Olga S. Ovchinnikova

Established and Emerging Atmospheric Pressure Surface Sampling/Ionization Techniques for Mass Spectrometry

The number and type of atmospheric pressure techniques suitable for sampling analytes from surfaces, forming ions from these analytes, and subsequently transporting these ions into vacuum for interrogation by MS have rapidly expanded over the last several years. Moreover, the literature in this area is complicated by an explosion in acronyms for these techniques, many of which provide no information relating to the chemical or physical processes involved. In this tutorial article, we sort this vast array of techniques into relatively few categories on the basis of the approaches used for surface sampling and ionization. For each technique, we explain, as best known, many of the underlying principles of operation, describe representative applications, and in some cases, discuss needed research or advancements and attempt to forecast their future analytical utility.

Comparison of residual stresses in Inconel 718 simple parts made by electron beam melting and direct laser metal sintering

Residual stress profiles were mapped using neutron diffraction in two simple prism builds of Inconel 718: one fabricated with electron beam melting (EBM) and the other with direct laser metal sintering. Spatially indexed stress-free cubes were obtained by electrical discharge machining (EDM) equivalent prisms of similar shape. The (311) interplanar spacings from the EDM sectioned sample were compared to the interplanar spacings calculated to fulfill stress and moment balance. We have shown that applying stress and moment balance is a necessary supplement to the measurements for the stress-free cubes with respect to accurate stress calculations in additively manufactured components. In addition, our work has shown that residual stresses in electron beam melted parts are much smaller than that of direct laser metal sintered parts most likely due to the powder preheating step in the EBM process.

Combining Laser Ablation/Liquid Phase Collection Surface Sampling and High-Performance Liquid Chromatography Electrospray Ionization Mass Spectrometry

This letter describes the coupling of ambient pressure transmission geometry laser ablation with a liquid phase sample collection method for surface sampling and ionization with subsequent mass spectral analysis. A commercially available autosampler was adapted to produce a liquid droplet at the end of the syringe injection needle while in close proximity to the surface to collect the sample plume produced by laser ablation. The sample collection was followed by either flow injection or a high-performance liquid chromatography (HPLC) separation of the extracted components and detection with electrospray ionization mass spectrometry (ESI-MS). To illustrate the analytical utility of this coupling, thin films of a commercial ink sample containing rhodamine 6G and of mixed isobaric rhodamine B and 6G dyes on glass microscope slides were analyzed. The flow injection and HPLC-ESI-MS analysis revealed successful laser ablation, capture, and with HPLC, the separation of the two compounds. The ablated circular area was about 70 μm in diameter for these experiments. The spatial sampling resolution afforded by the laser ablation, as well as the ability to use sample processing methods like HPLC between the sample collection and ionization steps, makes this combined surface sampling/ionization technique a highly versatile analytical tool.

Deciphering Halogen Competition in Organometallic Halide Perovskite Growth

Organometallic halide perovskites (OHPs) hold great promise for next-generation, low-cost optoelectronic devices. During the chemical synthesis and crystallization of OHP thin films, a major unresolved question is the competition between multiple halide species (e.g., I(-), Cl(-), Br(-)) in the formation of the mixed-halide perovskite crystals. Whether Cl(-) ions are successfully incorporated into the perovskite crystal structure or, alternatively, where they are located is not yet fully understood. Here, in situ X-ray diffraction measurements of crystallization dynamics are combined with ex situ TOF-SIMS chemical analysis to reveal that Br(-) or Cl(-) ions can promote crystal growth, yet reactive I(-) ions prevent them from incorporating into the lattice of the final perovskite crystal structure. The Cl(-) ions are located in the grain boundaries of the perovskite films. These findings significantly advance our understanding of the role of halogens during synthesis of hybrid perovskites and provide an insightful guidance to the engineering of high-quality perovskite films, essential for exploring superior-performing and cost-effective optoelectronic devices.

Combined Atomic Force Microscope-Based Topographical Imaging and Nanometer Scale Resolved Proximal Probe Thermal Desorption/Electrospray Ionization-Mass Spectrometry

Nanometer- scale proximal probe thermal desorption/electrospray ionization mass spectrometry (TD/ESI-MS) was demonstrated for molecular surface sampling of caffeine from a thin film using a 30 nm diameter nanothermal analysis (nano-TA) probe tip in an atomic force microscope (AFM) coupled via a vapor transfer line and ESI interface to a MS detection platform. Using a probe temperature of 350 °C and a spot sampling time of 30 s, conical desorption craters 250 nm in diameter and 100 nm deep were created as shown through subsequent topographical imaging of the surface within the same system. Automated sampling of a 5 × 2 array of spots, with 2 μm spacing between spots, and real time selective detection of the desorbed caffeine using tandem mass spectrometry was also demonstrated. Estimated from the crater volume (∼2 × 10(6) nm(3)), only about 10 amol (2 fg) of caffeine was liberated from each thermal desorption crater in the thin film. These results illustrate a relatively simple experimental setup and means to acquire in an automated fashion submicrometer scale spatial sampling resolution and mass spectral detection of materials amenable to TD. The ability to achieve MS-based chemical imaging with 250 nm scale spatial resolution with this system is anticipated.

Molecular Surface Sampling and Chemical Imaging using Proximal Probe Thermal Desorption/ Secondary Ionization Mass Spectrometry

Proximal probe thermal desorption/secondary ionization mass spectrometry was studied and applied to molecular surface sampling and chemical imaging using printed patterns on photopaper as test substrates. With the use of a circular cross section proximal probe with a tip diameter of 50 μm and fixed temperature (350 °C), the influence of probe-to-surface distance, lane scan spacing, and surface scan speed on signal quality and spatial resolution were studied and optimized. As a compromise between signal amplitude, signal reproducibility, and data acquisition time, a surface scan speed of 100 μm/s, probe-to-paper surface distance of 5 μm, and lane spacing of 10 μm were used for imaging. Under those conditions the proximal probe thermal desorption/secondary ionization mass spectrometry method was able to achieve a spatial resolution of about 50 μm as determined by the ability to distinguish surface patterns of known dimensions that were printed on the paper substrate. It is expected that spatial resolution and chemical image quality could be further improved by using probes of smaller cross section size and by incorporating a means to maintain a fixed optimal probe-to-surface distance real time, continuously adapting to the changing topography of the surface during a lane scan.

Atomic force microscope controlled topographical imaging and proximal probe thermal desorption/ionization mass spectrometry imaging.

This paper reports on the development of a hybrid atmospheric pressure atomic force microscopy/mass spectrometry imaging system utilizing nanothermal analysis probes for thermal desorption surface sampling with subsequent atmospheric pressure chemical ionization and mass analysis. The basic instrumental setup and the general operation of the system were discussed, and optimized performance metrics were presented. The ability to correlate topographic images of a surface with atomic force microscopy and a mass spectral chemical image of the same surface, utilizing the same probe without moving the sample from the system, was demonstrated. Co-registered mass spectral chemical images and atomic force microscopy topographical images were obtained from inked patterns on paper as well as from a living bacterial colony on an agar gel. Spatial resolution of the topography images based on pixel size (0.2 μm × 0.8 μm) was better than the resolution of the mass spectral images (2.5 μm × 2.0 μm), which were limited by current mass spectral data acquisition rate and system detection levels.

Combined chemical and topographic imaging at atmospheric pressure via microprobe laser desorption/ionization mass spectrometry–atomic force microscopy

The operational characteristics and imaging performance are described for a new instrument comprising an atomic force microscope coupled with a pulsed laser and a linear ion trap mass spectrometer. The operating mode of the atomic force microscope is used to produce topographic surface images having sub-micrometer spatial and height resolution. Spatially resolved mass spectra of ions, produced from the same surface via microprobe-mode laser desorption/ionization at atmospheric pressure, are also used to create a 100 x 100 microm chemical image. The effective spatial resolution of the image (approximately 2 microm) was constrained by the limit of detection (estimated to be 10(9)-10(10) molecules) rather than by the diameter of the focused laser spot or the step size of the sample stage. The instrument has the potential to be particularly useful for surface analysis scenarios in which chemical analysis of targeted topographic features is desired; consequently, it should have extensive application in a number of scientific areas. Because the number density of desorbed neutral species in laser desorption/ionization is known to be orders-of-magnitude greater than that of ions, it is expected that improvements in imaging performance can be realized by implementation of post-ionization methods.

Directing Matter: Toward Atomic-Scale 3D Nanofabrication

Enabling memristive, neuromorphic, and quantum-based computing as well as efficient mainstream energy storage and conversion technologies requires the next generation of materials customized at the atomic scale. This requires full control of atomic arrangement and bonding in three dimensions. The last two decades witnessed substantial industrial, academic, and government research efforts directed toward this goal through various lithographies and scanning-probe-based methods. These technologies emphasize 2D surface structures, with some limited 3D capability. Recently, a range of focused electron- and ion-based methods have demonstrated compelling alternative pathways to achieving atomically precise manufacturing of 3D structures in solids, liquids, and at interfaces. Electron and ion microscopies offer a platform that can simultaneously observe dynamic and static structures at the nano- and atomic scales and also induce structural rearrangements and chemical transformation. The addition of predictive modeling or rapid image analytics and feedback enables guiding these in a controlled manner. Here, we review the recent results that used focused electron and ion beams to create free-standing nanoscale 3D structures, radiolysis, and the fabrication potential with liquid precursors, epitaxial crystallization of amorphous oxides with atomic layer precision, as well as visualization and control of individual dopant motion within a 3D crystal lattice. These works lay the foundation for approaches to directing nanoscale level architectures and offer a potential roadmap to full 3D atomic control in materials. In this paper, we lay out the gaps that currently constrain the processing range of these platforms, reflect on indirect requirements, such as the integration of large-scale data analysis with theory, and discuss future prospects of these technologies.

Atomistic-Scale Simulations of Defect Formation in Graphene under Noble Gas Ion Irradiation

Despite the frequent use of noble gas ion irradiation of graphene, the atomistic-scale details, including the effects of dose, energy, and ion bombardment species on defect formation, and the associated dynamic processes involved in the irradiations and subsequent relaxation have not yet been thoroughly studied. Here, we simulated the irradiation of graphene with noble gas ions and the subsequent effects of annealing. Lattice defects, including nanopores, were generated after the annealing of the irradiated graphene, which was the result of structural relaxation that allowed the vacancy-type defects to coalesce into a larger defect. Larger nanopores were generated by irradiation with a series of heavier noble gas ions, due to a larger collision cross section that led to more detrimental effects in the graphene, and by a higher ion dose that increased the chance of displacing the carbon atoms from graphene. Overall trends in the evolution of defects with respect to a dose, as well as the defect characteristics, were in good agreement with experimental results. Additionally, the statistics in the defect types generated by different irradiating ions suggested that the most frequently observed defect types were Stone-Thrower-Wales (STW) defects for He(+) irradiation and monovacancy (MV) defects for all other ion irradiations.