Sub-nanometer Spatial Resolution Research Articles

Atom Probe Tomography of Apatites and Bone-Type Mineralized Tissues

Nanocrystalline biological apatites constitute the mineral phase of vertebrate bone and teeth. Beyond their central importance to the mechanical function of our skeleton, their extraordinarily large surface acts as the most important ion exchanger for essential and toxic ions in our body. However, the nanoscale structural and chemical complexity of apatite-based mineralized tissues is a formidable challenge to quantitative imaging. For example, even energy-filtered electron microscopy is not suitable for detection of small quantities of low atomic number elements typical for biological materials. Herein we show that laser-pulsed atom probe tomography, a technique that combines subnanometer spatial resolution with unbiased chemical sensitivity, is uniquely suited to the task. Common apatite end members share a number of features, but can clearly be distinguished by their spectrometric fingerprint. This fingerprint and the formation of molecular ions during field evaporation can be explained based on the chemistry of the apatite channel ion. Using end members for reference, we are able to interpret the spectra of bone and dentin samples, and generate the first three-dimensional reconstruction of 1.2 × 10(7) atoms in a dentin sample. The fibrous nature of the collagenous organic matrix in dentin is clearly recognizable in the reconstruction. Surprisingly, some fibers show selectivity in binding for sodium ions over magnesium ions, implying that an additional, chemical level of hierarchy is necessary to describe dentin structure. Furthermore, segregation of inorganic ions or small organic molecules to homophase interfaces (grain boundaries) is not apparent. This has implications for the platelet model for apatite biominerals.

Progress toward an aberration-corrected low energy electron microscope for DNA sequencing and surface analysis.

Monochromatic, aberration-corrected, dual-beam low energy electron microscopy (MAD-LEEM) is a novel imaging technique aimed at high resolution imaging of macromolecules, nanoparticles, and surfaces. MAD-LEEM combines three innovative electron-optical concepts in a single tool: a monochromator, a mirror aberration corrector, and dual electron beam illumination. The monochromator reduces the energy spread of the illuminating electron beam, which significantly improves spectroscopic and spatial resolution. The aberration corrector is needed to achieve subnanometer resolution at landing energies of a few hundred electronvolts. The dual flood illumination approach eliminates charging effects generated when a conventional, single-beam LEEM is used to image insulating specimens. The low landing energy of electrons in the range of 0 to a few hundred electronvolts is also critical for avoiding radiation damage, as high energy electrons with kilo-electron-volt kinetic energies cause irreversible damage to many specimens, in particular biological molecules. The performance of the key electron-optical components of MAD-LEEM, the aberration corrector combined with the objective lens and a magnetic beam separator, was simulated. Initial results indicate that an electrostatic electron mirror has negative spherical and chromatic aberration coefficients that can be tuned over a large parameter range. The negative aberrations generated by the electron mirror can be used to compensate the aberrations of the LEEM objective lens for a range of electron energies and provide a path to achieving subnanometer spatial resolution. First experimental results on characterizing DNA molecules immobilized on Au substrates in a LEEM are presented. Images obtained in a spin-polarized LEEM demonstrate that high contrast is achievable at low electron energies in the range of 1-10 eV and show that small changes in landing energy have a strong impact on the achievable contrast. The MAD-LEEM approach promises to significantly improve the performance of a LEEM for a wide range of applications in the biosciences, material sciences, and nanotechnology where nanometer scale resolution and analytical capabilities are required. In particular, the microscope has the potential of delivering images of unlabeled DNA strands with nucleotide-specific contrast. This simplifies specimen preparation and significantly eases the computational complexity needed to assemble the DNA sequence from individual reads.

Optoelectronic Properties of InAlN/GaN Distributed Bragg Reflector Heterostructure Examined by Valence Electron Energy Loss Spectroscopy

High-resolution monochromated electron energy loss spectroscopy (EELS) at subnanometric spatial resolution and <200 meV energy resolution has been used to assess the valence band properties of a distributed Bragg reflector multilayer heterostructure composed of InAlN lattice matched to GaN. This work thoroughly presents the collection of methods and computational tools put together for this task. Among these are zero-loss-peak subtraction and nonlinear fitting tools, and theoretical modeling of the electron scattering distribution. EELS analysis allows retrieval of a great amount of information: indium concentration in the InAlN layers is monitored through the local plasmon energy position and calculated using a bowing parameter version of Vegard Law. Also a dielectric characterization of the InAlN and GaN layers has been performed through Kramers-Kronig analysis of the Valence-EELS data, allowing band gap energy to be measured and an insight on the polytypism of the GaN layers.

High-resolution microscopy of plasmon field distributions by scanning tunneling luminescence and photoemission electron microscopies

Abstract The exploitation of plasmon resonances to promote the interaction between conjugated molecules and optical fields motivates intensive research. The objectives are to understand the mechanisms of plasmon-mediated interactions, and to realize molecularly- or atomically-precise metal nanostructures, combining field enhancements and optical antenna effects. In this review paper, we present examples of plasmonic-field mappings based on scanning tunneling microscope (STM)-induced light emission or multiphoton photoemission (PEEM), two techniques among those which offer todayʼs best spatial resolutions for plasmon microscopy. An unfamiliar property of the junction of an STM is its ability to behave as a highly localized source of light. It can be exploited to probe optoelectronic properties, in particular plasmonic fields, with ultimate subnanometer spatial resolution, an advantage balanced by a sometimes delicate deconvolution of local-probe influence. Alternatively, local-probe disadvantages can be overcome by imaging the photoemitted electrons, using well-established electron optics. This allows obtaining two-dimensional intensity maps reflecting the unperturbed distribution of the optical near field. This approach provides full field spectroscopic images with a routine spatial resolution of the order of 20 nm (down to 5 nm with recent aberration corrected instruments).

Nanoscale Chemical and Structural Characterization of Transient Metallic Nanowires using Aberration-Corrected STEM-EELS

Direct chemical and structural characterization of transient iron-nickel alloy nanowires was performed at subnanometer spatial resolution using probe spherical aberration-corrected scanning transmission electron microscopy and electron energy-loss spectroscopy. Nanowires with diameter less than 2 nm retaining their nominal bulk alloy composition were observed. In some cases, the nanowires were oxidized. Before rupture, a nanojunction as thin as three atoms in width could be imaged. The time-dependent structural analyses revealed the nanowire rupture mechanisms. It is found that the atoms on the {111} planes were the easiest to be removed by electron irradiation and fluctuations between low-energy and high-energy facets were observed. The hitherto unknown rich variety of structural and chemical behavior in alloyed magnetic nanojunctions should be considered for understanding their physical properties.

Surfactant Organic Molecules Restore Magnetism in Metal-Oxide Nanoparticle Surfaces

The properties of magnetic nanoparticles tend to be depressed by the unavoidable presence of a magnetically inactive surface layer. However, outstanding magnetic properties with a room-temperature magnetization near the bulk value can be produced by high-temperature synthesis methods involving capping with organic acid. The capping molecules are not magnetic, so the origin of the enhanced magnetization remains elusive. In this work, we present a real-space characterization on the subnanometer scale of the magnetic, chemical, and structural properties of iron-oxide nanoparticles via aberration-corrected scanning transmission electron microscopy. For the first time, electron magnetic chiral dichroism is used to map the magnetization of nanoparticles in real space with subnanometer spatial resolution. We find that the surface of the nanoparticles is magnetically ordered. Combining the results with density functional calculations, we establish how magnetization is restored in the surface layer. The bonding with the acid's O atoms results in O-Fe atomic configuration and distances close to bulk values. We conclude that the nature and number of molecules in the capping layer is an essential ingredient in the fabrication of nanoparticles with optimal magnetic properties.

Ge atom distribution in buried dome islands

Laser-assisted atom probe tomography microscopy is used to provide direct and quantitative compositional measurements of tri-dimensional Ge distribution in Ge dome islands buried by Si. Sub-nanometer spatial resolution 3D imaging shows that islands keep their facets after deposition of the Si cap, and that the island/substrate/Si cap interfaces are abrupt. The core of the domes contains 55% of Ge, while the island shell exhibits a constant composition of 15% of Ge. The {113} facets of the islands present a Ge enrichment up to 35%. The wetting layer composition is not homogeneous, varying from 9.5% to 30% of Ge.

(V)EELS Characterization of InAlN/GaN Distributed Bragg Reflectors

Ten-period InAlN/GaN distributed Bragg reflectors are examined by aberration corrected scanning transmission electron microscopy and by valence electron energy-loss spectroscopy (VEELS) with sub-nanometric spatial resolution and sub-eV energy dispersion. Deconvolution and peak subtraction methods, implemented in Matlab routines, are applied to the low loss region of the obtained VEEL spectra to retrieve information about the band gap energy and chemical composition, whereas a Kramers-Kronig transformation is used to retrieve the complex dielectric function of the examined material. The VEEL measurements reveal significant compositional variations in InAlN layers and show a ∼2nm thick InAlN layer with high indium content at each GaN/InAlN interface.

Microstructure and polarization fields in nitride semiconductors

The nitride semiconductors are widely used in high efficiency light emitting devices and are currently being considered for photovoltaic applications. The reduced symmetry in the wurtzite structure compared to cubic semiconductors results in the growth of large densities of crystalline defects and in the presence of strong spontaneous and piezoelectric polarization effects. A correlation between the microstructure and the polarization fields can be achieved with electron holography in the transmission electron microscope. Electron holograms thus obtained can provide energy band profiles with sub-nanometer spatial resolution. The phase of the electron beam is sensitive to the electrostatic potential, and a direct measurement of the latter can be achieved by making the electron beam signal that traverses the specimen interfere with a reference electron beam that travels through vacuum. This technique has been quite useful in probing the fields and charges at dislocations and at interfaces in semiconductors, and it is particularly useful to determine the piezoelectric effects in group III nitride semiconductor heterostructures. A review of applications to InGaN and AlGaN based heterostructures is presented in this paper.

High-resolution mapping of plasmonic modes: photoemission and scanning tunnelling luminescence microscopies

Photonic properties of dense metal nanostructures are currently under intense investigation because of the possible local enhancements of electromagnetic fields induced by plasmonic excitations. In this review paper, we present examples of plasmonic-field mappings based on multiphoton photoemission or STM-induced light emission, two techniques among those which offer today's best spatial resolutions for plasmon microscopy. By imaging the photoemitted electrons, using well-established electron optics, two-dimensional intensity maps reflecting the actual distribution of the optical near-field are obtained. The imaging technique involves no physical probe altering the measure. This approach provides full field spectroscopic images with a routine spatial resolution of the order of 20 nm (down to 2 nm with recent aberration corrected instruments). Alternatively, an unfamiliar property of the junction of scanning tunnelling microscope is its ability to behave as a highly localized source of light. It can be exploited to probe opto-electronic properties, in particular plasmonic fields, with ultimate subnanometre spatial resolution, an advantage balanced by a sometimes delicate deconvolution of local-probe influence.

Waveguide-enhanced grazing-incidence small-angle x-ray scattering of buried nanostructures in thin films

X-ray standing waves generated by the interference of the scattered x rays from parallel surfaces of a thin film, the so-called waveguide effect, can be used to enhance or reduce the scatterings from certain depths of the film. Used in combination with grazing-incidence small-angle x-ray scattering, this resonance effect provides depth sensitivity to extract buried structures in thin films of polymer and polymer/nanoparticle nanocomposite, which are not readily accessible by most surface techniques, such as scanning probe microscopy. We developed a rigorous theory of the diffuse scattering in the framework of the distorted-wave Born approximation using a discretization method analogous to Parratt's recursive formalism. In such a case, the distortion of the electric field of the unperturbed state from the nanostructures of interest is considered in a self-consistent manner. This theory allows a quantitative determination of the buried nanostructures when the x-ray waveguide enhancement is present or the size of the nanostructures of interest is comparable to or larger than the spatial frequency of electric-field intensity modulation. A unique capability afforded by this theory is that a nanometer or even subnanometer spatial resolution can be achieved in the depth information of the buried nanostructures, along with the in-plane correlation of the structures.

High quality InAlN single layers lattice-matched to GaN grown by molecular beam epitaxy

We report on properties of high quality ∼60 nm thick InAlN layers nearly in-plane lattice-matched to GaN, grown on c-plane GaN-on-sapphire templates by plasma-assisted molecular beam epitaxy. Excellent crystalline quality and low surface roughness are confirmed by X-ray diffraction, transmission electron microscopy, and atomic force microscopy. High annular dark field observations reveal a periodic in-plane indium content variation (8 nm period), whereas optical measurements evidence certain residual absorption below the band-gap. The indium fluctuation is estimated to be ± 1.2% around the nominal 17% indium content via plasmon energy oscillations assessed by electron energy loss spectroscopy with sub-nanometric spatial resolution.

Controlled Growth of Nanoparticles from Solution with In Situ Liquid Transmission Electron Microscopy

Direct visualization of lead sulfide nanoparticle growth is demonstrated by selectively decomposing a chemical precursor from a multicomponent solution using in situ liquid transmission electron microscopy. We demonstrate reproducible control over growth mechanisms that dictate the final morphology of nanostructures while observing growth in real-time with subnanometer spatial resolution. Furthermore, while an intense electron beam can initiate nanoparticle growth, it is also shown that a laser can trigger the reaction independently of the imaging electrons.

Biomimetic Crystallization of Ag2S Nanoclusters in Nanopore Assemblies

Self-organized nanocrystal architectures with subnanometric spatial resolution were obtained by mimicking the biological crystal growth. The key step of this facile, one-pot, biomimetic route is to induce the self-assembly of the artificial nanopore cucurbit[7]uril with metal ions, which generates supramolecular aggregates that recreate the physicochemical environment of biomineralization processes. The approach holds great promise for the fabrication of nanocrystal superstructures of functional materials, useful in optics, electronics, and catalysis.

Direct Imaging of Room Temperature Optical Absorption with Subnanometer Spatial Resolution

Optical absorption can detect individual molecules and nanostructures even in dissipative or strongly quenching environments where fluorescence signals are weak. Here we image optical absorption of individual carbon nanotubes with subnanometer resolution. We show that we can discriminate adjacent nanotubes on a length scale far below the diffraction limit. Then we compare optical absorption imaging of a defect in a single carbon nanotube (CNT) with conventional scanning tunneling microscopy (STM) and conventional current-voltage scan (I-V) bandgap profiles. We directly visualize the penetration depth σ' = 0.9 ± 0.3 nm of the CNT exciton state into the smaller bandgap region of the defect and derive a size σ = 1.8 ± 0.6 nm for the exciton state. Optical absorption provides a spectroscopic map of molecules simultaneously with conventional STM.

Three-Dimensional Atom Probe Tomography of Oxide, Anion, and Alkanethiolate Coatings on Gold

We have used three-dimensional atom probe tomography to analyze several nanometer-thick and monomolecular films on gold surfaces. High-purity gold wire was etched by electropolishing to create a sharp tip suitable for field evaporation with a radius of curvature of <100 nm. The near-surface region of a freshly etched gold tip was examined with the atom probe at subnanometer spatial resolution and with atom-level composition accuracy. A thin contaminant layer, primarily consisting of water and atmospheric gases, was observed on a fresh tip. This sample exhibited crystalline lattice spacings consistent with the interlayer spacing of {200} lattice planes of bulk gold. A thin oxide layer was created on the gold surface via plasma oxidation, and the thickness and composition of this layer was measured. Clear evidence of a nanometer-thick oxide layer was seen coating the gold tip, and the atomic composition of the oxide layer was consistent with the expected stoichiometry for gold oxide. Monomolecular anions layers of Br(-) and I(-) were created via adsorption from aqueous solutions onto the gold. Atom probe data verified the presence of the monomolecular anion layers on the gold surface, with ion density values consistent with literature values. A hexanethiolate monolayer was coated onto the gold tip, and atom probe analysis revealed a thin film whose ion fragments were consistent with the molecular composition of the monolayer and a surface coverage similar to that expected from literature. Details of the various coating compositions and structures are presented, along with discussion of the reconstruction issues associated with properly analyzing these thin-film systems.

Atom probe microscopy of three-dimensional distribution of silicon isotopes in Si28∕Si30 isotope superlattices with sub-nanometer spatial resolution

Laser-assisted atom probe microscopy of 2 nm period Si28∕Si30 isotope superlattices (SLs) is reported. Three-dimensional distributions of Si28 and Si30 stable isotopes are obtained with sub-nanometer spatial resolution. The depth resolution of the present atom probe analysis is much higher than that of secondary ion mass spectrometry (SIMS) even when SIMS is performed with a great care to reduce the artifact due to atomic mixing. Outlook of Si isotope SLs as ideal depth scales for SIMS and three-dimensional position standards for atom probe microscopy is discussed.

Ultralong spin coherence time in isotopically engineered diamond

As quantum mechanics ventures into the world of applications and engineering, materials science faces the necessity to design matter to quantum grade purity. For such materials, quantum effects define their physical behaviour and open completely new (quantum) perspectives for applications. Carbon-based materials are particularly good examples, highlighted by the fascinating quantum properties of, for example, nanotubes or graphene. Here, we demonstrate the synthesis and application of ultrapure isotopically controlled single-crystal chemical vapour deposition (CVD) diamond with a remarkably low concentration of paramagnetic impurities. The content of nuclear spins associated with the (13)C isotope was depleted to 0.3% and the concentration of other paramagnetic defects was measured to be <10(13) cm(-3). Being placed in such a spin-free lattice, single electron spins show the longest room-temperature spin dephasing times ever observed in solid-state systems (T2=1.8 ms). This benchmark will potentially allow observation of coherent coupling between spins separated by a few tens of nanometres, making it a versatile material for room-temperature quantum information processing devices. We also show that single electron spins in the same isotopically engineered CVD diamond can be used to detect external magnetic fields with a sensitivity reaching 4 nT Hz(-1/2) and subnanometre spatial resolution.

Pulsed synchrotron x-ray as a tool for providing molecular movies at 100-picosecond temporal and sub-nanometer spatial resolution

Time-resolved X-ray techniques utilizing pulsed nature of synchrotron radiation are becoming general and powerful tools to explore structural dynamics in materials and biological systems. The time-resolved technique enables to produce structural movies at 100-picosecond temporal and sub-nanometer spatial resolution. It will be fascinating to apply such capabilities to capture ultrafast cooperative phenomena in strongly-correlated electron systems, photochemical catalytic reaction dynamics in liquid or on solid surface, light-induced response of photosensitive protein molecules, etc. The time-resolved X-ray studies conducted at NW14, PF-AR, KEK will be presented.

Surface Residual Stress Measurement Using Curvature Interferometry

Surface roughness plays an important role in the delamination wear caused by rough surface contact. A recent dislocation model analysis predicts that nano-scale contacts of surface steps induce nucleation of dislocations leading to pro-load and anti-load dislocation segregation near the contact surface. Such dislocation segregation generates a sub-layer of tensile residual stress in a much thicker layer of compressive residual stress near the surface. The tensile sub-layer thickness is expected to be about 50 to 100 times the step height. In order to verify the predictions of the model analysis, contact experiments are carried out on polycrystalline aluminum surface to determine the existence of the tensile sub-layer. The variation of the residual stress along the thickness direction is measured using a newly developed high sensitivity curvature-measurement interferometer. The residual stress distribution measured with sub-nanometer spatial resolution indicates that contact loading leads to formation of a highly stressed sub-layer of tensile residual stress within a much thicker layer of compressive residual stress. Implications of tensile residual stress for delamination wear are discussed.