Dilute-Nitride Low-Dimensional Nanostructures Formed on Non-Planar Substrates

The properties of semiconductors heterostructures of nanoscopic dimensions change from that of bulk material according to the rules of quantum mechanics. The planar quantum wells (QWs) are widely used in various diode and laser devices thanks to the relative ease of fabrication and to their improved electronic and optical performance compared to bulk materials. Quantum effects become more apparent when the charge carriers are confined in more than 1 spatial dimension. Much scientific interest was initially dedicated to the quantum wire (QWR) structures, which confine carriers into a quasi-1D space. But their sensitivity to disorder and the development of efficient fabrication methods of quantum dots (QD) shifted the attention to this latter system. The carrier confinement in the three directions of space confers to these structures a discrete spectrum of energy states, with the state occupancy ruled by the Pauli exclusion principle. The prospective applications are numerous in domains such as ultra-low threshold lasers, quantum cryptography, true random numbers generation, quantum electrodynamics experiments, etc. One of the prominent semiconductor growth techniques is the metalorganic vapour phase epitaxy (MOVPE). We used this method to produce ordered QWRs and QDs at the bottom of V-shaped and tetrahedral recesses, respectively. These nanostructures form by the complimentary actions of nano-capillarity and growth rate anisotropy in these recesses etched in GaAs substrates. This fabrication process offers some key advantages over other methods. The emission energy is very well controlled, with a narrow inhomogeneous broadening and a high uniformity across the wafer. Combined with the highly precise control on the formation site, this offers the possibility of high-yield integration of one or even several nanostructures, e.g., into photonic crystal devices. Other advantages of this approach are the impressive tunability of the electronic potential within the nanostructures and the possible use of well-defined intraband transitions. However, the emission energy of V-groove QWRs and pyramidal QDs studied so far is quite limited due to the formation mechanism imposing a low degree of strain. Incorporation of nitrogen has dramatic effects on the band structure of GaAs-based materials. Dilute concentrations ( 250 meV). The substrate miscut and the surface corrugations are shown to play an important role in the N incorporation efficiency: QWs grown on large substrate misorientations emit at longer wavelength than those grown on usual (100)-"exact" substrates, while exhibiting a comparable luminescence efficiency. The importance of a uniform N distribution within the QW is stressed, which appears difficult to achieve when the effect of surface corrugation is combined with that of In segregation. The second part of the work focuses on the N incorporation into V-groove QWRs. Important emission redshifts are achieved, in the ∼ 250 meV range. We first detail the emission spectrum and assert the 1D-character of the carrier wavefunctions. The influence of various growth and structural parameters is explored, leading to the fabrication of QWRs emitting at 1.3 μm at room temperature. The evolution of the polarization properties with temperature is also characterized. The third main topic and primary goal of this thesis is the nitrogen incorporation into QDs formed in inverted pyramids etched on (111)B GaAs substrates. A study is first conducted to understand the effects of several growth and structural parameters on the emission properties of InGaAs QDs. Nitrogen incorporation into QDs is then successfully demonstrated. The monitoring of the lateral QWR emission energy suggests a peculiar N incorporation pattern, or a significant perturbation of the formation of these lateral nanostructures. By contrast to what achieved with QWs and QWR structures, only limited emission redshifts were achieved (∼ 75 meV). The QD linewidths, degree of linear polarization and fine structure splitting are significantly deteriorated when compared to the InGaAs counterparts. These results cast serious doubts on the perspective of high-quality GaAs-based QDs in pyramids emitting at long wavelength. Our results demonstrate that nitrogen does not have the potential to shift the emission wave-length of InGaAs pyramidal QDs up to 1.3 μm, while simultaneously satisfying strict quality requirements. But other material systems may offer such opportunities. We briefly explore the possibilities of growing InGaAs/InAlAs nanostructures on patterned InP wafers. This ongoing project may open new possibilities for exploiting the pyramidal QD system. A kinetic Monte-Carlo numerical algorithm was implemented, reproducing by deposition and diffusion processes the evolution of the pyramidal template during growth. The numerical experiments were compared with post-growth AFM measurements of real samples. The recesses are observed to strongly affect the monatomic step flow on the neighboring (111)B surfaces. The simulations especially evidence the strong attraction of the pyramid apex on the atoms of the surrounding area, tending to elevate the QD formation site from the nominal C3V symmetry toward a hexagonal one

Self-Reported Violence Experienced by Swiss Prehospital Emergency Care Providers.

Workplace violence is a serious and increasing problem in health care. Nevertheless, only few studies were carried out concerning this topic and then mainly in English-speaking countries. The objectives were to describe the acts of violence experienced by prehospital emergency care providers (PECPs) in the western part of Switzerland between January and December 2016 and to assess the consequences for subsequent PECPs behaviors. An observational cross-sectional study, carried out using an online survey, has been sent to all 416 PECPs in the Canton of Vaud, in the western, French-speaking, part of Switzerland. The survey contained items of demographic data and items to assess the type and consequence of violence sustained. This was classified as five types: verbal assault, intimidation, physical assault, sexual harassment, and sexual assault. 273 (65.6%) PECPs participated in the survey. During 2016, workplace violence was reported by 229 survey participants (83.9%). Most declared to be the victim of such violence between one and three times during the year. In all cases of violence described, the patient and/or a relative initiated aggressive behavior in 96% of cases. Verbal assaults were the most common (99.2% of all acts), followed by intimidation (72.8%), physical assault (69.6%), and sexual harassment (16.3%). Concerning physical assault, PECPs were predominantly victims of spitting and/or jostling (50%). After a violent event, in 50% of cases, the PECPs modified their behavior owing to the experience of workplace violence; 82% now wear protective vests, and 16% carry weapons for self-defense, such as pepper sprays. Seventy-five percent changed their intervention strategies, acting more carefully and using verbal de-escalation techniques or physical restraints for violent patients. Workplace violence is frequent and has significant consequences for PECPs. In order to increase their own security, they increased their protection. These results illustrate their feelings of insecurity, which may have deleterious effects on work satisfaction and motivation. Trial Registration. Our article does not report the results of a health care intervention on human participants

Challenges and opportunities for an efficiency boost of next generation Cu(In,Ga)Se2 solar cells: prospects for a paradigm shift

Cu(In,Ga)Se2 photovoltaic technology has notably progressed over the past years. Power conversion efficiencies above 23% were reached in spite of the polycrystalline nature of the absorber. Although efficiencies are still far from the practical limits, the material quality is approaching that of III?V compounds that yield the most efficient solar cells. The high carrier lifetime, low open circuit voltage deficit and external radiative efficiency in the single-digit percentage range suggest that the next efficiency boost may arise from the implementation of alternative device architectures. In this perspective paper, we describe the current challenges and pathways to enhance the power conversion efficiency of Cu(In,Ga)Se2 solar cells. Specifically, we suggest the use of non-graded absorbers, integration of charge selective contacts and maximization of photon recycling. We examine these concepts by a semi-empirical device modelling approach, and show that these strategies can lead to efficiencies of 29% under the AM1.5 global spectrum. An analysis of whether or not current state-of-the-art Cu(In,Ga)Se2 solar cells already benefit from photon recycling is also presented.This work received financial support partially from the Swiss State Secretary for Education, Research and Innovation (SERI) under contract number 17.00105 (EMPIR project HyMet) and from the Swiss Federal Office of Energy (SFOE) (SI/501614-01 “ImproCIS”). The EMPIR programme is co-financed by the Participating States and by the European Union's Horizon 2020 research and innovation programme

Current prevalence of self-reported interpersonal violence among adult patients seen at a university hospital emergency department in Switzerland.

To evaluate the current prevalence of self-reported interpersonal violence amongst patients consulting at the emergency department (ED) of a university hospital and to describe the characteristics of the violence sustained. Ours was a cross-sectional study using a modified version of the Partner Violence Screen questionnaire, which was distributed to every patient over 16 years old consulting at the ED between the 1st and 30th September 2016. Excluded were those incapable of decision-making, unable to understand owing to language difficulties, or in police detention. Questions pertained to violence endured during the year prior to their attendance at the ED and, where relevant, the date, place, and type of violence (physical or psychological), the perpetrator and the means used (firearms or other weapons). Demographic details were taken from the hospital records. Of 628 patients included (participation rate 86%), 19% were victims of violence, for 27% of whom it was the motive for ED attendance. The median age of these victims of violence was 28 years (interquartile range 22–43), 39% were female, 71% single and 38% foreign nationals. Typical characteristics of self-reported violence were: (1) violence sustained within the previous 24 h (26%); (2) perpetrators unknown (35%); (3) occurrence at a café, bar, restaurant or nightclub (32%); (4) use of knives (19%); (5) prior consumption of alcohol by the victims themselves (28%). Females were more susceptible to domestic violence than males (45 vs 7%), the latter mostly reporting public violence (64 vs 43% in women). The prevalence of self-reported interpersonal violence has reached one patient in five in our ED. Our results underline the importance of screening for this, as well as providing the means to offer specific follow-up. &nbsp

Charge carrier lifetime fluctuations and performance evaluation of Cu(In,Ga)Se2 absorbers via time-resolved-photoluminescence microscopy

The open-circuit voltage (VOC) is the main limitation to higher efficiencies of Cu(In,Ga)Se2 solar cells. One of the most critical parameters directly affecting VOC is the charge carrier lifetime. Therefore, it is essential to evaluate the extent to which inhomogeneities in material properties limit the carrier lifetime and how postdeposition treatments (PDTs) and growth conditions affect material properties. Time-resolved photoluminescence (TRPL) microscopy is employed at conditions similar to one sun to study carrier lifetime fluctuations in Cu(In,Ga)Se2 with light (Na) and heavy (Rb) alkalis, different substrates, and grown at different temperatures. PDT lowers the amplitude of minority carrier lifetime fluctuations, especially for Rb-treated samples. Upon PDT, the grains’ carrier lifetime increases, and the analysis suggests a reduction in grain boundary recombination. Furthermore, lifetime fluctuations have a small impact on device performance, whereas VOC calculated from TRPL (and continuous-wave PL) agrees with device values within the limits of investigated PDT samples. Finally, up to about half a per cent external radiative efficiencies are experimentally determined from TRPL metrics, and internal radiative efficiencies are approximated. The findings demonstrate that the highest absorber material quality investigated is still limited by nonradiative recombination (grain or grain boundary) and is comparable to state-of-the-art absorbers.This work received financial support in part from the Swiss State Secretary for Education, Research and Innovation (SERI) under Contract No. 17.00105 (EMPIR project HyMet) and from the Swiss Federal Office of Energy (SFOE) (SI/501614-01 ‘‘ImproCIS''). The EMPIR programme was cofinanced by the Participating States and by the European Union's Horizon 2020 research and innovation programme

Lateral charge carrier transport in Cu(In,Ga)Se2 studied by time-resolved photoluminescence mapping

Electronic transport in a semiconductor is key for the development of more efficient devices. In particular, the electronic transport parameters carrier lifetime and mobility are of paramount importance for the modeling, characterization, and development of new designs for solar cells and optoelectronic devices. Herein, time-resolved photoluminescence mapping under low injection and wide-field illumination conditions is used to measure the carrier lifetime and analyze the lateral charge carrier transport in Cu(In,Ga)Se2 absorbers grown at different temperatures, on different substrates, and subject to different postdeposition treatments (PDT) with light or heavy alkalis. To estimate the carrier mobility, numerical simulations of carrier diffusion transport to areas of increased recombination (defects) are used, similarly as observed experimentally. Mobilities are found in the range of 10–50 cm2 V−1 s−1, and effective minority carrier lifetime between 100 and 800 ns resulting in carrier diffusion lengths of 2–9 μm depending on the sample. Finally, the factors limiting carrier mobility and the implications of carrier diffusion on the measured carrier lifetimes are discussed.This work received financial support partially from the Swiss State Secretary for Education, Research and Innovation (SERI) under contract number 17.00105 (EMPIR project HyMet) and from the Swiss Federal Office of Energy (SFOE) (SI/501614-01 ‘‘ImproCIS’’). The EMPIR program was cofinanced by the Participating States and by the European Union's Horizon 2020 research and innovation program

Influence of Ga back grading on voltage loss in low-temperature co-evaporated Cu(In,Ga)Se2 thin film solar cells

The performance of Cu(In,Ga)Se2 (CIGS) solar cells is limited by the presence of the highly recombinative CIGS/Mo interface. The recombination at the CIGS/Mo interface is influential for the open circuit voltage (VOC) in high quality CIGS absorbers with increased charge carriers diffusion length. A quantitative understanding of the role of the Ga back grading height (ΔGGI) in suppressing back interface recombination is needed. In this work, we take advantage of a low temperature process to modify the ΔGGI while keeping the composition in the notch and front regions almost unchanged. Improvement in both VOC deficit and time-resolved photoluminescence lifetime are observed with increasing ΔGGI. With a combination of back surface modification experiments and numerical simulations, we quantify a voltage loss in ungraded devices of approximately 100 mV solely from the back interface recombination. Nice agreement between simulation and experimental data is reached while constraining the values of possible diffusion lengths. Our results suggest that a ΔGGI of about 0.50 is required to effectively suppress the back interface recombination, highlighting the importance of grading control in high-performance CIGS solar cells and devices.Bundesamt für Energie, Grant/Award Number: SI/501614-01; Horizon 2020 Framework Programme, Grant/Award Number: EMPIR project HyMet; Swiss State Secretary for Education, Research and Innovation (SERI), Grant/Award Number: 17.00105 (EMPIR project HyMet

Impact of RbF and NaF postdeposition treatments on charge carrier transport and recombination in Ga-graded Cu(In,Ga)Se2 solar cells

Two key strategies for enhancing the efficiency of Cu(In,Ga)Se2 solar cells are the bandgap gradient across the absorber and the incorporation of alkali atoms. The combined incorporation of Na and Rb into the absorber has brought large efficiency gains compared to Na-containing or alkali-free layers. Here, transient absorption spectroscopy is employed to study the effect of NaF or combined NaF+RbF postdeposition treatments (PDT) on minority carrier dynamics in different excitation volumes of typical composition-graded Cu(In,Ga)Se2 solar cells. Electron lifetimes are found to be highly dependent on the film composition and morphology, varying from tens of nanoseconds in the energy notch to only ≈100 ps in the Ga-rich region near the Mo-back contact. NaF PDT improves recombination lifetimes by a factor of 2–2.5 in all regions of the absorber, whereas the effectiveness of the RbF PDT is found to decrease for higher Ga-concentrations. Electron mobility measured in the absorber region with large grains is promoted by both alkali PDTs. The data suggest that NaF PDT passivates shallow defect states (Urbach tail) throughout the Cu(In,Ga)Se2 film (including the interior of large grains), whereas the additional RbF PDT is effective at grain boundary surfaces (predominantly in regions with medium to low Ga-concentrations).Y.-H.C. thanks the Ministry of Education of Taiwan for her Ph.D. scholarship, Dr. Michael Sachs, and Dr. Carlota Bozal-Ginesta from Imperial College London for the fruitful discussions and aid on TA data. J.R.D. would like to thank the UKRI Global Challenge Research Fund project SUNRISE (EP/P032591/1). L.S. acknowledges funding from the European Research Council (H2020-MSCA-IF-2016, Grant No. 749231). This work also received financial support partially from the Swiss State Secretary for Education, Research and Innovation (SERI) under contract number 17.00105 (EMPIR project HyMet). The EMPIR programme is co-financed by the Participating States and by the European Union's Horizon 2020 research and innovation programme

Insights from transient absorption spectroscopy into electron dynamics along the Ga-gradient in Cu(In,Ga)Se2 solar cells

Cu(In,Ga)Se2 solar cells have markedly increased their efficiency over the last decades currently reaching a record power conversion efficiency of 23.3%. Key aspects to this efficiency progress are the engineered bandgap gradient profile across the absorber depth, along with controlled incorporation of alkali atoms via post-deposition treatments. Whereas the impact of these treatments on the carrier lifetime has been extensively studied in ungraded Cu(In,Ga)Se2 films, the role of the Ga-gradient on carrier mobility has been less explored. Here, transient absorption spectroscopy (TAS) is utilized to investigate the impact of the Ga-gradient profile on charge carrier dynamics. Minority carriers excited in large Cu(In,Ga)Se2 grains with a [Ga]/([Ga]+[In]) ratio between 0.2–0.5 are found to drift-diffuse across ≈1/3 of the absorber layer to the engineered bandgap minimum within 2 ns, which corresponds to a mobility range of 8.7–58.9 cm2 V−1 s−1. In addition, the recombination times strongly depend on the Ga-content, ranging from 19.1 ns in the energy minimum to 85 ps in the high Ga-content region near the Mo-back contact. An analytical model, as well as drift-diffusion numerical simulations, fully decouple carrier transport and recombination behaviour in this complex composition-graded absorber structure, demonstrating the potential of TAS.Y.-H.C. Chang thanks the Ministry of Education of Taiwan for her Ph.D. scholarship, and Dr. Michael Sachs for fruitful discussions on TA data. J.R.D. would like to thank the UKRI Global Challenge Research Fund project SUNRISE (EP/P032591/1). L.S. acknowledges funding from the European Research Council (H2020-MSCA-IF-2016, Grant No. 749231). This work received financial support from the Swiss State Secretary for Education, Research and Innovation (SERI) under contract number 17.00105 (EMPIR project HyMet). The EMPIR programme is co-financed by the Participating States and by the European Union’s Horizon 2020 research and innovation programme

Silver-promoted high-performance (Ag,Cu)(In,Ga)Se2 thin-film solar cells grown at very low temperature

Achieving high power conversion efficiencies with Cu(In,Ga)Se2 (CIGS) solar cells grown at low temperature is challenging because of insufficient thermal energy for grain growth and defect annihilation, resulting in poor crystallinity, higher defect concentration, and degraded device performance. Herein, the possibilities for high-performing devices produced at very low temperatures (≤450 °C) are explored. By alloying CIGS with Ag by the precursor layer method, (Ag,Cu)(In,Ga)Se2 (ACIGS) solar cells grown at about 450 °C reach an efficiency of 20.1%. Only a small efficiency degradation (0.5% and 1.6% absolute) is observed for ACIGS absorbers deposited at 60 and 110 °C lower substrate temperature. CIGS devices exhibit a stronger efficiency degradation, driven by a decrease in the open-circuit voltage (Voc). The root cause of the Voc difference between ACIGS and CIGS devices is investigated by advanced characterization techniques, which show improved morphology, reduced tail states, and higher doping density in ACIGS absorbers. The proposed approach offers several benefits in view of depositions on temperature-sensitive substrates. Increased Cu diffusion promoted by Ag allows end-point detection in the three-stage process at the substrate temperatures below 300 °C. The modified process requires minimal modification of existing processes and equipment and shows the potential for the use of different flexible substrates and device architectures.This work received funding from the Swiss Federal Office of Energy (SFOE) under ImproCIS project (Contract no.: SI/501614-01) and from the Swiss State Secretary for Education, Research and Innovation (SERI) under contract number 17.00105 (EMPIR project HyMet). The EMPIR programme is co-financed by the participating States and by the European Union’s Horizon 2020 research and innovation programme under grant agreement No 850937. X.S. acknowledges funding from the ETH Zurich Postdoctoral Fellowship. M.K. acknowledges funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement No 850937. J.S. acknowledges funding from the Swiss National Science Foundation (grant number 200021_172764)