Super-resolution Optical Spectroscopy of Nanoscale Emitters within a Photonic Atom Probe.

Atom Probe Tomography (APT) is a microscopy technique allowing for the 3D reconstruction of the chemical composition of a nanoscale needle-shaped sample with a precision close to the atomic scale. The photonic atom probe (PAP) is an evolution of APT featuring in situ and operando detection of the photoluminescence signal. The optical signatures of the light-emitting centers can be correlated with the structural and chemical information obtained by the analysis of the evaporated ions. It becomes thus possible to discriminate and interpret the spectral signatures of different light emitters as close as 20 nm, well beyond the resolution limit set by the exciting laser wavelength. This technique opens up new perspectives for the study of the physics of low dimensional systems, defects and optoelectronic devices.

Conduction mechanisms and voltage drop during field electron emission from diamond needles.

We report results of experimental investigation of field electron emission from diamond nanoemitters. The measurements were performed with single crystal diamond needles fixed at tungsten tips. The voltage drop along diamond needles during emission was revealed and measured using electron energy spectroscopy. The observed linear dependence of the voltage drop in diamond on voltage applied to the tungsten tip is explained in the frame of a simple macroscopic electrical model combining Poole-Frenkel conduction along the diamond tip and Fowler-Nordheim tunneling at the diamond-vacuum junction. Experimental evidences of electron emission sensitivity to laser illumination are discussed for possible modification of diamond emitter characteristics and voltage drop.

Unraveling the Metastability of C n2+ ( n = 2-4) Clusters.

Pure carbon clusters have received considerable attention for a long time. However, fundamental questions, such as what the smallest stable carbon cluster dication is, remain unclear. We investigated the stability and fragmentation behavior of C n2+ ( n = 2-4) dications using state-of-the-art atom probe tomography. These small doubly charged carbon cluster ions were produced by laser-pulsed field evaporation from a tungsten carbide field emitter. Correlation analysis of the fragments detected in coincidence reveals that they only decay to C n-1+ + C+. During C22+ → C+ + C+, significant kinetic energy release (∼5.75-7.8 eV) is evidenced. Through advanced experimental data processing combined with ab initio calculations and simulations, we show that the field-evaporated diatomic 12C22+ dications are either in weakly bound 3Πu and 3Σg- states, quickly dissociating under the intense electric field, or in a deeply bound electronic 5Σu- state with lifetimes >180 ps.

Field-Dependent Measurement of GaAs Composition by Atom Probe Tomography.

The composition of GaAs measured by laser-assisted atom probe tomography may be inaccurate depending on the experimental conditions. In this work, we assess the role of the DC field and the impinging laser energy on such compositional bias. The DC field is found to have a major influence, while the laser energy has a weaker one within the range of parameters explored. The atomic fraction of Ga may vary from 0.55 at low-field conditions to 0.35 at high field. These results have been interpreted in terms of preferential evaporation of Ga at high field. The deficit of As is most likely explained by the formation of neutral As complexes either by direct ejection from the tip surface or upon the dissociation of large clusters. The study of multiple detection events supports this interpretation.

Carrier Localization in GaN/AlN Quantum Dots As Revealed by Three-Dimensional Multimicroscopy.

The localization of carrier states in GaN/AlN self-assembled quantum dots (QDs) is studied by correlative multimicroscopy relying on microphotoluminescence, electron tomography, and atom probe tomography (APT). Optically active field emission tip specimens were prepared by focused ion beam from an epitaxial film containing a stack of quantum dot layers and analyzed with different techniques applied subsequently on the same tip. The transition energies of single QDs were calculated in the framework of a 6-bands k.p model on the basis of APT and scanning transmission electron microscopy characterization showing that a good agreement between experimental and calculated energies can be obtained, overcoming the limitations of both techniques. The results indicate that holes effectively localize at interface fluctuations at the bottom of the QD, decreasing the extent of the wave function and the band-to-band transition energy. They also represent an important step toward the correlation of the three-dimensional atomic scale structural information with the optical properties of single light emitters based on quantum confinement.

Optimizing Atom Probe Analysis with Synchronous Laser Pulsing and Voltage Pulsing.

Atom probe has been developed for investigating materials at the atomic scale and in three dimensions by using either high-voltage (HV) pulses or laser pulses to trigger the field evaporation of surface atoms. In this paper, we propose an atom probe setup with pulsed evaporation achieved by simultaneous application of both methods. This provides a simple way to improve mass resolution without degrading the intrinsic spatial resolution of the instrument. The basic principle of this setup is the combination of both modes, but with a precise control of the delay (at a femtosecond timescale) between voltage and laser pulses. A home-made voltage pulse generator and an air-to-vacuum transmission system are discussed. The shape of the HV pulse presented at the sample apex is experimentally measured. Optimizing the delay between the voltage and the laser pulse improves the mass spectrum quality.

Dissociation Dynamics of Molecular Ions in High dc Electric Field.

In an atom probe, molecular ions can be field evaporated from the analyzed material and, then, can dissociate under the very intense electric field close to the field emitter. In this work, field evaporation of ZnO reveals the emission of Zn2O2(2+) ions and their dissociation into ZnO(+) ions. It is shown that the repulsion between the produced ZnO(+) ions is large enough to have a measurable effect on both the ion trajectories and times of flight. Comparison with numerical simulations of the ion trajectories gives information on the lifetime of the parent ions, the energy released by the dissociation and repulsion, and also the dissociation direction. This study not only opens the way to a new method to obtain information on the behavior of molecular ions in high electric fields by using an atom probe, but also opens up the interesting perspective to apply this technique to a wide class of materials and molecules.

Correlation of microphotoluminescence spectroscopy, scanning transmission electron microscopy, and atom probe tomography on a single nano-object containing an InGaN/GaN multiquantum well system.

A single nanoscale object containing a set of InGaN/GaN nonpolar multiple-quantum wells has been analyzed by microphotoluminescence spectroscopy (µPL), high-resolution scanning transmission electron microscopy (HR-STEM) and atom probe tomography (APT). The correlated measurements constitute a rich and coherent set of data supporting the interpretation that the observed µPL narrow emission lines, polarized perpendicularly to the crystal c-axis and with energies in the interval 2.9-3.3 eV, are related to exciton states localized in potential minima induced by the irregular 3D In distribution within the quantum well (QW) planes. This novel method opens up interesting perspectives, as it will be possible to apply it on a wide class of quantum confining emitters and nano-objects.

High-performance bulk thermoelectrics with all-scale hierarchical architectures.

With about two-thirds of all used energy being lost as waste heat, there is a compelling need for high-performance thermoelectric materials that can directly and reversibly convert heat to electrical energy. However, the practical realization of thermoelectric materials is limited by their hitherto low figure of merit, ZT, which governs the Carnot efficiency according to the second law of thermodynamics. The recent successful strategy of nanostructuring to reduce thermal conductivity has achieved record-high ZT values in the range 1.5-1.8 at 750-900 kelvin, but still falls short of the generally desired threshold value of 2. Nanostructures in bulk thermoelectrics allow effective phonon scattering of a significant portion of the phonon spectrum, but phonons with long mean free paths remain largely unaffected. Here we show that heat-carrying phonons with long mean free paths can be scattered by controlling and fine-tuning the mesoscale architecture of nanostructured thermoelectric materials. Thus, by considering sources of scattering on all relevant length scales in a hierarchical fashion--from atomic-scale lattice disorder and nanoscale endotaxial precipitates to mesoscale grain boundaries--we achieve the maximum reduction in lattice thermal conductivity and a large enhancement in the thermoelectric performance of PbTe. By taking such a panoscopic approach to the scattering of heat-carrying phonons across integrated length scales, we go beyond nanostructuring and demonstrate a ZT value of ∼2.2 at 915 kelvin in p-type PbTe endotaxially nanostructured with SrTe at a concentration of 4 mole per cent and mesostructured with powder processing and spark plasma sintering. This increase in ZT beyond the threshold of 2 highlights the role of, and need for, multiscale hierarchical architecture in controlling phonon scattering in bulk thermoelectrics, and offers a realistic prospect of the recovery of a significant portion of waste heat.