The interfacial structure of InP(100) in contact with HCl and H2SO4 studied by reflection anisotropy spectroscopy

Indium phosphide and derived compound semiconductors are materials often involved in high-efficiency solar water splitting due to their versatile opto-electronic properties. Surface corrosion, however, typically deteriorates the performance of photoelectrochemical solar cells based on this material class. It has been reported that (photo)electrochemical surface functionalisation protects the surface by combining etching and controlled corrosion. Nevertheless, the overall involved process is not fully understood. Therefore, access to the electrochemical interface structure under operando conditions is crucial for a more detailed understanding. One approach for gaining structural insight is the use of operando reflection anisotropy spectroscopy. This technique allows the time-resolved investigation of the interfacial structure while applying potentials in the electrolyte. In this study, p-doped InP(100) surfaces are cycled between anodic and cathodic potentials in two different electrolytes, hydrochloric acid and sulphuric acid. For low, 10 mM electrolyte concentrations, we observe a reversible processes related to the reduction of a surface oxide phase in the cathodic potential range which is reformed near open-circuit potentials. Higher concentrations of 0.5 N, however, already lead to initial surface corrosion.Comment: 10 pages, 6 figure

ESD Ideas: Photoelectrochemical carbon removal as negative emission technology

The pace of the transition to a low-carbon economy – especially in the fuels sector – is not high enough to achieve the 2 ∘C target limit for global warming by only cutting emissions. Most political roadmaps to tackle global warming implicitly rely on the timely availability of mature negative emission technologies, which actively invest energy to remove CO2 from the atmosphere and store it permanently. The models used as a basis for decarbonization policies typically assume an implementation of such large-scale negative emission technologies starting around the year 2030, ramped up to cause net negative emissions in the second half of the century and balancing earlier CO2 release. On average, a contribution of −10 Gt CO2 yr−1 is expected by 2050 (Anderson and Peters, 2016). A viable approach for negative emissions should (i) rely on a scalable and sustainable source of energy (solar), (ii) result in a safely storable product, (iii) be highly efficient in terms of water and energy use, to reduce the required land area and competition with water and food demands of a growing world population, and (iv) feature large-scale feasibility and affordability

Efficient direct solar-to-hydrogen conversion by in situ interface transformation of a tandem structure

Photosynthesis is nature’s route to convert intermittent solar irradiation into storable energy, while its use for an industrial energy supply is impaired by low efficiency. Artificial photosynthesis provides a promising alternative for efficient robust carbon-neutral renewable energy generation. The approach of direct hydrogen generation by photoelectrochemical water splitting utilizes customized tandem absorber structures to mimic the Z-scheme of natural photosynthesis. Here a combined chemical surface transformation of a tandem structure and catalyst deposition at ambient temperature yields photocurrents approaching the theoretical limit of the absorber and results in a solar-to-hydrogen efficiency of 14%. The potentiostatically assisted photoelectrode efficiency is 17%. Present benchmarks for integrated systems are clearly exceeded. Details of the in situ interface transformation, the electronic improvement and chemical passivation are presented. The surface functionalization procedure is widely applicable and can be precisely controlled, allowing further developments of high-efficiency robust hydrogen generators

Materials for light-induced water splitting: In situ controlled surface preparation of GaPN epilayers grown lattice-matched on Si(100)

Energy storage is a key challenge in solar-driven renewable energy conversion. We promote a photochemical diode based on dilute nitride GaPN grown lattice-matched on Si(100), which could reach both high photovoltaic efficiencies and evolve hydrogen directly without external bias. Homoepitaxial GaP(100) surface preparation was shown to have a significant impact on the semiconductor-water interface formation. Here, we grow a thin, pseudomorphic GaP nucleation buffer on almost single-domain Si(100) prior to GaPN growth and compare the GaP_(0.98)N_(0.02)/Si(100) surface preparation to established P- and Ga-rich surfaces of GaP/Si(100). We apply reflection anisotropy spectroscopy to study the surface preparation of GaP_(0.98)N_(0.02) in situ in vapor phase epitaxy ambient and benchmark the signals to low energy electron diffraction, photoelectron spectroscopy, and x-ray diffraction. While the preparation of the Ga-rich surface is hardly influenced by the presence of the nitrogen precursor 1,1-dimethylhydrazine (UDMH), we find that stabilization with UDMH after growth hinders well-defined formation of the V-rich GaP_(0.98)N_(0.02)/Si(100) surface. Additional features in the reflection anisotropy spectra are suggested to be related to nitrogen incorporation in the GaP bulk

A Finite Difference Representation of Neutrino Radiation Hydrodynamics in Spherically Symmetric General Relativistic Space-Time

We present an implicit finite difference representation for general relativistic radiation hydrodynamics in spherical symmetry. Our code, Agile-Boltztran, solves the Boltzmann transport equation for the angular and spectral neutrino distribution functions in self-consistent simulations of stellar core collapse and postbounce evolution. It implements a dynamically adaptive grid in comoving coordinates. Most macroscopically interesting physical quantities are defined by expectation values of the distribution function. We optimize the finite differencing of the microscopic transport equation for a consistent evolution of important expectation values. We test our code in simulations launched from progenitor stars with 13 solar masses and 40 solar masses. ~0.5 s after core collapse and bounce, the protoneutron star in the latter case reaches its maximum mass and collapses further to form a black hole. When the hydrostatic gravitational contraction sets in, we find a transient increase in electron flavor neutrino luminosities due to a change in the accretion rate. The muon- and tauon-neutrino luminosities and rms energies, however, continue to rise because previously shock-heated material with a non-degenerate electron gas starts to replace the cool degenerate material at their production site. We demonstrate this by supplementing the concept of neutrinospheres with a more detailed statistical description of the origin of escaping neutrinos. We compare the evolution of the 13 solar mass progenitor star to simulations with the MGFLD approximation, based on a recently developed flux limiter. We find similar results in the postbounce phase and validate this MGFLD approach for the spherically symmetric case with standard input physics.Comment: reformatted to 63 pages, 24 figures, to be published in ApJ

Subcapsular Orchiectomy in the Primary Therapy of Patients with Bone Metastasis in Advanced Prostate Cancer: An Anachronistic Intervention?

Background. The therapeutic impact of palliative androgen deprivation in metastatic prostate cancer is indisputable. Bilateral orchiectomy represents the traditional method of AD but was reduced during the last years in favor for treatment with LHRH analogues. Due to limited economic resources of the health care system, the economically priced definite surgical castration might experience a renaissance. Methods. In this single-center retrospective study, 83 consecutive patients with osseous metastasized prostate cancer were evaluated, who had primarily been treated by subcapsular bilateral orchiectomy. Response to therapy, time until therapy failure, overall survival time, psychological disorders due to loss of organ, and disease-associated and postoperative surgical complications were recorded. The median followup was 35 months (IQR: 26–46). Results. Patients' mean age at surgery was 72.1 (54–91) years. Six patients (7.2%) displayed immediate tumor progression after orchiectomy. Median time of tumor remission and overall survival time were 29 and 36 months, respectively. 14% of the study group showed minor postoperative complications. No psychological problems occurred following bilateral orchiectomy. Conclusion. Due to an effective and persistent oncological effectiveness, less morbidity, and absence of psychological implications, bilateral subcapsular orchiectomy seems to be a practicable and advisable alternative in the first-line therapy of metastasized PCa

Water-induced modifications of GaP(100) and InP(100) surfaces studied by photoelectron spectroscopy and reflection anisotropy spectroscopy

In this work, we investigate the initial interaction of water and oxygen with different surface reconstructions of GaP(100) applying photoelectron spectroscopy, low-energy electron diffraction, and reflection anisotropy spectroscopy. Surfaces were prepared by metal-organic vapour phase epitaxy, transferred to ultra-high vacuum, and exposed to oxygen or water vapour at room temperature. The (2 4) reconstructed, Ga-rich surface is more sensitive and reactive to adsorption, bearing a less ordered surface reconstruction upon exposure and indicating a mixture of dissociative and molecular water adsorption. The p(2 2)=c(4 2) P-rich surface, on the other hand, is less reactive, but shows a new surface symmetry after water adsorption. Correlating findings of photoelectron spectroscopy with reflection anisotropy spectroscopy could pave the way towards optical in-situ monitoring of electrochemical surface modifications with reflection anisotropy spectroscopy