepared via a simple exfoliation method by sonication. The structural and surface morphology of a deposited ink film was analyzed by scanning electron microscopy (SEM), Raman spectroscopy, and atomic force microscopy (AFM). The aerosol-printed MoS2 ink sensor has high sensitivity, with a conductivity increase by 6 orders of magnitude upon relative humidity increase from 10 to 95% at room temperature. The sensor also has fast response/recovery times and excellent repeatability. Possible mechanisms for the water-induced conductivity increase are discussed. An analytical model that encompasses two ionic conduction regimes, with a percolation transition to an insulating state below a low humidity threshold, describes the sensor response successfully. In conclusion, our work provides a low-cost and straightforward strategy for fabricating a high-performance humidity sensor and fundamental insights into the sensing mechanism.

Oxygen vacancy engineering of TaOx-based resistive memories by Zr doping for improved variability and synaptic behavior.

Resistive switching (RS) devices are promising forms of non-volatile memory. However, one of the biggest challenges for RS memory applications is the device-to-device (D2D) variability, which is related to the intrinsic stochastic formation and configuration of oxygen vacancy (VO) conductive filaments (CFs). In order to reduce the D2D variability, control over the formation and configuration of oxygen vacancies is paramount. In this study, we report on the Zr doping of TaOx-based RS devices prepared by pulsed-laser deposition as an efficient means of reducing the VOformation energy and increasing the confinement of CFs, thus reducing D2D variability. Our findings were supported by XPS, spectroscopic ellipsometry and electronic transport analysis. Zr-doped films showed increased VOconcentration and more localized VOs, due to the interaction with Zr. DC and pulse mode electrical characterization showed that the D2D variability was decreased by a factor of seven, the resistance window was doubled, and a more gradual and monotonic long-term potentiation/depression in pulse switching was achieved in forming-free Zr:TaOxdevices, thus displaying promising performance for artificial synapse applications.

Asymmetric effect of oxygen adsorption on electron and hole mobilities in bilayer graphene: long- and short-range scattering mechanisms.

We probe electron and hole mobilities in bilayer graphene under exposure to molecular oxygen. We find that the adsorbed oxygen reduces electron mobilities and increases hole mobilities in a reversible and activated process. Our experimental results indicate that hole mobilities increase due to the screening of long-range scatterers by oxygen molecules trapped between the graphene and the substrate. First principle calculations show that oxygen molecules induce resonant states close to the charge neutrality point. Electron coupling with such resonant states reduces the electron mobilities, causing a strong asymmetry between electron and hole transport. Our work demonstrates the importance of short-range scattering due to adsorbed species in the electronic transport in bilayer graphene on SiO2 substrates.

Fabrication of gas nanosensors and microsensors via local anodic oxidation.

A nanosensor and microsensor fabrication method employing scanning probe microscopy (SPM) is demonstrated. Within such process, nano- or microscale metal oxide (MoO(x) or TiO(x)) structures, constituting the active region of a sensor, are directly fabricated onto a microscopic metal track via SPM-assisted local anodic oxidation (LAO). Two distinct LAO routes, a slow (conventional) or a fast (unusual) one, are employed to produce nano- and microsensors, which are tested at different temperatures using CO2 and H2 as test gases. Sensitivities down to ppm levels are demonstrated, and the possibility of easy integration into microfabrication processes is also discussed.

Purity evaluation of carbon nanotube materials by thermogravimetric, TEM, and SEM methods.

Raw and purified samples of carbon nanotubes are considered as multicomponent systems with a distribution of carbonaceous, amorphous, multishell graphitic particles and nanotubes, together with the particles of metal compounds from the catalyst. With respect to the carbon nanotube fractions, a distribution of size, defect concentrations, and functionalities needs to be taken into account. In order to address the problem of quantitative evaluation of purity it is necessary to measure the quality and distribution of the carbon nanotubes. In this research conventional and high resolution thermogravimetry are applied to quantify different fractions of carbonaceous and metallic materials in raw and moderately purified single walled and multiwalled carbon nanotubes. For each oxidized fraction, defined by careful line shape analysis of the derivative thermogravimetric curves (DTG), the temperature of maximum rate of oxidation, the temperature range for this oxidation, related to the degree of homogeneity, and the amount of associated material is specified. The attribution of carbonaceous materials to each fraction in the distribution was based on SEM and TEM measurements and the literature. The MWNT purified sample with 1.6 wt% metal oxide was investigated by high resolution thermogravimetry (HRTG). The quantitative assessment for the carbonaceous fractions was 25 wt% of amorphous and high defect carbonaceous materials including nanotubes, 54 wt% MWNT and 20 wt% multishell graphitic particles. A qualitative evaluation of these fractions was obtained from the SEM and TEM images and supports these results. The accuracy of the values, taking into account other measurements performed on the same batch of material, should be more sensible than +/-4 wt%.

Synthesis of silica nanowires by active oxidation of silicon substrates.

Amorphous silica nanowires have been produced by thermal annealing of Si/SiO2/Ni substrate structures at 900 degrees C under an atmosphere of hexamethyldisilazane (HMDS) and hydrogen (H2). The wires have diameter ranging from 35 to 55 nm, which are controlled by the Ni particle size. It is demonstrated that the growth occurs through vapor-liquid-solid mechanisms, and it is proposed that the vapor source is volatile SiO generated from the etching of the Si substrate through active oxidation reactions. The role of the HMDS-H2 atmosphere in promoting such reactions is discussed.