Elemental Characterization of Al Nanoparticles Buried under a Cu Thin Film: TOF-SIMS vs STEM/EDX.

In this work, we present a comprehensive comparison of time-of-flight secondary ion mass spectrometry (TOF-SIMS) and scanning transmission electron microscopy combined with energy-dispersive X-ray spectroscopy (STEM/EDX), which are currently the most powerful elemental characterization techniques in the nano- and microscale. The potential and limitations of these methods are verified using a novel dedicated model sample consisting of Al nanoparticles buried under a 50 nm thick Cu thin film. The sample design based on the low concentration of nanoparticles allowed us to demonstrate the capability of TOF-SIMS to spatially resolve individual tens of nanometer large nanoparticles under ultrahigh vacuum (UHV) as well as high vacuum (HV) conditions. This is a remarkable achievement especially taking into account the very small quantities of the investigated Al content. Moreover, the imposed restriction on the Al nanoparticle location, i.e., only on the sample substrate, enabled us to prove that the measured Al signal represents the real distribution of Al nanoparticles and does not originate from the artifacts induced by the surface topology. The provided comparison of TOF-SIMS and STEM/EDX characteristics delivers guidelines for choosing the most optimal method for efficient characterization of nano-objects.

Combining surface-sensitive microscopies for analysis of biological tissues after neural device implantation.

In order to address the complexity of chemical analysis of biological systems, time-of-flight secondary ion mass spectrometry (ToF-SIMS), x-ray photoelectron spectroscopy (XPS), and x-ray photoemission electron microscopy (XPEEM) were used for combined surface imaging of a biological tissue formed around a surface neural device after implantation on a nonhuman primate brain. Results show patterns on biological tissue based on extracellular matrix (ECM) and phospholipid membrane (PM) molecular fragments, which were contrasted through principal component analysis of ToF-SIMS negative spectrum. This chemical differentiation may indicate severe inflammation on tissue with an early case of necrosis. Quantification of the elemental composition and the chemical bonding states on both ECM-rich and PM-rich features was possible through XPS analysis from survey and high-resolution spectra, respectively. Variable amounts of carbon (68%-80.5%), nitrogen (10%-2.4%), and oxygen (20.8%-16.5%) were detected on the surface of the biological tissue. Chlorine, phosphorous sodium, and sulfur were also identified in lower extends. Besides that, analysis of the C 1s high-resolution spectra for the same two regions (ECM and PM ones) showed that a compromise between C-C (41.8 at. %) and C-N/C-O (35.6 at. %) amounts may indicate a strong presence of amino acids and proteoglycans on the ECM fragment-rich region, while the great amount of C-C (70.1 at. %) on the PM fragment-rich region is attributed to the large chains of fatty acids connected to phospholipid molecules. The micrometer-scale imaging of these chemical states on tissue was accomplished through XPEEM analysis. The C-C presence was found uniformly distributed across the entire analyzed area, while C-N/C-O and C=O were in two distinct regions. The combination of ToF-SIMS, XPS, and XPEEM is shown here as a powerful, noninvasive approach to map out elemental and chemical properties of biological tissues, i.e., identification of chemically distinct regions, followed by quantification of the surface chemical composition in each distinct region.

3D Imaging of Nanoparticles in an Inorganic Matrix Using TOF-SIMS Validated with STEM and EDX.

Imaging nano-objects in complex systems such as nanocomposites using time-of-flight secondary ion mass spectrometry (TOF-SIMS) is a challenging task. Due to a very small amount of the material and a matrix effect, the number of generated secondary ions can be insufficient to represent a 3D elemental distribution despite being detected in a mass spectrum. Therefore, a model sample consisting of a ZrCuAg matrix with embedded Al nanoparticles is designed. A high mass difference between the light Al and heavy matrix components limits mass interference. The chemical structure measurements using a pulsed 60 keV Bi32+ beam or a continuous 30 keV Ga+ beam reveals distinct Al signal segregation. This can indicate a spatially resolved detection of single 10s of nanometer large particles and/or their agglomerates for the first time. However, TOF-SIMS images of 50 nm or smaller objects do not necessarily represent their exact size and shape but can rather be their convolutions with the primary ion beam shape. Therefore, the size of nanoparticles (25-64 nm) was measured using scanning transmission electron microscopy. Our studies prove the capability of TOF-SIMS to image chemical structure of nanohybrids which is expected to help building new functional materials and optimize their properties.

Identifying exposition to low oxygen environment in human macrophages using secondary ion mass spectrometry and multivariate analysis.

RATIONALE: Macrophages are innate immune cells presenting a strong phenotypic plasticity and deeply involved in tissue homeostasis. Oxygen environmental tension is a physical parameter that could influence their polarizations. In this study we use time-of-flight secondary ion mass spectrometry (TOF-SIMS) to describe how various polarizations are modified by a low oxygen exposure. METHODS: TOF-SIMS experiments were performed using an IONTOF ToF-SIMS 5-100 (ION-TOF GmbH, Munster, Germany). Analysis was performed using a pulsed 25 keV Bi3+ beam, sputtering was performed using a 250 eV Cs beam. Cells were fixed by paraformaldehyde before TOF-SIMS analysis. RESULTS: Multivariate analysis of the TOF-SIMS spectra provided ion species associated with the exposure of macrophages to low oxygen concentration. We were able to obtain some species, specific of a particular polarization, advocating for the use of macrophages as reporter cells of oxygen tension in tissues. CONCLUSIONS: Our study demonstrates that macrophage molecular signature to low oxygen environment is dependent on their polarization. TOF-SIMS shows the clear capability to produce species revealing this exposition. This result opens the way to the use of TOF-SIMS as a tool to explore hypoxia in human tissues.

Thin-Wall GaN/InAlN Multiple Quantum Well Tubes.

Thin-wall tubes composed of nitride semiconductors (III-N compounds) based on GaN/InAlN multiple quantum wells (MQWs) are fabricated by metal-organic vapor-phase epitaxy in a simple and full III-N approach. The synthesis of such MQW-tubes is based on the growth of N-polar c-axis vertical GaN wires surrounded by a core-shell MQW heterostructure followed by in situ selective etching using controlled H2/NH3 annealing at 1010 °C to remove the inner GaN wire part. After this process, well-defined MQW-based tubes having nonpolar m-plane orientation exhibit UV light near 330 nm up to room temperature, consistent with the emission of GaN/InAlN MQWs. Partially etched tubes reveal a quantum-dotlike signature originating from nanosized GaN residuals present inside the tubes. The possibility to fabricate in a simple way thin-wall III-N tubes composed of an embedded MQW-based active region offering controllable optical emission properties constitutes an important step forward to develop new nitride devices such as emitters, detectors or sensors based on tubelike nanostructures.

A novel PFIB sample preparation protocol for correlative 3D X-ray CNT and FIB-TOF-SIMS tomography.

We present a novel sample preparation method that allows correlative 3D X-ray Computed Nano-Tomography (CNT) and Focused Ion Beam Time-Of-Flight Secondary Ion Mass Spectrometry (FIB-TOF-SIMS) tomography to be performed on the same sample. In addition, our invention ensures that samples stay unmodified structurally and chemically between the subsequent experiments. The main principle is based on modifying the topography of the X-ray CNT experimental setup before FIB-TOF-SIMS measurements by incorporating a square washer around the sample. This affects the distribution of extraction field lines and therefore influences the trajectories of secondary ions that are now guided more efficiently towards the detector. As the result, secondary ion detection is significantly improved and higher, i.e. statistically better, signals are obtained.

State-of-the-Art Three-Dimensional Chemical Characterization of Solid Oxide Fuel Cell Using Focused Ion Beam Time-of-Flight Secondary Ion Mass Spectrometry Tomography.

In this paper the potential of time-of-flight secondary ion mass spectroscopy combined with focused ion beam technology to characterize the composition of a solid oxide fuel cell (SOFC) in three-dimension is demonstrated. The very high sensitivity of this method allows even very small amounts of elements/compounds to be detected and localized. Therefore, interlayer diffusion of elements between porous electrodes and presence of pollutants can be analyzed with a spatial resolution of the order of 100 nm. However, proper element recognition and mass interference still remain important issues. Here, we present a complete elemental analysis of the SOFC as well as techniques that help to validate the reliability of obtained results. A discussion on origins of probable artifacts is provided.

Preparation and Analysis of Atom Probe Tips by Xenon Focused Ion Beam Milling.

The damage and ion distribution induced in Si by an inductively coupled plasma Xe focused ion beam was investigated by atom probe tomography. By using predefined patterns it was possible to prepare the atom probe tips with a sub 50 nm end radius in the ion beam microscope. The atom probe reconstruction shows good agreement with simulated implantation profiles and interplanar distances extracted from spatial distribution maps. The elemental profiles of O and C indicate co-implantation during the milling process. The presence of small disc-shaped Xe clusters are also found in the three-dimensional reconstruction. These are attributed to the presence of Xe nanocrystals or bubbles that open during the evaporation process. The expected accumulated dose points to a loss of >95% of the Xe during analysis, which escapes undetected.

Measuring Compositions in Organic Depth Profiling: Results from a VAMAS Interlaboratory Study.

We report the results of a VAMAS (Versailles Project on Advanced Materials and Standards) interlaboratory study on the measurement of composition in organic depth profiling. Layered samples with known binary compositions of Irganox 1010 and either Irganox 1098 or Fmoc-pentafluoro-l-phenylalanine in each layer were manufactured in a single batch and distributed to more than 20 participating laboratories. The samples were analyzed using argon cluster ion sputtering and either X-ray photoelectron spectroscopy (XPS) or time-of-flight secondary ion mass spectrometry (ToF-SIMS) to generate depth profiles. Participants were asked to estimate the volume fractions in two of the layers and were provided with the compositions of all other layers. Participants using XPS provided volume fractions within 0.03 of the nominal values. Participants using ToF-SIMS either made no attempt, or used various methods that gave results ranging in error from 0.02 to over 0.10 in volume fraction, the latter representing a 50% relative error for a nominal volume fraction of 0.2. Error was predominantly caused by inadequacy in the ability to compensate for primary ion intensity variations and the matrix effect in SIMS. Matrix effects in these materials appear to be more pronounced as the number of atoms in both the primary analytical ion and the secondary ion increase. Using the participants' data we show that organic SIMS matrix effects can be measured and are remarkably consistent between instruments. We provide recommendations for identifying and compensating for matrix effects. Finally, we demonstrate, using a simple normalization method, that virtually all ToF-SIMS participants could have obtained estimates of volume fraction that were at least as accurate and consistent as XPS.

Quantitative analysis of Si/SiGeC superlattices using atom probe tomography.

SiGe and its alloys are used as key materials in innovative electronic devices. The analysis of these materials together with the localisation of dopants and impurities on a very fine scale is of crucial importance for better understanding their electronic properties. The quantification of carbon and germanium in an as-grown Si/SiGeC superlattice has been investigated using Atom Probe Tomography as a function of analysis conditions and sample anneal temperature. The mass spectrum is heavily influenced by the analysis conditions and chemical identification is needed. It was found that quantitative results are obtained using a intermediate electric field. The evaporation of carbon ions shows a strong spatial and temporal correlation. A series of annealed samples have been analysed, presenting an inhomogeneous carbon distribution, appearing in the shape of small clusters. These findings confirm previous results and give a better understanding of the processes occurring in these technologically important materials.

Quantitative investigation of SiGeC layers using atom probe tomography.

The quantification of carbon and germanium in a Si/SiGeC multilayer structure using atom probe tomography has been investigated as a function of analysis conditions. The best conditions for quantitative results are obtained using an intermediate electric field and laser power. Carbon evaporation shows strong spatial and temporal correlation. By using multi-ion event analysis, an evaporation mechanism is put forward to explain the modification of mass spectra as a function of electric field and laser power.

M-plane core-shell InGaN/GaN multiple-quantum-wells on GaN wires for electroluminescent devices.

Nonpolar InGaN/GaN multiple quantum wells (MQWs) grown on the {11-00} sidewalls of c-axis GaN wires have been grown by organometallic vapor phase epitaxy on c-sapphire substrates. The structural properties of single wires are studied in detail by scanning transmission electron microscopy and in a more original way by secondary ion mass spectroscopy to quantify defects, thickness (1-8 nm) and In-composition in the wells (∼16%). The core-shell MQW light emission characteristics (390-420 nm at 5 K) were investigated by cathodo- and photoluminescence demonstrating the absence of the quantum Stark effect as expected due to the nonpolar orientation. Finally, these radial nonpolar quantum wells were used in room-temperature single-wire electroluminescent devices emitting at 392 nm by exploiting sidewall emission.