Sub-nanometer Resolution Research Articles

Fake tilts in differential wavefront sensing.

Two-beam interferometry is a tool of high-precision length-metrology, where displacements are measured to within sub-nanometer resolution and accuracy. Differential wavefront sensing - via phase detection by segmented photodiodes - adds the capability of simultaneously measuring the target translation and rotation. This paper gives an analytical model explaining the observation of fake tilts by a combined x-ray and optical interferometer.

Multidimensional topography sensing simulating an AFM

Atomic force microscopy (AFM) is used in the semiconductor industry for inspection and quality control. Frequency modulated AFM (FM-AFM) extracts surface topography by measuring the frequency shift created by the Van der Waals (VdW) interaction forces between the tip and the sample. To improve the measurement speed and address complex geometries emerging in industrial microchip constructions, several enhancements are introduced. While most FM-AFM devices operate in a single vibrating mode, this article proposes a method for multidimensional sensing using frequency modulation of 2 orthogonal vibration modes, simultaneously. The concept was tested on a large-scale experimental system, where VdW forces were replaced by magnetic forces, using a magnetic tip and ferromagnetic samples. To emulate the VdW forces accurately, the designed ratio between the base frequency and frequency shift was kept to mimic a Nano-scale AFM. By utilizing an Autoresonance (AR) control scheme for faster locking onto resonance and a curve fitting frequency estimation algorithm it is possible to sense the minute changes in frequency experienced by several modes, simultaneously. Experimental results employ 3D relevant topographies such as inclined surfaces, steep walls and trenches that were reconstructed experimentally with 4 (μm) resolution or better. Downscaling to typical AFM dimensions would theoretically yield sub-nanometer resolution.

Nanomechanical Characterization of Vertical Nanopillars Using an MEMS-SPM Nano-Bending Testing Platform.

Nanomechanical characterization of vertically aligned micro- and nanopillars plays an important role in quality control of pillar-based sensors and devices. A microelectromechanical system based scanning probe microscope (MEMS-SPM) has been developed for quantitative measurement of the bending stiffness of micro- and nanopillars with high aspect ratios. The MEMS-SPM exhibits large in-plane displacement with subnanometric resolution and medium probing force beyond 100 micro-Newtons. A proof-of-principle experimental setup using an MEMS-SPM prototype has been built to experimentally determine the in-plane bending stiffness of silicon nanopillars with an aspect ratio higher than 10. Comparison between the experimental results and the analytical and FEM evaluation has been demonstrated. Measurement uncertainty analysis indicates that this nano-bending system is able to determine the pillar bending stiffness with an uncertainty better than 5%, provided that the pillars’ stiffness is close to the suspending stiffness of the MEMS-SPM. The MEMS-SPM measurement setup is capable of on-chip quantitative nanomechanical characterization of pillar-like nano-objects fabricated out of different materials.

A complete data processing workflow for cryo-ET and subtomogram averaging.

Electron cryotomography (CryoET) is currently the only method capable of visualizing cells in 3D at nanometer resolutions. While modern instruments produce massive amounts of tomography data containing extremely rich structural information, the data processing is very labor intensive and results are often limited by the skills of the personnel rather than the data. We present an integrated workflow that covers the entire tomography data processing pipeline, from automated tilt series alignment to subnanometer resolution subtomogram averaging. Resolution enhancement is made possible through the use of per-particle per-tilt CTF correction and alignment. The workflow greatly reduces human effort and increases throughput and is capable of determining protein structures at state-of-the-art resolutions for both purified macromolecules and cells.

Transmission Electron Microscope Using a Linear Accelerator.

High-voltage transmission electron microscopes (HVTEMs), which can visualize internal structures of micron thick samples, intrinsically have large instrument sizes because of the static voltage isolation. In this Letter, we develop a compact HVTEM, employing a linear accelerator, a subpicosecond beam chopper, and a linear decelerator. 100kV electrons initially accelerated by a static field are accelerated at radio frequency (rf) up to 500kV, transmitting through the sample and finally rf decelerated down to 200kV to be imaged through a 200kV energy filter. 500kV imaging, as well as subnanometer resolution at 200kV, have been demonstrated.

Dielectric-Screening Reduction-Induced Large Transport Gap in Suspended Sub-10 nm Graphene Nanoribbon Functional Devices.

The predicted quasiparticle energy gap of more than 1 eV in sub-6 nm graphene nanoribbons (GNRs) is elusive, as it is strongly suppressed by the substrate dielectric screening. The number of techniques that can produce suspended high-quality and electrically contacted GNRs is small. The helium ion beam milling technique is capable of achieving sub-5 nm patterning; however, the functional device fabrication and the electrical characteristics are not yet reported. Here, the electrical transport measurement of suspended ≈6 nm wide mono- and bilayer GNR functional devices is reported, which are obtained through sub-nanometer resolution helium ion beam milling with controlled total helium ion budget. The transport gap opening of 0.16-0.8 eV is observed at room temperature. The measured transport gap of the different edge orientated GNRs is in good agreement with first-principles simulation results. The enhanced electron-electron interaction and reduced dielectric screening in the suspended quasi-1D GNRs and anti-ferromagnetic coupling between opposite edges in the zigzag GNRs substantiate the observed large transport gap.

Optical force microscopy: combining light with atomic force microscopy for nanomaterial identification

Abstract Scanning probe techniques have evolved significantly in recent years to detect surface morphology of materials down to subnanometer resolution, but without revealing spectroscopic information. In this review, we discuss recent advances in scanning probe techniques that capitalize on light-induced forces for studying nanomaterials down to molecular specificities with nanometer spatial resolution.

Characterizing Individual Protein Aggregates by Infrared Nanospectroscopy and Atomic Force Microscopy.

The phenomenon of protein misfolding and aggregation results in the formation of highly heterogeneous protein aggregates, which are associated with neurodegenerative conditions such as Alzheimer's and Parkinson's diseases. In particular low molecular weight aggregates, amyloid oligomers, have been shown to possess generic cytotoxic properties and are implicated as neurotoxins in many forms of dementia. We illustrate the use of methods based on atomic force microscopy (AFM) to address the challenging task of characterizing the morphological, structural and chemical properties of these aggregates, which are difficult to study using conventional structural methods or bulk biophysical methods because of their heterogeneity and transient nature. Scanning probe microscopy approaches are now capable of investigating the morphology of amyloid aggregates with sub-nanometer resolution. We show here that infrared (IR) nanospectroscopy (AFM-IR), which simultaneously exploits the high resolution of AFM and the chemical recognition power of IR spectroscopy, can go further and enable the characterization of the structural properties of individual protein aggregates, and thus offer insights into the aggregation mechanisms. Since the approach that we describe can be applied also to the investigations of the interactions of protein assemblies with small molecules and antibodies, it can deliver fundamental information to develop new therapeutic compounds to diagnose or treat neurodegenerative disorders.

High-Resolution Imaging of Maltoporin LamB while Quantifying the Free-Energy Landscape and Asymmetry of Sugar Binding.

Maltoporins are a family of membrane proteins that facilitate the diffusion of hydrophilic molecules and maltosaccharides across the outer membrane of Gram-negative bacteria. Two contradicting models propose the sugar binding, uptake, and transport by maltoporins to be either symmetric or asymmetric. Here, we address this contradiction and introduce force-distance-based atomic force microscopy to image single maltoporin LamB trimers in the membrane at sub-nanometer resolution and simultaneously quantify the binding of different malto-oligosaccharides. We assay subtle differences of the binding free-energy landscape of maltotriose, maltotetraose, and maltopentaose, which quantifies how binding strength and affinity increase with the malto-oligosaccharide chain length. The ligand-binding parameters change considerably by mutating the extracellular loop 3, which folds into and constricts the transmembrane pore of LamB. By recording LamB topographs and structurally mapping binding events at sub-nanometer resolution, we observe LamB to preferentially bind maltodextrin from the periplasmic side, which shows sugar binding and uptake to be asymmetric. The study introduces atomic force microscopy as an analytical nanoscopic tool that can differentiate among the factors modulating and models describing the binding and uptake of substrates by membrane proteins.

High Throughput Grain Mapping with Sub-Nanometer Resolution by 4D-STEM

High Throughput Grain Mapping with Sub-Nanometer Resolution by 4D-STEM

Nanoscale Spatially Resolved Mapping of Uranium Enrichment in Actinide-Bearing Materials

Spatially resolved analysis of uranium isotopes in small volumes of actinide-bearing materials is critical for a variety of technical disciplines, including earth and planetary sciences, environmental monitoring, bioremediation, and the nuclear fuel cycle. However, achieving sub-nanometer scale spatial resolution for such isotopic analysis is currently a challenge. By using atom probe tomography, a three dimensional nanoscale characterization technique, we demonstrate unprecidented nanoscale mapping of uranium isotopic enrichment with high sensitivity across various microstructural interfaces within small volumes (100 nm3) of depleted and low enriched uranium alloyed with 10 wt % molybdenum with different nominal enrichments of 0.20 and 19.75% 235U respectively. The approach presented here can be applied to study nanoscale variations of isotopic abundances in the broad class of actinide-bearing materials, providing unique insights into their origin and thermo-mechanical processing routes.

Atom Probe Tomography for Catalysis Applications: A Review

Atom probe tomography is a well-established analytical instrument for imaging the 3D structure and composition of materials with high mass resolution, sub-nanometer spatial resolution and ppm elemental sensitivity. Thanks to recent hardware developments in Atom Probe Tomography (APT), combined with progress on site-specific focused ion beam (FIB)-based sample preparation methods and improved data treatment software, complex materials can now be routinely investigated. From model samples to complex, usable porous structures, there is currently a growing interest in the analysis of catalytic materials. APT is able to probe the end state of atomic-scale processes, providing information needed to improve the synthesis of catalysts and to unravel structure/composition/reactivity relationships. This review focuses on the study of catalytic materials with increasing complexity (tip-sample, unsupported and supported nanoparticles, powders, self-supported catalysts and zeolites), as well as sample preparation methods developed to obtain suitable specimens for APT experiments.

Arbitrary function resonance tuner of the optical microcavity with sub-MHz resolution.

Tuning the resonance frequency of an optical whispering gallery mode microcavity is extremely important in its various applications. Here we report the design and implementation of a function resonance tuner of an optical microcavity with a resolution of about 650kHz (7pm at 1450nm band). A piezoelectric nano-positioner is used to mechanically compress the microsphere in its axial direction. Furthermore, the resonance can be periodically tuned as an arbitrary function, such as the sine and sigmoid functions, with over 99% fitting accuracy. This Letter greatly expands the application of ultrahigh quality factor microresonators in a multi-mode coupling system or time-floquet system.

Electron Bessel beam diffraction for precise and accurate nanoscale strain mapping

Strain has a strong effect on the properties of materials and the performance of electronic devices. Their ever shrinking size translates into a constant demand for accurate and precise measurement methods with a very high spatial resolution. In this regard, transmission electron microscopes are key instruments thanks to their ability to map strain with a subnanometer resolution. Here, we present a method to measure strain at the nanometer scale based on the diffraction of electron Bessel beams. We demonstrate that our method offers a strain sensitivity better than 2.5 × 10−4 and an accuracy of 1.5 × 10−3, competing with, or outperforming, the best existing methods with a simple and easy to use experimental setup.

Three-dimensional subnanoscale imaging of unit cell doubling due to octahedral tilting and cation modulation in strained perovskite thin films

Determining the 3-dimensional crystallography of a material with sub-nanometre resolution is essential to understanding strain effects in epitaxial thin films. A new scanning transmission electron microscopy imaging technique is demonstrated that visualises the presence and strength of atomic movements leading to a period doubling of the unit cell along the beam direction, using the intensity in an extra Laue zone ring in the back focal plane recorded using a pixelated detector method. This method is used together with conventional atomic resolution imaging in the plane perpendicular to the beam direction to gain information about the 3D crystal structure in an epitaxial thin film of LaFeO3 sandwiched between a substrate of (111) SrTiO3 and a top layer of La0.7Sr0.3MnO3. It is found that a hitherto unreported structure of LaFeO3 is formed under the unusual combination of compressive strain and (111) growth, which is triclinic with a periodicity doubling from primitive perovskite along one of the three <110> directions lying in the growth plane. This results from a combination of La-site modulation along the beam direction, and modulation of oxygen positions resulting from octahedral tilting. This transition to the period-doubled cell is suppressed near both the substrate and near the La0.7Sr0.3MnO3 top layer due to the clamping of the octahedral tilting by the absence of tilting in the substrate and due to an incompatible tilt pattern being present in the La0.7Sr0.3MnO3 layer. This work shows a rapid and easy way of scanning for such transitions in thin films or other systems where disorder-order transitions or domain structures may be present and does not require the use of atomic resolution imaging, and could be done on any scanning TEM instrument equipped with a suitable camera.

Atomic Force Spectroscopy on Ionic Liquids

Ionic liquids have become of significant relevance in chemistry, as they can serve as environmentally-friendly solvents, electrolytes, and lubricants with bespoke properties. In particular for electrochemical applications, an understanding of the interface structure between the ionic liquid and an electrified interface is needed to model and optimize the reactions taking place on the solid surface. As with ionic liquids, the interplay between electrostatic forces and steric effects leads to an intrinsic heterogeneity, as the structure of the ionic liquid above an electrified interface cannot be described by the classical electrical double layer model. Instead, a layered solvation layer is present with a structure that depends on the material combination of the ionic liquid and substrate. In order to experimentally monitor this structure, atomic force spectroscopy (AFS) has become the method of choice. By measuring the force acting on a sharp microfabricated tip while approaching the surface in an ionic liquid, it has become possible to map the solvation layers with sub-nanometer resolution. In this review, we provide an overview of the AFS studies on ionic liquids published in recent years that illustrate how the interface is formed and how it can be modified by applying electrical potential or by adding impurities and solvents.

Atomic force microscopy with integrated on-chip interferometric readout

The most common readout technique used in atomic force microscopy (AFM) is based on optical beam deflection (OBD), which relies on monitoring deflection of the cantilever probe by measuring the position of the laser beam reflected from the free end of the AFM cantilever. Although systems using the OBD readout can achieve subnanometre displacement resolution and video rate imaging speeds, its main limitation is size, which is difficult to minimise, thus limiting multiprobe imaging capability. Currently, system miniaturisation has been accommodated by adopting on-chip electrical readout solutions, often at the expense of measurement sensitivity. To date, no cost-effective AFM readout solution exists without sacrificing either measurement sensitivity, system miniaturisation, or multiprobe array scalability.In this paper we present an AFM probe with integrated on-chip optical interferometric readout based on silicon photonics. Our AFM probe combines the advantages of subnanometre resolution of optical readouts with on-chip miniaturisation. The adopted approach determines deflection of the cantilever using an integrated on-chip photonics waveguide by monitoring the separation between the sensing cantilever and an interrogating grating. The implemented methodology provides ultimate interferometric resolution and sensitivity, on-chip miniaturisation, and array scalability, which makes possible ultrafast multiprobe-array AFM imaging.Using a Digital Instruments D3000 AFM retrofitted with our cantilever probe and integrated readout, we report sub-nanometre AFM topography images obtained on reference samples. We demonstrate RMS static AFM noise level of 19 pm, outperforming the operation of this system in its standard, optical beam deflection configuration (51 pm). The noise spectrum measurements of our probe indicate that the integrated readout is shot noise limited, achieving a deflection noise density (DND) of 36fm/Hz.

3D push-pull heterodyne interferometer for SPM metrology.

A three-coordinate heterodyne laser interferometer has been developed to measure the displacement of the probe microscope scanner with a subnanometer resolution that provides traceability of measurements to the standard of meter through the wavelength of a stabilized He-Ne laser. Main sources of errors are investigated, and their influence is minimized so that the resulting measurement uncertainty of the system does not exceed 0.2nm, and the resolution is 0.01nm. The investigation of metrological characteristics of the three-coordinate interferometer was carried out with a scanning probe microscopy (SPM) NanoScan-3D using TGZ-type calibration gratings. The values measured with SPM fell within the 95% confidence interval given by Physikalisch-Technische Bundesanstalt (PTB) (Germany). SPM equipped with a laser interferometer was used to measure the characteristics of dynamic etalons of geometric dimensions.

Atomic Resolution Imaging of the Cathode-Electrolyte Interface on a LiMn2O4 Electrode

Understanding the nature and composition of the cathode-electrolyte interface (CEI) layer in lithium-ion cells is a key element for the development of safer and longer lasting batteries. The CEI layer is a passivation layer formed, after electrolyte decomposition, on the surface of a positive electrode in lithium-ion batteries. Analogous to the solid electrolyte interface (SEI) on the anode, it is usually thinner (~5 nm vs 10-100 nm) and composed of poor ion-conductors that cause an additional resistance to the Li+ ions path [1]–[3]. Different surface sensitive techniques have been previously used to study the composition of the CEI layer and a model for its formation has been proposed [4]. However, its structure and composition are not fully understood yet and experimental techniques with sub-nanometer resolution are needed for an accurate characterization of this layer. Atom probe tomography (APT) is probably the best candidate, being a powerful technique for three-dimensional analysis of sub-nanometer structures and compositional variations that can achieve atomic resolution, along with chemical sensitivity for Li [5], [6]. In this work we successfully investigated for the first time the CEI layer formation on the surface of a LiMn2O4 (LMO) electrode using the APT technique. A commercial LMO cathode (from MTI) was calendared for ten days in a cell using standard 1M LiPF6 electrolyte in EC:DMC, and lithium metal as a counter and reference electrode. Three-electrode impedance measurements were performed at the OCV with regular intervals to observe and resolve the growth of the CEI layer on the cathode from the growth of the SEI layer on the lithium metal anode. After disassembling the cell, we prepared the sample for APT analysis and determined with atomic resolution the composition and structure of the CEI. A mixed layered- and mosaic-structure was observed, consisting of two inner Mn-rich layers adsorbed on the LMO surface and an external mosaic structure, mainly composed by LiF, Li2O and Li-carboxylates.

Effect of Varying Co Content in PtCo Nanoparticles on the Performance of PEM Fuel Cells

PtCo alloy catalysts are leading cathode candidates for PEMFC because of their relatively high activity and durability. Although it is known that during fuel cell operation the dissolution of Co results in loss of oxygen reduction reaction activity and that the migration of Co2+ into the membrane can have a negative impact on fuel cell high-current-density performance, the detailed mechanisms are unclear. Thus there are opportunities for PtCo alloy optimization to minimize these losses. Here, we focused on dealloyed PtCo catalysts with varying degrees of acid leaching in an attempt to vary the Pt-rich shell content while maintaining the Pt-to-Co core composition. While the specific activity of the catalyst decreased with reducing Co content, as expected, the high current fuel cell performance improved. Post-mortem analyses were done to quantify the amount of Co2+ in the membrane. Mathematical modelling was used to help interpret the voltage losses at high current density. We also employed newly developed nanobeam electron diffraction techniques to measure local crystal structure across the PtCo core-shell nanoparticles at subnanometer resolution. This allows us to correlate lattice strain relaxation and defect sites to the apparent catalyst kinetic activity. This work was partially supported by the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy under grant DE-EE0007271.