Detecting Dissociation Dynamics of Phosphorus Molecular Ions by Atom Probe Tomography.

Dissociation processes involving phosphorus cations were investigated during laser-assisted atom probe tomography of crystalline indium phosphide (InP). This technique not only allows the formation of medium-sized phosphorus cations by means of femtosecond laser pulses under ultrahigh vacuum and high electric field conditions but also allows one to study the time-resolved dissociation dynamics. Data reveal the formation of cations up to P232+ and their subsequent dissociation into two smaller Pk+ cations (k > 2). The use of a time- and position-sensitive detector combined with numerical calculations provided information related to the molecule orientation, decay time, and kinetic energy release during dissociation phenomena. Results suggest that the dissociation processes are most likely due to the emission of Pk2+ cations in excited states and their subsequent decay in low field regions during their flight toward the detector. This study provides operative guidelines to obtain information on dissociation processes using a tomographic atom probe as a reaction microscope and indicates the current capabilities and limitations of such an approach.

A photonic atom probe coupling 3D atomic scale analysis with in situ photoluminescence spectroscopy.

Laser enhanced field evaporation of surface atoms in laser-assisted Atom Probe Tomography (APT) can simultaneously excite photoluminescence in semiconductor or insulating specimens. An atom probe equipped with appropriate focalization and collection optics has been coupled with an in situ micro-photoluminescence (µPL) bench that can be operated during APT analysis. The photonic atom probe instrument we have developed operates at frequencies up to 500 kHz and is controlled by 150 fs laser pulses tunable in energy in a large spectral range (spanning from deep UV to near IR). Micro-PL spectroscopy is performed using a 320 mm focal length spectrometer equipped with a CCD camera for time-integrated and with a streak camera for time-resolved acquisitions. An example of application of this instrument on a multi-quantum well oxide heterostructure sample illustrates the potential of this new generation of tomographic atom probes.

Multi-microscopy nanoscale characterization of the doping profile in a hybrid Mg/Ge-doped tunnel junction.

A multi-microscopy investigation of a GaN tunnel junction (TJ) grown on an InGaN-based light emitting diode (LED) has been performed. The TJ consists of a heavily Ge-doped n-type GaN layer grown by ammonia-based molecular-beam epitaxy on a heavily Mg-doped p-type GaN thin layer, grown by metalorganic vapor phase epitaxy. A correlation of atom probe tomography, electron holography and secondary ion mass spectrometry has been performed in order to investigate the nm-scale distribution of both Mg and Ge at the TJ. Experimental results reveal that Mg segregates at the TJ interface, and diffuses into the Ge-doped layer. As a result, the dopant concentration and distribution differ significantly from the nominal values. Despite this, electron holography reveals a TJ depletion width of ∼7 nm, in agreement with band diagram simulations using the experimentally determined dopant distribution.

Dissociation of GaN2+ and AlN2+ in APT: Analysis of experimental measurements.

The use of a tip-shaped sample for the atom probe tomography technique offers the unique opportunity to analyze the dynamics of molecular ions in strong DC fields. We investigate here the stability of AlN2+ and GaN2+ dications emitted from an Al0.25Ga0.75N sample in a joint theoretical and experimental study. Despite the strong chemical resemblance of these two molecules, we observe only stable AlN2+, while GaN2+ can only be observed as a transient species. We simulate the emission dynamics of these ions on field-perturbed potential energy surfaces obtained from quantum chemical calculations. We show that the dissociation is governed by two independent processes. For all bound states, a mechanical dissociation is induced by the distortion of the potential energy surface in the close vicinity of the emitting tip. In the specific case of GaN2+, the relatively small electric dipole of the dication in its ground 13Σ- and excited 11Δ states induces a weak coupling with the electric field so that the mechanical dissociation into Ga+ + N+ lasts for sufficient time to be observed. By contrast, the AlN2+ mechanical dissociation leads to Al2+ + N which cannot be observed as a correlated event. For some deeply bound singlet excited states, the spin-orbit coupling with lower energy triplet states gives another chance of dissociation by system inter-system crossing with specific patterns observed experimentally in a correlated time of flight map.

Compositional accuracy of atom probe tomography measurements in GaN: Impact of experimental parameters and multiple evaporation events.

A systematic study of the biases occurring in the measurement of the composition of GaN by Atom Probe Tomography was carried out, in which the role of surface electric field and laser pulse intensity has been investigated. Our data confirm that the electric field is the main factor influencing the measured composition, which exhibits a deficiency of N at low field and a deficiency of Ga at high field. The deficiency of Ga at high field is interpreted in terms of preferential evaporation of Ga. The detailed analysis of multiple evaporation events reveals that the measured composition is not affected by pile-up phenomena occurring in detection system. The analysis of correlation histograms yields the signature of the production of neutral N2 due to the dissociation of GaN32+ ions. However, the amount of N2 neutral molecules that can be detected cannot account for the N deficiency found at low field. Therefore, we propose that further mechanisms of neutral N evaporation could be represented by dissociation reactions such as GaN+→ Ga++ N and GaN2+→ Ga2++ N.

Optical Contactless Measurement of Electric Field-Induced Tensile Stress in Diamond Nanoscale Needles.

The application of a high electrostatic field at the apex of monocrystalline diamond nanoscale needles induces an energy splitting of the photoluminescence lines of color centers. In particular, the splitting of the zero-phonon line of the neutral nitrogen-vacancy complex (NV0) has been studied within a laser-assisted tomographic atom probe equipped with an in situ microphotoluminescence bench. The measured quadratic dependence of the energy splitting on the applied voltage corresponds to the stress generated on the metal-like apex surface by the electrostatic field. Tensile stress up to 7 GPa has thus been measured in the proximity of the needle apex. Furthermore, the stress scales along the needle shank inversely proportionally to its axial cross section. We demonstrate thus a method for contactless piezo-spectroscopy of nanoscale systems by electrostatic field regulation for the study of their mechanical properties. These results also provide an experimental confirmation to the models of dielectrics surface metallization under high electrostatic field.

Electronic structure and stability of the SiO2+ dications produced in tomographic atom probe experiments.

The molecular electronic states of the SiO2+ dication have been investigated in a joint theoretical and experimental analysis. The use of a tip-shaped sample for tomographic atom probe analysis offers the unique opportunity to produce and to analyze the lifetime of some excited states of this dication. The perturbation brought by the large electric field of the polarized tip along the ion trajectory is analyzed by means of molecular dynamics simulation. For the typical electric fields used in the experiment, the lowest energy triplet states spontaneously dissociate, while the lowest energy singlet states do not. We show that the emission process leads to the formation of some excited singlet state, which dissociates by means of spin-orbit coupling with lower-energy triplet states to produce specific patterns associated with Si+ + O+ and Si2+ + O dissociation channels. These patterns are recorded and observed experimentally in a correlated time-of-flight map.

Core-shell InGaN/GaN nanowire light emitting diodes analyzed by electron beam induced current microscopy and cathodoluminescence mapping.

We report on the electron beam induced current (EBIC) microscopy and cathodoluminescence (CL) characterization correlated with compositional analysis of light emitting diodes based on core/shell InGaN/GaN nanowire arrays. The EBIC mapping of cleaved fully operational devices allows to probe the electrical properties of the active region with a nanoscale resolution. In particular, the electrical activity of the p-n junction on the m-planes and on the semi-polar planes of individual nanowires is assessed in top view and cross-sectional geometries. The EBIC maps combined with CL characterization demonstrate the impact of the compositional gradients along the wire axis on the electrical and optical signals: the reduction of the EBIC signal toward the nanowire top is accompanied by an increase of the CL intensity. This effect is interpreted as a consequence of the In and Al gradients in the quantum well and in the electron blocking layer, which influence the carrier extraction efficiency. The interface between the nanowire core and the radially grown layer is shown to produce in some cases a transitory EBIC signal. This observation is explained by the presence of charged traps at this interface, which can be saturated by electron irradiation.

Experimental and theoretical analysis of transport properties of core-shell wire light emitting diodes probed by electron beam induced current microscopy.

We report a systematic experimental and theoretical investigation of core-shell InGaN/GaN single wire light-emitting diodes (LEDs) using electron beam induced current (EBIC) microscopy. The wires were grown by catalyst-free MOVPE and processed into single wire LEDs using electron beam lithography on dispersed wires. The influence of the acceleration voltage and of the applied bias on the EBIC maps was investigated. We show that the EBIC maps provide information both on the minority carrier effects (i.e. on the local p-n junction collection efficiency) and on the majority carrier effects (i.e. the transport efficiency from the excited region toward the contacts). Because of a finite core and shell resistance a non-negligible current redistribution into the p-n junction takes place during the majority carrier transport. A theoretical model for transport in a core-shell wire is developed, allowing to explain the dependence of the EBIC profiles on the experimental parameters (the electron beam acceleration voltage and the bias applied on the device) and on the structural parameters of the wire (core and shell resistance, shunt resistance, etc). Comparison between simulated and experimental profiles provides valuable information concerning the structure inhomogeneities and gives insight into the wire electrical parameters.

Integrated photonic platform based on InGaN/GaN nanowire emitters and detectors.

We report the fabrication of a photonic platform consisting of single wire light-emitting diodes (LED) and photodetectors optically coupled by waveguides. MOVPE-grown (metal-organic vapor-phase epitaxy) InGaN/GaN p-n junction core-shell nanowires have been used for device fabrication. To achieve a good spectral matching between the emission wavelength and the detection range, different active regions containing either five narrow InGaN/GaN quantum wells or one wide InGaN segment were employed for the LED and the detector, respectively. The communication wavelength is ∼400 nm. The devices are realized by means of electron beam lithography on Si/SiO2 templates and connected by ∼100 µm long nonrectilinear SiN waveguides. The photodetector current trace shows signal variation correlated with the LED on/off switching with a fast transition time below 0.5 s.

Optical properties of GaN-based nanowires containing a single Al(0.14)Ga(0.86)N/GaN quantum disc.

The optical properties of wurtzite GaN nanowires containing single Al0.14Ga0.86N/GaN quantum discs of different thickness have been investigated. The dependence of the photoluminescence (PL) transition energy on the quantum disc thickness and the thickness of a lateral AlGaN shell has been simulated in the framework of a three-dimensional effective mass model, accounting for the presence of a lateral AlGaN shell, strain state and the piezoelectric and spontaneous polarization. The predicted transition energies are in good agreement with the statistics realized on more than 40 single nanowire emission spectra and PL spectra of ensembles of nanowires. The emission spectra of the single quantum discs exhibit a Lorentzian shape with a homogeneous line width as low as 3 meV. Finally, we discuss the dependence of the interband transition energy on diameter.

Visualizing highly localized luminescence in GaN/AlN heterostructures in nanowires.

The optical properties of a stack of GaN/AlN quantum discs (QDiscs) in a GaN nanowire have been studied by spatially resolved cathodoluminescence (CL) at the nanoscale (nanoCL) using a scanning transmission electron microscope (STEM) operating in spectrum imaging mode. For the electron beam excitation in the QDisc region, the luminescence signal is highly localized, with spatial extent as low as 5 nm, due to the high band gap difference between GaN and AlN. This allows the discrimination between the emission of neighbouring QDiscs and evidencing the presence of lateral inclusions, about 3 nm thick and 20 nm long rods (quantum rods, QRods), grown unintentionally on the nanowire sidewalls. These structures, also observed by STEM dark-field imaging, are proved to be optically active in nanoCL, emitting at similar, but usually shorter, wavelengths with respect to most QDiscs.

Photoluminescence polarization in strained GaN/AlGaN core/shell nanowires.

The optical polarization properties of GaN/AlGaN core/shell nanowire (NW) heterostructures have been investigated using polarization resolved micro-photoluminescence (µ-PL) and interpreted in terms of a strain-dependent 6 × 6 k·p theoretical model. The NW heterostructures were fabricated in two steps: the Si-doped n-type c-axis GaN NW cores were grown by molecular beam epitaxy (MBE) and then epitaxially overgrown using halide vapor phase epitaxy (HVPE) to form Mg-doped AlGaN shells. The emission of the uncoated strain-free GaN NW core is found to be polarized perpendicular to the c-axis, while the GaN core compressively strained by the AlGaN shell exhibits a polarization parallel to the NW c-axis. The luminescence of the AlGaN shell is weakly polarized perpendicular to the c-axis due to the tensile axial strain in the shell.

Photovoltaic properties of GaAsP core-shell nanowires on Si(001) substrate.

We report on the growth and electro-optical studies of photovoltaic properties of GaAsP nanowires. Low density GaAsP nanowires were grown by Au assisted MOVPE on Si(001) substrates using a two step procedure to form a radial p-n junction. The STEM analyses show that the nanowires have cubic structure with the alloy composition GaAs0.88P0.12 in the nanowire core and GaAs0.76P0.24 in the shell. The nanowire ensembles were processed in the form of sub-millimeter size mesas. The photovoltaic properties were characterized by optical beam induced current (OBIC) and electronic beam induced current (EBIC) maps. Both OBIC and EBIC maps show that the photovoltage is generated by the nanowires; however, a strong signal variation from wire to wire is observed. Only one out of six connected nanowires produce a measurable signal. These strong fluctuations can be tentatively explained by the variation of the resistance of the nanowire-to-substrate connection, which is highly sensitive to the quality of the Si-GaAsP interface. This study demonstrates the importance of the spatially resolved charge collection microscopy techniques for the diagnosis of failures in nanowire photovoltaic devices.

Ultraviolet photodetector based on GaN/AlN quantum disks in a single nanowire.

We report the demonstration of single-nanowire photodetectors relying on carrier generation in GaN/AlN QDiscs. Two nanowire samples containing QDiscs of different thicknesses are analyzed and compared to a reference binary n-i-n GaN nanowire sample. The responsivity of a single wire QDisc detector is as high as 2 x 10(3) A/W at lambda = 300 nm at room temperature. We show that the insertion of an axial heterostructure drastically reduces the dark current with respect to the binary nanowires and enhances the photosensitivity factor (i.e., the ratio between the photocurrent and the dark current) up to 5 x 10(2) for an incoming light intensity of 5 mW/cm(2). Photocurrent spectroscopy allows identification of the spectral contribution related to carriers generated within large QDiscs, which lies below the GaN band gap due to the quantum confined Stark effect.