Isolating the photovoltaic junction: atomic layer deposited TiO2-RuO2 alloy Schottky contacts for silicon photoanodes

We synthesized nanoscale TiO2-RuO2 alloys by atomic layer deposition (ALD) that possess a high work function and are highly conductive. As such, they function as good Schottky contacts to extract photogenerated holes from n-type silicon while simultaneously interfacing with water oxidation catalysts. The ratio of TiO2 to RuO2 can be precisely controlled by the number of ALD cycles for each precursor. Increasing the composition above 16% Ru sets the electronic conductivity and the metal work function. No significant Ohmic loss for hole transport is measured as film thickness increases from 3 to 45 nm for alloy compositions >= 16% Ru. Silicon photoanodes with a 2 nm SiO2 layer that are coated by these alloy Schottky contacts having compositions in the range of 13-46% Ru exhibit average photovoltages of 525 mV, with a maximum photovoltage of 570 mV achieved. Depositing TiO2-RuO2 alloys on nSi sets a high effective work function for the Schottky junction with the semiconductor substrate, thus generating a large photovoltage that is isolated from the properties of an overlying oxygen evolution catalyst or protection layer

Design principles for maximizing photovoltage in metal-oxide-protected water-splitting photoanodes

Metal oxide protection layers for photoanodes may enable the development of large-scale solar fuel and solar chemical synthesis, but the poor photovoltages often reported so far will severely limit their performance. Here we report a novel observation of photovoltage loss associated with a charge extraction barrier imposed by the protection layer, and, by eliminating it, achieve photovoltages as high as 630mV, the maximum reported so far for water-splitting silicon photoanodes. The loss mechanism is systematically probed in metal-insulator-semiconductor Schottky junction cells compared to buried junction p(+) n cells, revealing the need to maintain a characteristic hole density at the semiconductor/insulator interface. A leaky-capacitor model related to the dielectric properties of the protective oxide explains this loss, achieving excellent agreement with the data. From these findings, we formulate design principles for simultaneous optimization of built-in field, interface quality, and hole extraction to maximize the photovoltage of oxide-protected water-splitting anodes

CARBON AND OXYGEN ISOTOPIC ANALYSIS: BUG, CHEROKEE, AND PATTERSON CANYON FIELDS, SAN JUAN COUNTY, UTAH

Over 400 million barrels (64 million m{sup 3}) of oil have been produced from the shallow-shelf carbonate reservoirs in the Pennsylvanian (Desmoinesian) Paradox Formation in the Paradox Basin, Utah and Colorado. With the exception of the giant Greater Aneth field, the other 100 plus oil fields in the basin typically contain 2 to 10 million barrels (0.3-1.6 million m{sup 3}) of original oil in place. Most of these fields are characterized by high initial production rates followed by a very short productive life (primary), and hence premature abandonment. Only 15 to 25 percent of the original oil in place is recoverable during primary production from conventional vertical wells. An extensive and successful horizontal drilling program has been conducted in the giant Greater Aneth field. However, to date, only two horizontal wells have been drilled in small Ismay and Desert Creek fields. The results from these wells were disappointing due to poor understanding of the carbonate facies and diagenetic fabrics that create reservoir heterogeneity. These small fields, and similar fields in the basin, are at high risk of premature abandonment. At least 200 million barrels (31.8 million m{sup 3}) of oil will be left behind in these small fields because current development practices leave compartments of the heterogeneous reservoirs undrained. Through proper geological evaluation of the reservoirs, production may be increased by 20 to 50 percent through the drilling of low-cost single or multilateral horizontal legs from existing vertical development wells. In addition, horizontal drilling from existing wells minimizes surface disturbances and costs for field development, particularly in the environmentally sensitive areas of southeastern Utah and southwestern Colorado

Engineering interfacial silicon dioxide for improved metal-insulator-semiconductor silicon photoanode water splitting performance

Silicon photoanodes protected by atomic layer deposited (ALD) TiO2 show promise as components of water splitting devices that may enable the large-scale production of solar fuels and chemicals. Minimizing the resistance of the oxide corrosion protection layer is essential for fabricating efficient devices with good fill factor. Recent literature reports have shown that the interfacial SiO2 layer, interposed between the protective ALD-TiO2 and the Si anode, acts as a tunnel oxide that limits hole conduction from the photoabsorbing substrate to the surface oxygen evolution catalyst. Herein, we report a significant reduction of bilayer resistance, achieved by forming stable, ultrathin (<1.3 nm) SiO2 layers, allowing fabrication of water splitting photoanodes with hole conductances near the maximum achievable with the given catalyst and Si substrate. Three methods for controlling the SiO2 interlayer thickness on the Si(100) surface for ALD-TiO2 protected anodes were employed: (1) TiO2 deposition directly on an HF-etched Si(100) surface, (2) TiO2 deposition after SiO2 atomic layer deposition on an HF-etched Si(100) surface, and (3) oxygen scavenging, post-TiO2 deposition to decompose the SiO2 layer using a Ti overlayer. Each of these methods provides a progressively superior means of reliably thinning the interfacial SiO2 layer, enabling the fabrication of efficient and stable water oxidation silicon anodes

Field and chirality effects on electrochemical charge transfer rates: Spin dependent electrochemistry

This work examines whether electrochemical redox reactions are sensitive to the electron spin orientation by examining the effects of magnetic field and molecular chirality on the charge transfer process. The working electrode is either a ferromagnetic nickel film or a nickel film that is coated with an ultrathin (5\u201330 nm) gold overlayer. The electrode is coated with a self-assembled monolayer that immobilizes a redox couple containing chiral molecular units, either the redox active dye toluidine blue O with a chiral cysteine linking unit or cytochrome c. By varying the direction of magnetization of the nickel, toward or away from the adsorbed layer, we demonstrate that the electrochemical current depends on the orientation of the electrons\u2019 spin. In the case of cytochrome c, the spin selectivity of the reduction is extremely high, namely, the reduction occurs mainly with electrons having their spin-aligned antiparallel to their velocity

Understanding resonant charge transport through weakly coupled single-molecule junctions

Off-resonant charge transport through molecular junctions has been extensively studied since the advent of single-molecule electronics and it is now well understood within the framework of the non-interacting Landauer approach. Conversely, gaining a qualitative and quantitative understanding of the resonant transport regime has proven more elusive. Here, we study resonant charge transport through graphene-based zinc-porphyrin junctions. We experimentally demonstrate an inadequacy of the non-interacting Landauer theory as well as the conventional single-mode Franck-Condon model. Instead, we model the overall charge transport as a sequence of non-adiabatic electron transfers, the rates of which depend on both outer and inner-sphere vibrational interactions. We show that the transport properties of our molecular junctions are determined by a combination of electron-electron and electron-vibrational coupling, and are sensitive to the interactions with the wider local environment. Furthermore, we assess the importance of nuclear tunnelling and examine the suitability of semi-classical Marcus theory as a description of charge transport in molecular devices.Comment: version accepted in Nature Communications; SI available at https://researchportal.hw.ac.uk/en/publications/understanding-resonant-charge-transport-through-weakly-coupled-s

Assessment and intervention issues and models in School Psychology : the case of Europe and North America

As práticas da Psicologia Escolar parecem ser cada vez mais marcadas pelas necessidades de referenciação/diagnóstico de crianças para o subsistema de educação especial, em detrimento do desenho e implementação de intervenções dirigidas aos problemas específicos dos alunos. A aparente insatisfação dos psicólogos escolares com essa tendência, bem como as dificuldades na utilização de modelos categoriais de diagnóstico em contexto escolar, têm dado origem à progressiva implementação de modelos alternativos de avaliação e intervenção, principalmente de modelos Response to Intervention, Curriculum-Based Measurement e Problem Solving. A controvérsia quanto à natureza verdadeiramente alternativa desses modelos parece, no entanto, longe de se esgotar. Neste artigo são discutidas vantagens e limitações dos diferentes modelos, de acordo com a melhor evidência disponível na literatura, e são ainda equacionadas as suas implicações nas práticas da Psicologia Escolar. Practices in School Psychology seem to be increasingly restricted to referrals/diagnosis of children for the sub-system of special education instead of being focused on the design and implementation of interventions for students with specific problems. The apparent dissatisfaction of school psychologists with this trend and the difficulties dealing with categorical diagnostic models within the school context have stimulated a movement toward the implementation of alternative assessment and intervention models, such as Response to Intervention, Curriculum-Based Measurement and Problem-Solving. However, the controversy about the true alternative nature of these models seems far from being exhausted. The aim of this paper is to discuss the benefits and limitations of the different models according to the best evidence available. We also consider the implications for practices in School PsychologyPractices in School Psychology seem to be increasingly restricted to referrals/diagnosis of children for the sub-system of special education instead of being focused on the design and implementation of interventions for students with specific problems. The apparent dissatisfaction of school psychologists with this trend and the difficulties dealing with categorical diagnostic models within the school context have stimulated a movement toward the implementation of alternative assessment and intervention models, such as Response to Intervention, Curriculum-Based Measurement and Problem-Solving. However, the controversy about the true alternative nature of these models seems far from being exhausted. The aim of this paper is to discuss the benefits and limitations of the different models according to the best evidence available. We also consider the implications for practices in School Psychology(undefined

Weak temperature dependence of P (+) H A (-) recombination in mutant Rhodobacter sphaeroides reaction centers

International audienceIn contrast with findings on the wild-type Rhodobacter sphaeroides reaction center, biexponential P (+) H A (-) → PH A charge recombination is shown to be weakly dependent on temperature between 78 and 298 K in three variants with single amino acids exchanged in the vicinity of primary electron acceptors. These mutated reaction centers have diverse overall kinetics of charge recombination, spanning an average lifetime from ~2 to ~20 ns. Despite these differences a protein relaxation model applied previously to wild-type reaction centers was successfully used to relate the observed kinetics to the temporal evolution of the free energy level of the state P (+) H A (-) relative to P (+) B A (-) . We conclude that the observed variety in the kinetics of charge recombination, together with their weak temperature dependence, is caused by a combination of factors that are each affected to a different extent by the point mutations in a particular mutant complex. These are as follows: (1) the initial free energy gap between the states P (+) B A (-) and P (+) H A (-) , (2) the intrinsic rate of P (+) B A (-) → PB A charge recombination, and (3) the rate of protein relaxation in response to the appearance of the charge separated states. In the case of a mutant which displays rapid P (+) H A (-) recombination (ELL), most of this recombination occurs in an unrelaxed protein in which P (+) B A (-) and P (+) H A (-) are almost isoenergetic. In contrast, in a mutant in which P (+) H A (-) recombination is relatively slow (GML), most of the recombination occurs in a relaxed protein in which P (+) H A (-) is much lower in energy than P (+) H A (-) . The weak temperature dependence in the ELL reaction center and a YLH mutant was modeled in two ways: (1) by assuming that the initial P (+) B A (-) and P (+) H A (-) states in an unrelaxed protein are isoenergetic, whereas the final free energy gap between these states following the protein relaxation is large (~250 meV or more), independent of temperature and (2) by assuming that the initial and final free energy gaps between P (+) B A (-) and P (+) H A (-) are moderate and temperature dependent. In the case of the GML mutant, it was concluded that the free energy gap between P (+) B A (-) and P (+) H A (-) is large at all times