Unmixing noisy co-registered spectrum images of multicomponent nanostructures.

Analytical electron microscopy plays a key role in the development of novel nanomaterials. Electron energy-loss spectroscopy (EELS) and energy-dispersive X-ray spectroscopy (EDX) datasets are typically processed to isolate the background-subtracted elemental signal. Multivariate tools have emerged as powerful methods to blindly map the components, which addresses some of the shortcomings of the traditional methods. Here, we demonstrate the superior performance of a new multivariate optimization method using a challenging EELS and EDX dataset. The dataset was recorded from a spectrum image P-type metal-oxide-semiconductor stack with 7 components exhibiting heavy spectral overlap and a low signal-to-noise ratio. Compared to peak integration, independent component analysis, Baysian Linear Unmixing and Non-negative matrix factorization, the method proposed was the only one to identify the EELS spectra of all 7 components with the corresponding abundance profiles. Using the abundance of each component, it was possible to retrieve the EDX spectra of all the components, which were otherwise impossible to isolate, regardless of the method used. We expect that this robust method will bring a significant improvement for the chemical analysis of nanomaterials, especially for weak signals, dose-sensitive specimen or signals suffering heavy spectral overlap.

Uprooting defects to enable high-performance III-V optoelectronic devices on silicon.

The monolithic integration of III-V compound semiconductor devices with silicon presents physical and technological challenges, linked to the creation of defects during the deposition process. Herein, a new defect elimination strategy in highly mismatched heteroepitaxy is demonstrated to achieve a ultra-low dislocation density, epi-ready Ge/Si virtual substrate on a wafer scale, using a highly scalable process. Dislocations are eliminated from the epilayer through dislocation-selective electrochemical deep etching followed by thermal annealing, which creates nanovoids that attract dislocations, facilitating their subsequent annihilation. The averaged dislocation density is reduced by over three orders of magnitude, from ~108 cm-2 to a lower-limit of ~104 cm-2 for 1.5 µm thick Ge layer. The optical properties indicate a strong enhancement of luminescence efficiency in GaAs grown on this virtual substrate. Collectively, this work demonstrates the promise for transfer of this technology to industrial-scale production of integrated photonic and optoelectronic devices on Si platforms in a cost-effective way.

Cu(II) galvanic reduction and deposition onto iron nano- and microparticles: resulting morphologies and growth mechanisms.

The galvanic reduction of heavy metal ions by zerovalent iron nanoparticles is a key process occurring extensively in wastewater remediation, as well as for the synthesis of materials, including catalysts. In this work, we studied the growth of copper species on nano- and micrometer-sized iron particles and investigated the morphologies of the resulting structures. The growth proceeds via sacrificial oxidation of iron particles and reduction of Cu(2+) cations from aqueous solutions. Based on the results of transmission and scanning electron microscopy (TEM and SEM), coupled with energy-dispersive X-ray spectroscopy (EDX), electron energy loss spectroscopy (EELS), and X-ray photoelectron spectroscopy (XPS), we proposed two growth mechanisms for the morphologies seen for the copper exposed nano- and microiron particles at varying copper/iron ratios. We observed that, in low Cu/Fe ratios (≤1/100), copper particles decorated the oxide shell of the iron nano/microparticles, while in higher Cu/Fe ratios (≥1/10), Cu-rich hollow structures were formed. Iron microparticles also led to the formation of interesting Cu-fern structures. This study provides insight into the fate of particles used in remediation, as well as recommendations for the synthesis of well-defined materials tailored for precise applications.

Performances of an 80-200 kV microscope employing a cold-FEG and an aberration-corrected objective lens.

The performances of a newly developed 80-200 kV cold field emission gun (CFEG) transmission electron microscope (TEM) integrating a spherical aberration corrector for a TEM image-forming lens have been evaluated. To begin, we show that the stability of both emission and probe currents makes use of this new CFEG much friendlier. The energy spread of electrons emitted from the CFEG has been measured as a function of emission current and shows a very last 0.26 eV energy resolution at 200 kV and even 0.23 eV at 80 kV. The combination of the CFEG and the CEOS™ aberration corrector, associated with enhanced mechanical and electrical stabilities of this new microscope, allows reaching an information transfer below 75 pm at 200 and 80 pm at 80 kV. This unseen resolution at 200 kV has allowed us to study the structure of CoPt nanoparticles by observing direct images of their atomic arrangement along the high indexes zone axis. We have evidenced the presence of defects in these nanostructures that are not parallel to the electron beam. The precise stoichiometry of two iron oxides, FeO and Fe2O3, has been determined from an analysis of iron valence state that was obtained from a direct analysis of EELS fine structures spectrum of the two oxides.

Correcting scanning instabilities from images of periodic structures.

A method for measuring and correcting the row displacement errors in lattice images acquired using scanning based methods is presented. This type of distortion is apparent in lattice-resolved images acquired using scanning-based techniques such as scanning transmission electron microscopy (STEM) and translates to vertical streaks convolving every feature in Fourier space. This paper presents a method to measure and correct the distortion based on the phase analysis of the streaks in Fourier space. The validity and the precision of the method is demonstrated using a model image and two experimental STEM images of Si <110> thin film and a 5 nm CoPt disordered nanocrystal. The algorithm is implemented in a freely available Digital Micrograph™ script.

Quantitative energy dispersive X-ray microanalysis of electron beam-sensitive alloyed nanoparticles.

An energy dispersive X-ray spectrometry (EDXS) method is developed to evaluate the composition of alloyed nanoparticles (NPs) where one of the alloying elements is removed under the electron beam during microanalysis with a transmission electron microscope (TEM). The method is demonstrated for alloyed Au-Ag NPs of a diameter ranging from 6 to 20 nm produced by laser evaporation of a water-suspended Ag-Au powder mixture of varying composition. Series of EDXS spectra are recorded for 30 NPs from samples with five different Ag:Au ratios revealing Ag depletion from NPs during electron irradiation. By studying the evolution of NPs composition as a function of dose, the initial Ag content for each NP is extrapolated. The rate of Ag depletion is discussed in terms of sputtering and knock-on damage. On average, approximately one Ag atom is lost from the NP for each Ag L X-ray detected. To assess the limitations of microanalysis in these sensitive nanoscale structures, the concept of detectability limit is adapted to our method. This benchmark is then evaluated for Ag in Au-Ag NPs of various sizes and acquisition times. This study should be regarded as a guide for the design of analytical TEM measurements of beam-sensitive NPs.

Multiple quantum well AlGaAs nanowires.

This letter reports on the growth, structure, and luminescent properties of individual multiple quantum well (MQW) AlGaAs nanowires (NWs). The composition modulations (MQWs) are obtained by alternating the elemental flux of Al and Ga during the molecular beam epitaxy growth of the AlGaAs wire on GaAs (111)B substrates. Transmission electron microscopy and energy dispersive X-ray spectroscopy performed on individual NWs are consistent with a configuration composed of conical segments stacked along the NW axis. Microphotoluminescence measurements and confocal microscopy showed enhanced light emission from the MQW NWs as compared to nonsegmented NWs due to carrier confinement and sidewall passivation.

Polymerization from the surface of single-walled carbon nanotubes - preparation and characterization of nanocomposites.

Single-walled carbon nanotubes were functionalized along their sidewalls with phenol groups using the 1,3-dipolar cycloaddition reaction. These phenols could be further derivatized with 2-bromoisobutyryl bromide, resulting in the attachment of atom transfer radical polymerization initiators to the sidewalls of the nanotubes. These initiators were found to be active in the polymerization of methyl methacrylate and tert-butyl acrylate from the surface of the nanotubes. However, the polymerizations were not controlled, leading to the production of high molecular weight polymers with relatively large polydispersities. The resulting polymerized nanotubes were analyzed by IR, Raman spectroscopy, DSC, TEM, and AFM. The nanotubes functionalized with poly(methyl methacrylate) were found to be insoluble, while those functionalized with poly(tert-butyl acrylate) were soluble in a variety of organic solvents. The tert-butyl groups of these appended polymers could also be removed to produce nanotubes functionalized with poly(acrylic acid), resulting in structures that are soluble in aqueous solutions.