Laser-assisted atom probe tomography (APT) and high-resolution dark-field electron holography (HR... more Laser-assisted atom probe tomography (APT) and high-resolution dark-field electron holography (HR-DFEH) were performed to investigate the composition of a polar [0001] GaN/AlxGa1 − xN/InyGa1 − yN light emitting diode. In particular, the III-site fraction of both AlxGa1 − xN and InyGa1 − yN alloys was studied adopting a comparative approach. HR-DFEH allows mapping the projected strain with a subnanometer spatial resolution which is used for the calculation of the two-dimensional alloy composition distribution. APT provides three-dimensional alloys composition distribution with a nanometer spatial resolution. However, here we reveal that important inaccuracies affect local composition measurements. A Ga-poor composition is obtained in high DC-electric field regions. Moreover, such inaccuracies may be locally enhanced where the [0001] pole intersects the surface of the analyzed specimen, leading to a lower fraction of Ga measured. III-site fractions closer to the nominal values were me...
The use of a tip-shaped sample for the atom probe tomography technique offers the unique opportun... more 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...
We have investigated the morphology of a nanotip under femtosecond laser pulse illumination and a... more We have investigated the morphology of a nanotip under femtosecond laser pulse illumination and a high electric field. We show that both the symmetry and the local radius of the tip change with the direction of laser polarization as against the tip axis. The experiments were performed on the very same GaN nanotip by laser-assisted atom probe tomography and electron tomography. This allowed an accurate assessment of the tip features by following the order of evaporation of single atoms from the surface. A change of atom emission sites was observed when a change of the angle between the tip axis and the linearly polarized electric field of the laser was imposed. This enables an optical control of field-evaporation sites. A close optical control of the tip morphology on a scale below 10 nm is thus achievable. Calculations of the field at nanotip apex and absorption maps support the experimental observations. Based on the present study, methods can be developed for reshaping nanotips at...
A systematic study of the biases occurring in the measurement of the composition of GaN by Atom P... more 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 N due to the dissociation of GaN ions. However, the amount of N 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...
We report a correlative microscopy study of a sample containing three stacks of InGaN/GaN quantum... more We report a correlative microscopy study of a sample containing three stacks of InGaN/GaN quantum dots (QDs) grown at different substrate temperature, each stack consisting of 3 layers of QDs. Decreasing the substrate temperature along the growth axis leads to the proliferation of structural defects. However, the luminescence intensity increases towards the surface, in spite of the higher density of threading dislocations, revealing that the QD layers closer to the substrate behave as traps for non-radiative point defects. During atom probe tomography experiments combined with in-situ micro-photoluminescence, it was possible to isolate the optical emission of a single QD located in the topmost QD stack, closer to the sample surface. The single QD emission line displayed a spectral shift during the experiment confirming the relaxation of elastic strain due to material evaporation during atom probe tomography.
Cerium oxide sol-gel-derived thin films were crystallized by pulsed excimer laser annealing (ELA)... more Cerium oxide sol-gel-derived thin films were crystallized by pulsed excimer laser annealing (ELA). X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman Spectroscopy (RS), and Fourier transform infrared (FTIR) were employed to analyze the effect of laser fluence and number of pulses on the structural and morphological properties of the irradiated films. XRD and RS results, supported by thermal simulations, confirmed crystallization into cubic cerium oxide starting from 40 mJcm−2. SEM micrographs showed that an increased number of pulses induced the formation of porous and complex nanostructured surfaces, different from the morphology obtained on thermally annealed films. Finally, water contact angle measurements revealed that the films showed a characteristic hydrophobic “petal effect”. Graphical Abstract
By collecting simultaneously optical and chemical/morphological data from nanoscale volumes, the ... more By collecting simultaneously optical and chemical/morphological data from nanoscale volumes, the Photonic Atom Probe (PAP) can be applied not only to the study of the relationship between optical and structural properties of quantum emitter but also to evaluate the influence of other factors, such as the presence of point defects, on the photoluminescence. Through the analysis of multiple layers of InGaN/GaN quantum dots (QDs), grown so that the density of structural defects is higher with increasing distance from the substrate, we establish that the light emission is higher in the regions exhibiting a higher presence of structural defects. While the presence of intrinsic point defects with non-radiative recombination properties remains elusive, our result is consistent with the fact that QD layers closer to the substrate behave as traps for non-radiative point defects. This result demonstrates the potential of the PAP as a technique for the study of the optical properties of defect...
In the last years technologies related to photovoltaic energy have rapidly developed and the inte... more In the last years technologies related to photovoltaic energy have rapidly developed and the interest on renewable energy power source substantially increased. In particular, cost reduction and appropriate feed-in tariff contributed to the increase of photovoltaic installation, especially in Germany and Italy. However, for several technologies, the observed experimental efficiency of solar cells is still far from the theoretical maximum efficiency, and thus there is still room for improvement. In this framework the research and development of new materials and new solar devices is mandatory. In this thesis the morphological and optical properties of thin films of nanocrystalline silicon oxynitride (nc-SiON) have been investigated. This material has been studied in view of its application in Si based heterojunction solar cells (HIT). Actually, a-Si:H is used now in these cells as emitter layer. Amorphous SiO_x N_y has already shown excellent properties, such as: electrical conductivi...
Laser-assisted atom probe tomography (APT) and high-resolution dark-field electron holography (HR... more Laser-assisted atom probe tomography (APT) and high-resolution dark-field electron holography (HR-DFEH) were performed to investigate the composition of a polar [0001] GaN/AlxGa1 − xN/InyGa1 − yN light emitting diode. In particular, the III-site fraction of both AlxGa1 − xN and InyGa1 − yN alloys was studied adopting a comparative approach. HR-DFEH allows mapping the projected strain with a subnanometer spatial resolution which is used for the calculation of the two-dimensional alloy composition distribution. APT provides three-dimensional alloys composition distribution with a nanometer spatial resolution. However, here we reveal that important inaccuracies affect local composition measurements. A Ga-poor composition is obtained in high DC-electric field regions. Moreover, such inaccuracies may be locally enhanced where the [0001] pole intersects the surface of the analyzed specimen, leading to a lower fraction of Ga measured. III-site fractions closer to the nominal values were me...
The use of a tip-shaped sample for the atom probe tomography technique offers the unique opportun... more 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...
We have investigated the morphology of a nanotip under femtosecond laser pulse illumination and a... more We have investigated the morphology of a nanotip under femtosecond laser pulse illumination and a high electric field. We show that both the symmetry and the local radius of the tip change with the direction of laser polarization as against the tip axis. The experiments were performed on the very same GaN nanotip by laser-assisted atom probe tomography and electron tomography. This allowed an accurate assessment of the tip features by following the order of evaporation of single atoms from the surface. A change of atom emission sites was observed when a change of the angle between the tip axis and the linearly polarized electric field of the laser was imposed. This enables an optical control of field-evaporation sites. A close optical control of the tip morphology on a scale below 10 nm is thus achievable. Calculations of the field at nanotip apex and absorption maps support the experimental observations. Based on the present study, methods can be developed for reshaping nanotips at...
A systematic study of the biases occurring in the measurement of the composition of GaN by Atom P... more 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 N due to the dissociation of GaN ions. However, the amount of N 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...
We report a correlative microscopy study of a sample containing three stacks of InGaN/GaN quantum... more We report a correlative microscopy study of a sample containing three stacks of InGaN/GaN quantum dots (QDs) grown at different substrate temperature, each stack consisting of 3 layers of QDs. Decreasing the substrate temperature along the growth axis leads to the proliferation of structural defects. However, the luminescence intensity increases towards the surface, in spite of the higher density of threading dislocations, revealing that the QD layers closer to the substrate behave as traps for non-radiative point defects. During atom probe tomography experiments combined with in-situ micro-photoluminescence, it was possible to isolate the optical emission of a single QD located in the topmost QD stack, closer to the sample surface. The single QD emission line displayed a spectral shift during the experiment confirming the relaxation of elastic strain due to material evaporation during atom probe tomography.
Cerium oxide sol-gel-derived thin films were crystallized by pulsed excimer laser annealing (ELA)... more Cerium oxide sol-gel-derived thin films were crystallized by pulsed excimer laser annealing (ELA). X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman Spectroscopy (RS), and Fourier transform infrared (FTIR) were employed to analyze the effect of laser fluence and number of pulses on the structural and morphological properties of the irradiated films. XRD and RS results, supported by thermal simulations, confirmed crystallization into cubic cerium oxide starting from 40 mJcm−2. SEM micrographs showed that an increased number of pulses induced the formation of porous and complex nanostructured surfaces, different from the morphology obtained on thermally annealed films. Finally, water contact angle measurements revealed that the films showed a characteristic hydrophobic “petal effect”. Graphical Abstract
By collecting simultaneously optical and chemical/morphological data from nanoscale volumes, the ... more By collecting simultaneously optical and chemical/morphological data from nanoscale volumes, the Photonic Atom Probe (PAP) can be applied not only to the study of the relationship between optical and structural properties of quantum emitter but also to evaluate the influence of other factors, such as the presence of point defects, on the photoluminescence. Through the analysis of multiple layers of InGaN/GaN quantum dots (QDs), grown so that the density of structural defects is higher with increasing distance from the substrate, we establish that the light emission is higher in the regions exhibiting a higher presence of structural defects. While the presence of intrinsic point defects with non-radiative recombination properties remains elusive, our result is consistent with the fact that QD layers closer to the substrate behave as traps for non-radiative point defects. This result demonstrates the potential of the PAP as a technique for the study of the optical properties of defect...
In the last years technologies related to photovoltaic energy have rapidly developed and the inte... more In the last years technologies related to photovoltaic energy have rapidly developed and the interest on renewable energy power source substantially increased. In particular, cost reduction and appropriate feed-in tariff contributed to the increase of photovoltaic installation, especially in Germany and Italy. However, for several technologies, the observed experimental efficiency of solar cells is still far from the theoretical maximum efficiency, and thus there is still room for improvement. In this framework the research and development of new materials and new solar devices is mandatory. In this thesis the morphological and optical properties of thin films of nanocrystalline silicon oxynitride (nc-SiON) have been investigated. This material has been studied in view of its application in Si based heterojunction solar cells (HIT). Actually, a-Si:H is used now in these cells as emitter layer. Amorphous SiO_x N_y has already shown excellent properties, such as: electrical conductivi...
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