Deep electron and hole polarons and bipolarons in amorphous oxide

Amorphous (a)-HfO2 is a prototype high dielectric constant insulator with wide technological applications. Using ab initio calculations we show that excess electrons and holes can trap in a-HfO2 in energetically much deeper polaron states than in the crystalline monoclinic phase. The electrons and holes localize at precursor sites, such as elongated Hf-O bonds or undercoordinated Hf and O atoms, and the polaronic relaxation is amplified by the local disorder of amorphous network. Single electron polarons produce states in the gap at ∼2 eV below the bottom of the conduction band with average trapping energies of 1.0 eV. Two electrons can form even deeper bipolaron states on the same site. Holes are typically localized on undercoordinated O ions with average trapping energies of 1.4 eV. These results advance our general understanding of charge trapping in amorphous oxides by demonstrating that deep polaron states are inherent and do not require any bond rupture to form precursor sites

Intrinsic Charge Trapping in Amorphous Oxide Films: Status and Challenges

We review the current understanding of intrinsic electron and hole trapping in insulating amorphous oxide films on semiconductor and metal substrates. The experimental and theoretical evidences are provided for the existence of intrinsic deep electron and hole trap states caused by the disorder of amorphous metal oxide films. We start from presenting the results for amorphous (a) HfO<sub>2</sub>, chosen due to the availability of highest purity amorphous films, which is vital for studying their intrinsic electronic properties. Exhaustive photo-depopulation spectroscopy (EPDS) measurements and theoretical calculations using density functional theory (DFT) shed light on the atomic nature of electronic gap states responsible for deep electron trapping observed in a-HfO<sub>2</sub>. We review theoretical methods used for creating models of amorphous structures and electronic structure calculations of amorphous oxides and outline some of the challenges in modelling defects in amorphous materials. We then discuss theoretical models of electron polarons and bi-polarons in a-HfO<sub>2</sub> and demonstrate that these intrinsic states originate from low-coordinated ions and elongated metal-oxygen bonds in the amorphous oxide network. Similarly, holes can be captured at under-coordinated O sites. We then discuss electron and hole trapping in other amorphous oxides, such as a-SiO<sub>2</sub>, a-Al<sub>2</sub>O<sub>3</sub>, a-TiO<sub>2</sub>. We propose that the presence of low-coordinated ions in amorphous oxides with electron states of significant p and d character near the conduction band minimum (CBM) can lead to electron trapping and that deep hole trapping should be common to all amorphous oxides. Finally, we demonstrate that bi-electron trapping in a-HfO<sub>2</sub> and a-SiO<sub>2</sub> weakens Hf(Si)-O bonds and significantly reduces barriers for forming Frenkel defects, neutral O vacancies and O<sup>2-</sup> ions in these materials. These results should be useful for better understanding of electronic properties and structural evolution of thin amorphous films under carrier injection conditions

Electron trapping in ferroelectric HfO2

Charge trapping study at 300 and 77 K in ferroelectric (annealed Al- or Si-doped) and nonferroelectric (unannealed and/or undoped) HfO 2 films grown by atomic layer deposition reveals the presence of “deep” and “shallow” electron traps with volume concentrations in the 10 19 − cm − 3 range. The concentration of deep traps responsible for electron trapping at 300 K is virtually insensitive to the oxide doping by Al or Si but slightly decreases in films crystallized by high-temperature annealing in oxygen-free ambient. This behavior indicates that the trapping sites are intrinsic and probably related to disorder in HfO 2 rather than to the oxygen deficiency of the film. Electron injection at 77 K allowed us to fill shallow electron traps energetically distributed at ∼0.2 eV. These electrons are mobile and populate states with thermal ionization energies in the range ∼0.6–0.7 eV below the HfO 2 conduction band (CB). The trap energy depth and marginal sensitivity of their concentration to crystallization annealing or film doping with Si or Al suggests that these traps are associated with boundaries between crystalline grains and interfaces between crystalline and amorphous regions in HfO 2 films. This hypothesis is supported by density functional theory calculations of electron trapping at surfaces of monoclinic, tetragonal, and orthorhombic phases of HfO 2 . The calculated trap states are consistent with the observed thermal ionization (0.7–1.0 eV below the HfO 2 CB) and photoionization energies (in the range of 2.0–3.5 eV below the HfO 2 CB) and support their intrinsic polaronic nature

Improved measurement of the K+->pi+nu(nu)over-bar branching ratio

An additional event near the upper kinematic limit for K+-->pi(+)nu(nu) over bar has been observed by experiment E949 at Brookhaven National Laboratory. Combining previously reported and new data, the branching ratio is B(K+-->pi(+)nu(nu) over bar)=(1.47(-0.89)(+1.30))x10(-10) based on three events observed in the pion momentum region 211<P<229 MeV/c. At the measured central value of the branching ratio, the additional event had a signal-to-background ratio of 0.9

Intrinsic electron trapping in amorphous oxide

We demonstrate that electron trapping at intrinsic precursor sites is endemic in non-glass-forming amorphous oxide films. The energy distributions of trapped electron states in ultra-pure prototype amorphous (a)-HfO2 insulator obtained from exhaustive photo-depopulation experiments demonstrate electron states in the energy range of 2–3 eV below the oxide conduction band. These energy distributions are compared to the results of density functional calculations of a-HfO2 models of realistic density. The experimental results can be explained by the presence of intrinsic charge trapping sites formed by under-coordinated Hf cations and elongated Hf–O bonds in a-HfO2. These charge trapping states can capture up to two electrons, forming polarons and bi-polarons. The corresponding trapping sites are different from the dangling-bond type defects responsible for trapping in glass-forming oxides, such as SiO2, in that the traps are formed without bonds being broken. Furthermore, introduction of hydrogen causes formation of somewhat energetically deeper electron traps when a proton is immobilized next to the trapped electron bi-polaron. The proposed novel mechanism of intrinsic charge trapping in a-HfO2 represents a new paradigm for charge trapping in a broad class of non-glass-forming amorphous insulators

Intrinsic electron traps in atomic-layer deposited HfO2 insulators

Analysis of photodepopulation of electron traps in HfO2 films grown by atomic layer deposition is shown to provide the trap energy distribution across the entire oxide bandgap. The presence is revealed of two kinds of deep electron traps energetically distributed at around Et ≈ 2.0 eV and Et ≈ 3.0 eV below the oxide conduction band. Comparison of the trapped electron energy distributions in HfO2 layers prepared using different precursors or subjected to thermal treatment suggests that these centers are intrinsic in origin. However, the common assumption that these would implicate O vacancies cannot explain the charging behavior of HfO2, suggesting that alternative defect models should be considered

Downregulation of Chloroplast RPS1 Negatively Modulates Nuclear Heat-Responsive Expression of HsfA2 and Its Target Genes in Arabidopsis

Heat stress commonly leads to inhibition of photosynthesis in higher plants. The transcriptional induction of heat stress-responsive genes represents the first line of inducible defense against imbalances in cellular homeostasis. Although heat stress transcription factor HsfA2 and its downstream target genes are well studied, the regulatory mechanisms by which HsfA2 is activated in response to heat stress remain elusive. Here, we show that chloroplast ribosomal protein S1 (RPS1) is a heat-responsive protein and functions in protein biosynthesis in chloroplast. Knockdown of RPS1 expression in the rps1 mutant nearly eliminates the heat stress-activated expression of HsfA2 and its target genes, leading to a considerable loss of heat tolerance. We further confirm the relationship existed between the downregulation of RPS1 expression and the loss of heat tolerance by generating RNA interference-transgenic lines of RPS1. Consistent with the notion that the inhibited activation of HsfA2 in response to heat stress in the rps1 mutant causes heat-susceptibility, we further demonstrate that overexpression of HsfA2 with a viral promoter leads to constitutive expressions of its target genes in the rps1 mutant, which is sufficient to reestablish lost heat tolerance and recovers heat-susceptible thylakoid stability to wild-type levels. Our findings reveal a heat-responsive retrograde pathway in which chloroplast translation capacity is a critical factor in heat-responsive activation of HsfA2 and its target genes required for cellular homeostasis under heat stress. Thus, RPS1 is an essential yet previously unknown determinant involved in retrograde activation of heat stress responses in higher plants

Frequently asked questions about chlorophyll fluorescence, the sequel

[EN] Using chlorophyll (Chl) a fluorescence many aspects of the photosynthetic apparatus can be studied, both in vitro and, noninvasively, in vivo. Complementary techniques can help to interpret changes in the Chl a fluorescence kinetics. Kalaji et al. (Photosynth Res 122: 121-158, 2014a) addressed several questions about instruments, methods and applications based on Chl a fluorescence. Here, additionalChl a fluorescence-related topics are discussed again in a question and answer format. 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Biochim Biophys Acta 1553:302–308Debus RJ (1992) The manganese and calcium ions of photosynthetic oxygen evolution. Biochim Biophys Acta 1102:269–352Degl’Innocenti E, Guidi L, Soldatini GF (2002) Characteriz

Equitable representation in councils: theory and an application to the United Nations Security Council

We analyze democratic equity in council voting games (CVGs). In a CVG, a voting body containing all members delegates decision-making to a (time-varying) subset of its members, as describes, e.g., the relationship between the United Nations General Assembly and the United Nations Security Council (UNSC). We develop a theoretical framework for analyzing democratic equitability in CVGs at both the country and region levels, and for different assumptions regarding preference correlation. We apply the framework to evaluate the equitability of the UNSC, and the claims of those who seek to reform it. We find that the individual permanent members are overrepresented by between 21.3 times (United Kingdom) and 3.8 times (China) from a country-level perspective, while from a region perspective Eastern Europe is the most heavily overrepresented region with more than twice its equitable representation, and Africa the most heavily underrepresented. Our equity measures do not preclude some UNSC members from exercising veto rights, however

Interactive effects of pressurized ventilation, water depth and substrate conditions on Phragmites australis

Pressurized ventilation acts to increase the oxygen supply to roots and rhizomes in some species of emergent plants. In a greenhouse experiment, we investigated how pressurized ventilation affected growth, biomass allocation and mineral content of Phragmites australis in two water depths (15 cm or 75 cm) and two substrates (organic sediment or sand). Through perforating each stem above the water surface, pressurized ventilation was inhibited without affecting oxygen diffusion. In controls, 10-20% of the stems were perforated to make certain that lack of efflux sites would not limit pressurized ventilation. Plants with inhibited pressurized ventilation had lower oxygen concentrations in their stem bases than control plants. Growth was lower in plants with inhibited pressurized ventilation compared to controls except when plants grew in a combination of sand and shallow water. In plants grown in an organic sediment, but not in those grown in sand, inhibition of pressurized ventilation resulted in decreased biomass allocation to soil roots but increased allocation to aquatic roots. Stem perforation affected the tissue concentrations of nitrogen, phosphorus, magnesium, manganese and aluminium but not of calcium or iron. We suggest that the lower growth in plants with inhibited pressurized ventilation was caused by decreased mineral uptake, which may have resulted from the decreased proportional allocation to soil root weight, from decreased mineral availability or from impaired root function. In plants grown in sand in shallow water, diffusion seemed to cover the oxygen demand, as pressurized ventilation did not affect growth