Filament Growth and Related Instabilities during Adsorbate Suppressed Electrodeposition.

Anisotropic growth of a single filament on a microelectrode is demonstrated by galvanostatic electrodeposition in a bistable passive-active critical system. Specifically, a Cu filament is formed by disruption of a passivating polyether-halide bilayer triggered by metal deposition with positive feedback guiding highly localized deposition. For macroscale electrodes, complex passive-active Turing patterns develop, while for micrometer-sized electrodes, bifurcation is frustrated and a single active zone develops, which is reinforced by hemispherical transport. As deposition proceeds, hemispherical symmetry is broken with lateral propagation of a single filament while an increasing fraction of the applied current supports expansion of the passive sidewall area that eventually leads to termination of anisotropic growth. Different polyether suppressors alter the dynamic range between passive and active growth that determines the shape and extent of filament formation. The impact of electrode area, geometry, and applied current on morphological evolution was also briefly examined. The results highlight the utility of appropriately scaled microelectrodes in the study of growth instabilities during breakdown of additive suppressed layers in critical electrodeposition systems.

Selected Area Electron Beam Induced Deposition of Pt and W for EBSD Backgrounds.

Applying high-resolution electron backscatter diffraction (HR-EBSD) to materials without regions that are amenable to the acquisition of backgrounds for static flat fielding (background subtraction) can cause analysis problems. To address this difficulty, the efficacy of electron beam induced deposition (EBID) of material as a source for an amorphous background signal is assessed and found to be practical. Using EBID material for EBSD backgrounds allows single crystal and large-grained samples to be analyzed using HR-EBSD for strain and small angle rotation measurement.

In-situ elastic strain mapping during micromechanical testing using EBSD.

Compared to more commonly used strain measurement techniques, electron backscatter diffraction (EBSD) offers improved spatial resolution and measurement sensitivity. Additionally, EBSD can provide the full deformation tensor, whereas other techniques, such as digital image correlation (DIC), are limited to only in-plane strains and rotations. In this work, EBSD was used to measure strains and rotations in-situ during testing of a single-crystal silicon micromechanical test specimen. The theta-like specimen geometry was chosen due to the complex and spatially-varying strain states that exist in the circular frame of the sample during testing, as well as the nominally uniform strains in the central web. Full-field strain maps were generated for each strain and rotation component and compared to those from finite element analyses (FEA), showing strong agreement in all cases. Additionally, potential sources of error and their impact on both measurement accuracy and uncertainty are discussed.

Multi-environment Nanocalorimeter with Electrical Contacts for Use in the Scanning Electron Microscope.

We have developed a versatile nanocalorimeter sensor which allows imaging and electrical measurements of samples under different gaseous environments using the scanning electron microscope (SEM) and can simultaneously measure the sample temperature and associated heat of reaction. This new sensor consists of four independent heating/sensing elements for nanocalorimetry and eight electrodes for electrical measurements, all mounted on a 50 nm thick, 250 µm × 250 µm suspended silicon nitride membrane. This membrane is highly electron transparent and mechanically robust enabling in situ SEM observation under realistic temperatures, environmental conditions and pressures up to one atmosphere. To demonstrate this new capability, we report here on 1) in situ SEM-nanocalorimetry study of melting and solidification of polyethylene oxide, 2) the temperature dependence of conductivity of a nanowire; 3) the electron beam induced current measurements (EBID) of a nanowire in vacuum and air. Furthermore, the sensor is easily adaptable to operate in liquid environment and is compatible with most existing SEM. This versatile platform couples nanocalorimetry with in situ SEM imaging under various gaseous and liquid environments and is applicable to materials research, nanotechnology, energy, catalysis and biomedical applications.

Detecting Carbon in Carbon: Exploiting Differential Charging to Obtain Information on the Chemical Identity and Spatial Location of Carbon Nanotube Aggregates in Composites by Imaging X-ray Photoelectron Spectroscopy.

To better assess risks associated with nano-enabled products including multiwalled carbon nanotubes (MWCNT) within polymer matrices, it is important to understand how MWCNT are dispersed throughout the composite. The current study presents a method which employs imaging X-ray photoelectron spectroscopy (XPS) to chemically detect spatially segregated MWCNT rich regions at an epoxy composites surface by exploiting differential charging. MWCNT do not charge due to high conductivity and have previously been shown to energetically separate from their insulating surroundings when characterized by XPS. XPS in imaging mode revealed that these conductive regions were spatially separated due to micrometer-scale MWCNT aggregation and poor dispersion during the formation of the composite. Three MWCNT concentrations were studied; (1, 4 and 5) % by mass MWCNT within an epoxy matrix. Images acquired in periodic energy intervals were processed using custom algorithms designed to efficiently extract spectra from regions of interest. As a result, chemical and electrical information on aggregate and non-aggregate portions of the composite was extracted. Raman imaging and scanning electron microscopy were employed as orthogonal techniques for validating this XPS-based methodology. Results demonstrate that XPS imaging of differentially charging MWCNT composite samples is an effective means for assessing dispersion quality.

Accurate flexural spring constant calibration of colloid probe cantilevers using scanning laser Doppler vibrometry.

Calibration of the flexural spring constant for atomic force microscope (AFM) colloid probe cantilevers provides significant challenges. The presence of a large attached spherical added mass complicates many of the more common calibration techniques such as reference cantilever, Sader, and added mass. Even the most promising option, AFM thermal calibration, can encounter difficulties during the optical lever sensitivity measurement due to strong adhesion and friction between the sphere and a surface. This may cause buckling of the end of the cantilever and hysteresis in the approach-retract curves resulting in increased uncertainty in the calibration. Most recently, a laser Doppler vibrometry thermal method has been used to accurately calibrate the normal spring constant of a wide variety of tipped and tipless commercial cantilevers. This paper describes a variant of the technique, scanning laser Doppler vibrometry, optimized for colloid probe cantilevers and capable of spring constant calibration uncertainties near ±1%.

Smart Electronic Laboratory Notebooks for the NIST Research Environment.

Laboratory notebooks have been a staple of scientific research for centuries for organizing and documenting ideas and experiments. Modern laboratories are increasingly reliant on electronic data collection and analysis, so it seems inevitable that the digital revolution should come to the ordinary laboratory notebook. The most important aspect of this transition is to make the shift as comfortable and intuitive as possible, so that the creative process that is the hallmark of scientific investigation and engineering achievement is maintained, and ideally enhanced. The smart electronic laboratory notebooks described in this paper represent a paradigm shift from the old pen and paper style notebooks and provide a host of powerful operational and documentation capabilities in an intuitive format that is available anywhere at any time.

Experimental determination of mode correction factors for thermal method spring constant calibration of AFM cantilevers using laser Doppler vibrometry.

Mode correction factors (MCFs) represent a significant adjustment to the spring constant values measured using the thermal cantilever calibration method. Usually, the ideal factor of 0.971 for a tipless rectangular cantilever is used, which adjusts the value by 3% for the first flexural mode. An experimental method for determining MCFs has been developed that relies on measuring the areas under the first few resonance peaks for the flexural mode type. Using this method, it has been shown that MCFs for the first flexural mode of commercially available atomic force microscope cantilevers actually vary from 0.95 to 1.0, depending on the shape and end mass of the cantilever. Triangular shaped cantilevers tend to lower MCFs with tipless versions providing the lowest values. Added masses (including tips) tend to increase the first flexural mode's MCF to higher values with large colloid probes at the high extreme. Using this understanding and applying it to the recently developed laser Doppler vibrometry thermal calibration method it is now possible to achieve very accurate and precise cantilever spring constant calibrations (uncertainties close to ±1%) with commonly available commercial cantilevers such as tipped rectangular and triangular cantilevers, and colloid probes.

Surface mediated assembly of small, metastable gold nanoclusters.

The unique properties of metallic nanoclusters are attractive for numerous commercial and industrial applications but are generally less stable than nanocrystals. Thus, developing methodologies for stabilizing nanoclusters and retaining their enhanced functionality is of great interest. We report the assembly of PPh3-protected Au9 clusters from a heterogeneous mixture into films consisting of sub 3 nm nanocluster assemblies. The depositing nanoclusters are metastable in solution, but the resulting nanocluster assemblies are stabilized indefinitely in air or fresh solvent. The films exhibit distinct structure from Au nanoparticles observed by X-ray diffraction, and film dissolution data support the preservation of small nanoclusters. UV-Vis spectroscopy, electrospray ionization mass spectrometry, X-ray photoelectron spectroscopy and electron microscopy are used to elucidate information regarding the nanocluster formation and assembly mechanism. Preferential deposition of nanocluster assemblies can be achieved on multiple substrates, including polymer, Cr, Si, SiO2, SiNx, and metal-organic frameworks (MOFs). Unlike other vapor phase coating processes, nanocluster assembly on the MIL-68(In) MOF crystal is capable of preferentially coating the external surface and stabilizing the crystal structure in hydrothermal conditions, which should enhance their storage, separation and delivery capabilities.