Nanometer Accuracy Research Articles

Micro-Refractometry and Local-Field Mapping with Single Molecules

The refractive index n is one of the most important materials parameters of solids and, in recent years, has become the subject of significant interdisciplinary interest, especially in nanostructures and meta-materials. It is, in principle, a macroscopic quantity, so its meaning on a length scale of a few nanometers, i.e., well below the wavelength of light, is not clear a priori and is related to methods of its measurement on this length scale. Here we introduce a novel experimental approach for mapping the effective local value [Formula: see text] of the refractive index in solid films and the analysis of related local-field enhancement effects. The approach is based on the imaging and spectroscopy of single chromophore molecules at cryogenic temperatures. Since the fluorescence lifetime T1 of dye molecules in a transparent matrix depends on the refractive index due to the local density of the electromagnetic field (i.e., of the photon states), one can obtain the local [Formula: see text] values in the surroundings of individual chromophores simply by measuring their T1 times. Spatial mapping of the local [Formula: see text] values is accomplished by localizing the corresponding chromophores withnanometer accuracy. We demonstrate this approach for a polycrystalline n-hexadecane film doped with terrylene. Unexpectedly large fluctuations of local-field effects and effective [Formula: see text] values (the latter between 1.1 and 1.9) were found.

Revealing the Activity Distribution of a Single Nanocatalyst by Locating Single Nanobubbles with Super-Resolution Microscopy

It is challenging to uncover the catalytic activity at different locations of a single nanocatalyst for gas-generating reactions in real time. This research uses super-resolution microscopy to localize the center of single nanobubbles and reveal the local activity distribution at several to tens of nanometers accuracy. The distances between the centers of the nanobubbles and the center of the nanoplate usually distribute in a certain range from 0 to 500 nm, with the maximum population exhibiting at ∼200 nm. This research also shows that more nanobubbles appear near the tips of the Pd-Ag nanoplate compared with the edges, which indicates higher activity at the tips. In addition, the relationship between the location, lifetime, and turnover rate of the nanobubbles was also carefully studied. This work presents an effective, high-resolution method to localize the activity distribution of nanocatalysts during gas-generating reactions, such as photocatalytic water splitting, dehydrogenation, and electro-oxidation.

Full-field measurement with nanometric accuracy of 3D superficial displacements by digital profile correlation: A powerful tool for mechanics of materials

In recent decades, technological innovations have prompted the development of pioneering materials that attempt to satisfy new and forthcoming needs. The innovation in these materials is usually from their peculiar properties, which in many cases make them uniquely appropriate for a specific application. In this context, the development of innovative measurement techniques can provide more comprehensive understanding and knowledge of these materials' properties, often non-conventional and not easily retrieved by standard procedures. In order to obtain a full-field 3D displacement vector of a surface under investigation, the author proposes the combination of two well-known measurement techniques: the Confocal Microscopy (CM) and the two-dimensional Digital Image Correlation (2D-DIC). Specifically, CM has demonstrated its ability to successfully attain microscopic topography on a highly finished surface with sub-micrometric roughness, and such a technique could be used as a carrier to successfully apply the 2D-DIC algorithm. By this approach, it is not difficult to reach an accuracy of a few nanometers on the displacement measurement. The feasibility of the procedure proposed herein was demonstrated by two case studies: a tensile test of a Ni-alloy edge crack specimen, and a hardness test carried out on a thick AISI 1040 disk.

Nanoscale Mapping Functional Sites on Nanoparticles by Points Accumulation for Imaging in Nanoscale Topography (PAINT).

The ability of nanoparticles to selectively recognize a molecular target constitutes the key toward nanomedicine applications such as drug delivery and diagnostics. The activity of such devices is mediated by the presence of multiple copies of functional molecules on the nanostructure surface. Therefore, understanding the number and the distribution of nanoparticle functional groups is of utmost importance for the rational design of effective materials. Analytical methods are available, but to obtain quantitative information at the level of single particles and single functional sites, i. e., going beyond the ensemble, remains highly challenging. Here we introduce the use of an optical nanoscopy technique, DNA points accumulation for imaging in nanoscale topography (DNA-PAINT), to address this issue. Combining subdiffraction spatial resolution with molecular selectivity and sensitivity, DNA-PAINT provides both geometrical and functional information at the level of a single nanostructure. We show how DNA-PAINT can be used to image and quantify relevant functional proteins such as antibodies and streptavidin on nanoparticles and microparticles with nanometric accuracy in 3D and multiple colors. The generality and the applicability of our method without the need for fluorescent labeling hold great promise for the robust quantitative nanocharacterization of functional nanomaterials.

Fiducial-aided on-machine positioning method for precision manufacturing of optical freeform surfaces.

There are still significant challenges in the accurate positioning of optical freeform surfaces on the machine tool and the measurement instrument due to the high accuracy requirement and their complex shapes. This paper proposes a Fiducial-aided On-machine Positioning method (FAOPM) that combines on-machine measurement and off-machine measurement to precisely position optical freeform surfaces during the precision manufacturing cycle including rough machining, fine machining, measurement, and error compensation. The FAOPM makes use of fiducials which are firstly measured on a coordinate measuring machine with nanometric accuracy to generate a Fiducial-aided Computer Aided Design (FA-CAD) of the designed optical surface, then the developed on-machine measuring device obtains the accurate positions of the fiducials after remounting in the machining coordinate system. Finally the relative position of the workpiece is identified so that the associated cutting paths and compensation tool path can be easily generated. Several optical freeform surfaces were experimentally machined to prove the capability of the proposed method. The results indicate that the positions of the workpiece during the precision manufacturing and measurement cycle were precisely achieved and the form accuracy of the optical freeform surfaces was remarkable improved based on the FAOPM.

Engineering Surface Vacancy to Stabilize High-Voltage Battery Cathodes

In this issue of Chem, Cao and co-workers report a stabilization strategy for high-voltage lithium-ion battery cathodes down to the atomic scale. Using LiNi0.5Mn1.5O4 as a model, the authors demonstrated a protocol for precisely modulating the interstitial lattice sites on the material surface, showing the promising capability to improve electrochemical cyclability.

Construction of Uniform Cobalt-Based Nanoshells and Its Potential for Improving Li-Ion Battery Performance.

Surface cobalt doping is an effective and economic way to improve the electrochemical performance of cathode materials. Herein, by tuning the precipitation kinetics of Co2+, we demonstrate an aqueous-based protocol to grow uniform basic cobaltous carbonate coating layer onto different substrates, and the thickness of the coating layer can be adjusted precisely in nanometer accuracy. Accordingly, by sintering the cobalt-coated LiNi0.5Mn1.5O4 cathode materials, an epitaxial cobalt-doped surface layer will be formed, which will act as a protective layer without hindering charge transfer. Consequently, improved battery performance is obtained because of the suppression of interfacial degradation.

Three-dimensional single-molecule localization with nanometer accuracy using Metal-Induced Energy Transfer (MIET) imaging.

Our paper presents the first theoretical and experimental study using single-molecule Metal-Induced Energy Transfer (smMIET) for localizing single fluorescent molecules in three dimensions. Metal-Induced Energy Transfer describes the resonant energy transfer from the excited state of a fluorescent emitter to surface plasmons in a metal nanostructure. This energy transfer is strongly distance-dependent and can be used to localize an emitter along one dimension. We have used Metal-Induced Energy Transfer in the past for localizing fluorescent emitters with nanometer accuracy along the optical axis of a microscope. The combination of smMIET with single-molecule localization based super-resolution microscopy that provides nanometer lateral localization accuracy offers the prospect of achieving isotropic nanometer localization accuracy in all three spatial dimensions. We give a thorough theoretical explanation and analysis of smMIET, describe its experimental requirements, also in its combination with lateral single-molecule localization techniques, and present first proof-of-principle experiments using dye molecules immobilized on top of a silica spacer, and of dye molecules embedded in thin polymer films.

Monitoring two-coordinate positioning by means of optical spectral coding

Based on spectral coding of broadband radiation, a technique has been developed that makes it possible to monitor the position of a two-coordinate stage and to control its movement with nanometer accuracy. A distinctive feature of the technique is that it makes it possible to monitor the absolute position of the stage without any preliminary calibration. Such devices may be of interest for high-precision systems where the probe is required to move to a given point of the sample with nanometric accuracy.

Two-dimensional arbitrary nano-manipulation on a plasmonic metasurface.

In this Letter, we report on a plasmonic nano-ellipse metasurface with the purpose of trapping and two-dimensional (2D) arbitrary transport of nanoparticles by means of rotating the polarization of an excitation beam. The locations of hot spots within a metasurface are polarization dependent, thus making it possible to turn on/off the adjacent hot spots and then convey the trapped target by rotating the incident polarization state. For the case of a metasurface with a unit cell of perpendicularly orientated nano-ellipses, the hot spots with higher intensities are located at both apexes of the nano-ellipse whose major axis is parallel to the direction of polarization. When the polarization gradually rotates to its counterpart direction, the trapped particle may move around the ellipse and transfer to the most adjacent ellipse, due to the unbalanced trap potentials around the nano-ellipse. Clockwise and counterclockwise rotation would guide the particle in a different direction, which makes it possible to convey the particle arbitrarily within the plasmonic metasurface by setting a time sequence of polarization rotation. As confirmed by the three-dimensional finite-difference time-domain analysis, our design offers a novel scheme of 2D arbitrary transport with nanometer accuracy, which could be used in many on-chip optofluidic applications.

Identification of the critical depth-of-cut through a 2D image of the cutting region resulting from taper cutting of brittle materials

An automatic identification method for obtaining the critical depth-of-cut (DoC) of brittle materials with nanometric accuracy and sub-nanometric uncertainty is proposed in this paper. With this method, a two-dimensional (2D) microscopic image of the taper cutting region is captured and further processed by image analysis to extract the margin of generated micro-cracks in the imaging plane. Meanwhile, an analytical model is formulated to describe the theoretical curve of the projected cutting points on the imaging plane with respect to a specified DoC during the whole cutting process. By adopting differential evolution algorithm-based minimization, the critical DoC can be identified by minimizing the deviation between the extracted margin and the theoretical curve. The proposed method is demonstrated through both numerical simulation and experimental analysis. Compared with conventional 2D- and 3D-microscopic-image-based methods, determination of the critical DoC in this study uses the envelope profile rather than the onset point of the generated cracks, providing a more objective approach with smaller uncertainty.

Axial Colocalization of Single Molecules with Nanometer Accuracy Using Metal-Induced Energy Transfer.

Single-molecule localization based super-resolution microscopy has revolutionized optical microscopy and routinely allows for resolving structural details down to a few nanometers. However, there exists a rather large discrepancy between lateral and axial localization accuracy, the latter typically three to five times worse than the former. Here, we use single-molecule metal-induced energy transfer (smMIET) to localize single molecules along the optical axis, and to measure their axial distance with an accuracy of 5 nm. smMIET relies only on fluorescence lifetime measurements and does not require additional complex optical setups.

Precision PGC demodulation for homodyne interferometer modulated with a combined sinusoidal and triangular signal.

A precision PGC demodulation for homodyne interferometer modulated with a combined sinusoidal and triangular signal is proposed. Using a triangular signal as additional modulation, a continuous phase-shifted interference signal for ellipse fitting is generated whether the measured object is in static or moving state. The real-time ellipse fitting and correction of the AC amplitudes and DC offsets of the quadrature components in PGC demodulation can be realized. The merit of this modulation is that it can eliminate thoroughly the periodic nonlinearity resulting from the influences of light intensity disturbance, the drift of modulation depth, the carrier phase delay, and non-ideal performance of the low pass filters in the conversional PGC demodulation. The principle and realization of the signal processing with the combined modulation signal are described in detail. The experiments of accuracy and rate evaluations of ellipse fitting, nanometer, and millimeter displacement measurements were performed to verify the feasibility of the proposed demodulation. The experimental results show that the elliptical parameters of the quadrature components can be achieved precisely in real time and nanometer accuracy was realized in displacement measurements.

High-Fidelity 3D-Nanoprinting via Focused Electron Beams: Growth Fundamentals

While 3D-printing is currently experiencing significant growth and having a significant impact on science and technology, the expansion into the nanoworld is still a highly challenging task. Among the increasing number of approaches, focused electron-beam-induced deposition (FEBID) was recently demonstrated to be a viable candidate toward a generic direct-write fabrication technology with spatial nanometer accuracy for complex shaped 3D-nanoarchitectures. In this comprehensive study, we explore the parameter space for 3D-FEBID and investigate the implications of individual and interdependent parameters on freestanding nanosegments, which act as a fundamental building block for complex 3D-structures. In particular, the study provides new basic insights such as precursor transport limitations and angle dependent growth rates, both essential for high-fidelity fabrication. Complemented by practical aspects, we provide both basic insights in 3D-growth dynamics and technical guidance for specific process adapti...

A New Method (Sigma-SHREC) for Two-Color Fluorescent Distance Measurements with Nanometer Accuracy

A New Method (Sigma-SHREC) for Two-Color Fluorescent Distance Measurements with Nanometer Accuracy

Extinction spectra of suspensions of microspheres: determination of the spectral refractive index and particle size distribution with nanometer accuracy.

A method is presented to infer simultaneously the wavelength-dependent real refractive index (RI) of the material of microspheres and their size distribution from extinction measurements of particle suspensions. To derive the averaged spectral optical extinction cross section of the microspheres from such ensemble measurements, we determined the particle concentration by flow cytometry to an accuracy of typically 2% and adjusted the particle concentration to ensure that perturbations due to multiple scattering are negligible. For analysis of the extinction spectra, we employ Mie theory, a series-expansion representation of the refractive index and nonlinear numerical optimization. In contrast to other approaches, our method offers the advantage to simultaneously determine size, size distribution, and spectral refractive index of ensembles of microparticles including uncertainty estimation.

Combined use of confocal microscopy and DIC for 3D displacement vector measurement

In the present paper the author describes the potential offered by the combined use of the Confocal Microscopy (CM) and Digital Image Correlation (DIC) to resolve the whole displacement vector in full-field fashion and with nanometric accuracy. By means of two different configurations of the same portion of the area under investigation, the surface profile retrieved at microscopic level by the CM functioned as a carrier for the DIC algorithm, both for a polished surface and an engineering standard roughness. The in-plane displacement components obtained by DIC were then used to extract the out-of-plane component from the profile information. After describing all steps that are necessary for applying the procedure, preliminary results of an indentation tests carried out on a polished steel specimen are reported and discussed.

Three-Dimensional Tracking of Quantum Dot-Conjugated Molecules in Living Cells.

Here, we describe protocols for three-dimensional tracking of single quantum dot-conjugated molecules with nanometer accuracy in living cells using conventional fluorescence microscopy. The technique exploits out-of-focus images of single emitters combined with an automated pattern-recognition open-source software that fits the images with proper model functions to extract the emitter coordinates. We describe protocols for targeting quantum dots to both membrane components and cytosolic proteins.

Probing Chromatin Structure with Magnetic Tweezers.

Magnetic tweezers form a unique tool to study the topology and mechanical properties of chromatin fibers. Chromatin is a complex of DNA and proteins that folds the DNA in such a way that meter-long stretches of DNA fit into the micron-sized cell nucleus. Moreover, it regulates accessibility of the genome to the cellular replication, transcription, and repair machinery. However, the structure and mechanisms that govern chromatin folding remain poorly understood, despite recent spectacular improvements in high-resolution imaging techniques. Single-molecule force spectroscopy techniques can directly measure both the extension of individual chromatin fragments with nanometer accuracy and the forces involved in the (un)folding of single chromatin fibers. Here, we report detailed methods that allow one to successfully prepare in vitro reconstituted chromatin fibers for use in magnetic tweezers-based force spectroscopy. The higher-order structure of different chromatin fibers can be inferred from fitting a statistical mechanics model to the force-extension data. These methods for quantifying chromatin folding can be extended to study many other processes involving chromatin, such as the epigenetic regulation of transcription.

Single-Cell Optical Distortion Correction and Label-Free 3D Cell Shape Reconstruction on Lattices of Nanostructures.

Imaging techniques can be compromised by aberrations. Especially when imaging through biological specimens, sample-induced distortions can limit localization accuracy. In particular, this phenomenon affects localization microscopy, traction force measurements, and single-particle tracking, which offer high-resolution insights into biological tissue. Here we present a method for quantifying and correcting the optical distortions induced by single, adherent, living cells. The technique uses periodically patterned gold nanostructures as a reference framework to quantify optically induced displacements with micrometer-scale sampling density and an accuracy of a few nanometers. The 3D cell shape and a simplified geometrical optics approach are then utilized to remap the microscope image. Our experiments reveal displacements of up to several hundred nanometers, and in corrected images these distortions are reduced by a factor of 3. Conversely, the relationship between cell shape and distortion provides a novel method of 3D cell shape reconstruction from a single image, enabling label-free 3D cell analysis.