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Chromium contamination is a serious environmental issue in areas affected by leather tanning and metal plating, and green rust sulfate has been tested extensively as a potential material for in situ chemical reduction of hexavalent chromium in groundwater. Reported products and mechanisms for the reaction have varied, most likely because of green rust’s layered structure, as reduction at outer and interlayer surfaces might produce different reaction products with variable stabilities. Based on studies of Cr(III) oxidation by biogenic Mn (IV) oxides, Cr mobility in oxic soils is controlled by the solubility of the Cr(III)-bearing phase. Therefore, careful engineering of green rust properties, i.e., crystal/particle size, morphology, structure, and electron availability, is essential for its optimization as a remediation reagent. In the present study, pure green rust sulfate and green rust sulfate with Al, Mg and Zn substitutions were synthesized and reacted with identical chromate (CrO42−) solutions. The reaction products were characterized by X-ray diffraction, pair distribution function analysis, X-ray absorption spectroscopy and transmission electron microscopy and treated with synthetic δ-MnO2 to assess how easily Cr(III) in the products could be oxidized. It was found that Mg substitution had the most beneficial effect on Cr lability in the product. Less than 2.5% of the Cr(III) present in the reacted Mg-GR was reoxidized by δ-MnO2 within 14 days, and the particle structure and Cr speciation observed during X-ray scattering and absorption analyses of this product suggested that Cr(VI) was reduced in its interlayer. Reduction in the interlayer lead to the linkage of newly-formed Cr(III) to hydroxyl groups in the adjacent octahedral layers, which resulted in increased structural coherency between these layers, distinctive rim domains, sequestration of Cr(III) in insoluble Fe oxide bonding environments resistant to reoxidation and partial transformation to Cr(III)-substituted feroxyhyte. Based on the results of this study of hexavalent chromium reduction by green rust sulfate and other studies, further improvements can also be made to this remediation technique by reacting chromate with a large excess of green rust sulfate, which provides excess Fe(II) that can catalyze transformation to more crystalline iron oxides, and synthesis of the reactant under alkaline conditions, which has been shown to favor chromium reduction in the interlayer of Fe(II)-bearing phyllosilicates.

The inelastic background of hard x-ray photoelectron spectroscopy data is analyzed to paint a depth-resolved picture of the CdS/Cu(In,Ga)Se2 (CdS/CIGSe) layer structure. The CdS/CIGSe interface is the central component in next-generation chalcopyrite thin-film photovoltaic devices. By analyzing both, the (unscattered) core-level peaks and the inelastic background, and by varying the excitation photon energy from 2.1 up to 14 keV, we can derive photoemission information over a broad range of electron kinetic energies and, hence, sampling depths. With this complementary information, the CdS film thickness of a CdS/CIGSe interface can be accurately determined as a function of the CdS deposition time. For the thinner CdS films, the film thickness can be shown to vary laterally. Furthermore, small amounts of Se and process-related Rb can be detected in a thin (∼2 nm) surface layer of all investigated CdS films.

Hackmanites, a variety of sodalite with the general formula Na$_{8}$Al$_{6}$Si$_{6}$O$_{24}$(Cl,S)$_{2}$, are a family of nature-based smart materials having the ability for reversible photochromism upon UV or X-ray exposure. Being nontoxic, cheap, and durable, hackmanite would be an optimal material for the visual detection of the presence of X-rays in simple portable systems. However, its X-ray-induced coloring abilities are so far known only qualitatively. In this work, a combination of experimental and computational methods is used to reveal the mechanism of X-ray-induced color changing in these materials. Finally, their use is demonstrated both in color intensity-based X-ray dosimetry and photochromic X-ray imaging.

The electronic structures of four precursors for organic���inorganic hybrid perovskites, namely, methylammonium chloride and iodide, as well as formamidinium bromide and iodide, are investigated by X-ray emission (XE) spectroscopy at the carbon and nitrogen K-edges. The XE spectra are analyzed based on density functional theory calculations. We simulate the XE spectra at the Kohn���Sham level for ground-state geometries and carry out detailed analyses of the molecular orbitals and the electronic density of states to give a thorough understanding of the spectra. Major parts of the spectra can be described by the model of the corresponding isolated organic cation, whereas high-emission energy peaks in the nitrogen K-edge XE spectra arise from electronic transitions involving hybrids of the molecular and atomic orbitals of the cations and halides, respectively. We find that the interaction of the methylammonium cation is stronger with the chlorine than with the iodine anion. Furthermore, our detailed theoretical analysis highlights the strong influence of ultrafast proton dynamics in the core-excited states, which is an intrinsic effect of the XE process. The inclusion of this effect is necessary for an accurate description of the experimental nitrogen K-edge X-ray emission spectra and gives information on the hydrogen-bonding strengths in the different precursor materials.

Among all iron oxides, hematite (α-Fe2O3), goethite (α-FeOOH), and ferrihydrite (FeOOH⋅nH2O) are the most common mineral species. While immobilization of Mo6+ by surface adsorption on ferric oxides has been studied extensively, the mechanisms of incorporation in their structure have been researched little. The objective of this study was to investigate the relation between Mo content and its structural incorporation in hematite, goethite, and six-line ferrihydrite by a combination of X-ray absorption spectroscopy (XAS), powder X-ray diffraction (pXRD), and inductively-coupled plasma optical emission spectrometry (ICP-OES). Synthesized in the presence of Mo, the hematite, goethite, and six-line ferrihydrite phases incorporated up to 8.52, 0.03, and 17.49 wt. % Mo, respectively. For hematite and goethite, pXRD analyses did not indicate the presence of separate Mo phases. Refined unit-cell parameters correlated with increasing Mo concentration in hematite and goethite. The unit-cell parameters indicated an increase in structural disorder within both phases and, therefore, supported the structural incorporation of Mo in hematite and goethite. Analysis of pXRD measurements of Mo-bearing six-line ferrihydrites revealed small amounts of coprecipitated akaganéite. X-ray absorption near edge structure (XANES) measurements at the Mo L3-edge indicated a strong distortion of the MoO6 octahedra in all three phases. Fitting of extended X-ray absorption fine structure (EXAFS) spectra of the Mo K-edge supported the presence of such distorted octahedra in a coordination environment similar to the Fe position in the investigated specimen. Incorporation of Mo6+ at the Fe3+-position for both hematite and goethite resulted in the formation of one Fe vacancy in close proximity to the newly incorporated Mo6+ and, therefore, charge balance within the hematite and goethite structures.

Physical review / B 102(19), 195414 (1-9) (2020). doi:10.1103/PhysRevB.102.195414, Self-organized silicide nanowires are considered as building blocks of future nanoelectronics and have been intensively investigated. In nanostructures, the lattice vibrational waves (phonons) deviate drastically from those in bulk crystals, which gives rise to anomalies in thermodynamic, elastic, electronic, and magnetic properties. Hence a thorough understanding of the physical properties of these materials requires a comprehensive investigation of the lattice dynamics as a function of the nanowire size. We performed a systematic lattice dynamics study of endotaxial FeSi$_2$ nanowires, forming the metastable, surface-stabilized $\alpha$ phase, which are in-plane embedded into the Si(110) surface. The average widths of the nanowires ranged from 24 to 3 nm, and their lengths ranged from several micrometers to about 100 nm. The Fe-partial phonon density of states, obtained by nuclear inelastic scattering, exhibits a broadening of the spectral features with decreasing nanowire width. The experimental data obtained along and across the nanowires unveiled a pronounced vibrational anisotropy that originates from the specific orientation of the tetragonal $\alpha$−FeSi$_2$ unit cell on the Si(110) surface. The results from first-principles calculations are fully consistent with the experimental observations and allow for a comprehensive understanding of the lattice dynamics of endotaxial silicide nanowires., Published by Inst., Woodbury, NY

The phase purity of a series of ZnAl 4(OH) 12SO 4· nH 2O layered double hydroxides (ZnAl 4-LDH) obtained from a reaction of bayerite (Al(OH) 3) with an excess of zinc(II) sulfate under hydrothermal conditions was investigated as a function of the reaction temperature, the duration of the hydrothermal treatment, and the zinc(II) concentration. The product quality, i.e., crystalline impurities, Al impurities, and bulk Zn:Al ratio, were assessed by powder X-ray diffraction (PXRD), 27Al MAS NMR, and elemental analysis. Structural characterization of a stoichiometric ZnAl 4-LDH (120 °C, 9 days, and 2.8 M Zn(II)) showed a well-defined structure of the metal ion layer as evidenced by a single, well-defined Zn environment: i.e., no Zn substitution on the Al sites according to Zn k-edge EXAFS and PXRD. Furthermore, nearly all of the 12 different 1H atoms in the -OH groups and 4 27Al resonances could be assigned using 1H, 27Al NMR correlation experiments recorded with ultrafast MAS. The interlayer water content is variable on the basis of thermogravimetric analysis and changes in the 1H MAS NMR spectra with temperature. A composition of ZnAl 4(OH) 12(SO 4)·2.6H 2O was obtained from a combination of these techniques and confirmed that ZnAl 4-LDH is isostructural with the mineral nickelalumite (NiAl 4(OH) 12SO 4·3H 2O).

Selenium is of special interest in different research fields due to its narrow range between beneficial and toxic effects. On a global scale, Se deficiency is more widespread. Biofortification measures have successfully been applied to specifically increase Se concentrations in food crops. Still not much is known about the behaviour and long-term fate of externally supplied Se. Over many years, natural but external selenate is regularly introduced into the soil-plant system via irrigation at our study sites in Punjab which makes it also an ideal natural analogue to investigate the long term effect of biofortification. For our study, we combined total and species specific analysis of Se in soil and plant material. Selenium is clearly enriched in all investigated topsoils (0-15 cm) with concentrations of 1.5-13.0 mg kg-1 despite similar background Se concentrations (0.5 ± 0.1 mg kg-1) below 15 cm depth. Irrigation is indicated to be the primary source of excess Se. Processes like Se species transformation, uptake by plants and plant material decomposition further influence both the Se speciation and extent of Se enrichment in the soils. The Se concentration in different plants and plant parts is alarmingly high showing concentrations of up to 738 mg kg-1 in wheat. Irrigation induced selenate can be considered as an easily available short term pool of Se for plants and thus strongly controls their total Se concentration and speciation. The long-term pool of Se in the topsoil mainly consists of selenite and organic Se species. These species are readily retained but still sufficiently mobile to be taken up by plants. The formation of elemental Se can be considered as a non-available Se pool and is thus, the major cause of Se immobilization and long-term enrichment of Se in the soils. Our study clearly shows that biofortification with selenate, despite its effectiveness, bears the risk of easily increasing Se levels in plants to toxic levels and producing food with less favourable inorganic Se species if not done with care. Excess selenate is either lost due to biomethylation or immobilized within the soil which has to be considered as highly negative from both an economic and ecological point of few.

This study investigates redox transitions associated with the adsorption of Cr(VI) on commonly occurring soil components (silicates, oxides and humic acids) and their synthetic mixtures by coupling the mechanistic surface complexation modeling with spectroscopic and isotopic analyses. The mixtures of soil components were prepared to reflect the composition of the real anthroposol sample, determined by X-ray Powder Diffraction (XRD), total organic carbon (TOC) measurement and extraction methods. The effect of different initial Cr(VI) concentrations (2×10−2, 5×10−4, 10−4, 10−5, and 10−6M), background electrolyte (10−3, 10−2, and 10−1M KNO3), pH values (3–9), and sorbate/sorbent ratios (2g/L - 20g/L) were investigated. Maghemite and ferrihydrite were confirmed to be the main phases controlling Cr(VI) adsorption with increasing Cr(VI) concentration. Humic acids were primarily responsible for Cr(VI) reduction, especially at low pH values. The reduction of Cr(VI) was also proved in case of illite and kaolinite by XAS and isotopic analyses. Illite revealed higher reduction capacity in comparison with kaolinite based on XAS measurements. Chromium isotopic fractionation, resulting from Cr(VI) reduction, was the highest in the case of humic acids, followed by kaolinite and illite. However, a dissolution of intrinsic Cr originally present within kaolinite and illite might affect the final Cr isotopic composition of the supernatants due to its different Cr isotopic signature. In general, the combination of three different approaches was confirmed to offer more comprehensive information about Cr(VI) adsorption and/or reduction in soils. Detailed studies using soil mixtures can help to predict how the soil components affect Cr(VI) behavior in natural soils and possibly could improve the environmental remediation processes. Keywords: Chromate reduction, Soil component mixtures, Adsorption modeling, Cr isotopes, X-ray absorption spectroscopy

The efficacy of in vitro Cr(VI) reduction by green rust sulfate suggests that this mineral is potentially useful for remediation of Cr-contaminated groundwater. Previous investigations studied this reaction but did not sufficiently characterize the intermediates and end products at chromate (CrO42&minus, ) concentrations typical of contaminant plumes, hindering identification of the dominant reaction mechanisms under these conditions. In this study, batch reactions at varying chromate concentrations and suspension densities were performed and the intermediate and final products of this reaction were analyzed using X-ray absorption spectroscopy and electron microscopy. This reaction produces particles that maintain the initial hexagonal morphology of green rust but have been topotactically transformed into a poorly crystalline Fe(III) oxyhydroxysulfate and are coated by a Cr (oxy) hydroxide layer that results from chromate reduction at the surface. Recent studies of the behavior of Cr(III) (oxy) hydroxides in soils have revealed that reductive transformation of CrO42&minus, is reversible in the presence of Mn(IV) oxides, limiting the applicability of green rust for Cr remediation in some soils. The linkage of Cr redox speciation to existing Fe and Mn biogeochemical cycles in soils implies that modification of green rust particles to produce an insoluble, Cr(III)-bearing Fe oxide product may increase the efficacy of this technique.

CAT-ACT - the hard X-ray beamline for CATalysis and ACTinide/radionuclide research at the KIT synchrotron radiation facility ANKA - is dedicated to X-ray spectroscopy, including "flux hungry" photon-in/photon-out and correlative techniques and combines state-of-the-art optics with a unique infrastructure for radionuclide and catalysis research. Measurements can be performed at photon energies varying between 3.4 keV and 55 keV, thus encompassing the actinide M- and L-edge or potassium K-edge up to the K-edges of the lanthanide series such as cerium. Well-established X-ray absorption fine structure spectroscopy in transmission and fluorescence detection modes is available in combination with high energy-resolution X-ray emission spectroscopy or X-ray diffraction techniques. The modular beamline design with two alternately operated in-line experimental stations enables sufficient flexibility to adapt sample environments and detection systems to many scientific challenges. The ACT experimental station focuses on various aspects of nuclear waste disposal within the mission of the Helmholtz association to contribute to the solution of one of the greatest scientific and social challenges of our time - the safe disposal of heat producing, highly radioactive waste forms from nuclear energy production. It augments present capabilities at the INE-Beamline by increasing the flux and extending the energy range into the hard X-ray regime. The CAT experimental station focuses on catalytic materials, e.g., for energy-related and exhaust gas catalysis. Characterization of catalytically active materials under realistic reaction conditions and the development of in situ and operando cells for sample environments close to industrial reactors are essential aspects at CAT.

We present new data about the chemical and structural characteristics of bauxite residue (BR) from Greek Al industry, using a combination of microscopic, analytical, and spectroscopic techniques. SEM-EDS indicated a homogeneous dominant “Al-Fe-Ca-Ti-Si-Na-Cr matrix”, appearing at the microscale. The bulk chemical analyses showed considerable levels of Th (111 μg g−1), along with minor U (15 μg g−1), which are responsible for radioactivity (355 and 133 Bq kg−1 for 232Th and 238U, respectively) with a total dose rate of 295 nGy h−1. Leaching experiments, in conjunction with SF-ICP-MS, using Mediterranean seawater from Greece, indicated significant release of V, depending on S/L ratio, and negligible release of Th at least after 12 months leaching. STEM-EDS/EELS & HR-STEM-HAADF study of the leached BR at the nanoscale revealed that the significant immobility of Th4+ is due to its incorporation into an insoluble perovskite-type phase with major composition of Ca0.8Na0.2TiO3 and crystallites observed in nanoscale. The Th LIII-edge EXAFS spectra demonstrated that Th4+ ions, which are hosted in this novel nano-perovskite of BR, occupy Ca2+ sites, rather than Ti4+ sites. That is most likely the reason of no Th release in Mediterranean seawater.

The Tres Marias carbonate-hosted Zn-Ge deposit in Chihuahua, Mexico contains willemite [Zn$_{2}$SiO$_{4}$] with unusually high concentrations of minor and trace elements (e.g., Pb, Ge, As, P, V); Pb concentrations are as high as 2 wt %, and Ge may reach 4000 ppm (average 900 ppm). Electron microprobe analyses and synchrotron X-ray fluorescence maps show that Zn and Ge, as well as Zn and Pb are negatively correlated, whereas Ge and Pb are positively correlated across zoned willemite crystals. In cathodoluminescence (CL) images, those areas of willemite having high trace element concentrations have no, or low CL intensities, whereas zones low in trace elements (except for P) display bright blue CL colors. X-ray absorption fine structure (XAFS) spectroscopy was used to characterize the chemical nature of Ge and Pb in willemite. Comparisons to reference spectra of natural and artificial substances points to the presence of Ge$^{4+}$ and Pb$^{2+}$ in Tres Marias willemite. No evidence for Pb$^{4+}$ was detected. Oscillatory zonation reflects trace element incorporation into willemite from the oxidation of primary Ge-bearing sphalerite and galena (PbS) by siliceous aqueous fluids.

The usefulness of full field transmission spectroscopy is shown using the example of mandible of the stick insect Peruphasma schultei. An advanced data evaluation tool chain with an energy drift correction and highly reproducible automatic background correction is presented. The results show significant difference between the top and the bottom of the mandible of an adult stick insect.

We present new data about the chemical and structural characteristics of bauxite residue (BR) from Greek Al industry, using a combination of microscopic, analytical, and spectroscopic techniques. SEM-EDS indicated a homogeneous dominant “Al-Fe-Ca-Ti-Si-Na-Cr matrix”, appearing at the microscale. The bulk chemical analyses showed considerable levels of Th (111 μg g−1), along with minor U (15 μg g−1), which are responsible for radioactivity (355 and 133 Bq kg−1 for 232Th and 238U, respectively) with a total dose rate of 295 nGy h−1. Leaching experiments, in conjunction with SFICP- MS, using Mediterranean seawater from Greece, indicated significant release of V, depending on S/L ratio, and negligible release of Th at least after 12 months leaching. STEM-EDS/EELS & HR-STEMHAADF study of the leached BR at the nanoscale revealed that the significant immobility of Th4+ is due to its incorporation into an insoluble perovskite-type phase with major composition of Ca0.8Na0.2TiO3 and crystallites observed in nanoscale. The Th LIII-edge EXAFS spectra demonstrated that Th4+ ions, which are hosted in this novel nano-perovskite of BR, occupy Ca2+ sites, rather than Ti4+ sites. That is most likely the reason of no Th release in Mediterranean seawater.

The dissolution parameters of calcium carbonates play a key role in agriculture as they regulate the plant nutrients uptake and buffer the pH-value of the soil. The combination of μXRF, μXAS and μXRD mapping in the hard X-ray regime for the examination of both short- and long range order in natural limestones revealed that their dissolution properties depend both on the crystallinity of the mineral phases and their composition. The results particularly show that in many cases the presence of magnesium inhibits dissolution of the phases.

Up to now, no consensus exists about the electronic nature of phosphorus (P) as donor for SiO2-embedded silicon nanocrystals (SiNCs). Here, we report on hybrid density functional theory (h-DFT) calculations of P in the SiNC/SiO2 system matching our experimental findings. Relevant P configurations within SiNCs, at SiNC surfaces, within the sub-oxide interface shell and in the SiO2 matrix were evaluated. Atom probe tomography (APT) and its statistical evaluation provide detailed spatial P distributions. For the first time, we obtain ionisation states of P atoms in the SiNC/SiO2 system at room temperature using X-ray absorption near edge structure (XANES) spectroscopy, eliminating structural artefacts due to sputtering as occurring in XPS. K energies of P in SiO2 and SiNC/SiO2 superlattices (SLs) were calibrated with non-degenerate P-doped Si wafers. "Equation missing" results confirm measured core level energies, connecting and explaining XANES spectra with h-DFT electronic structures. While P can diffuse into SiNCs and predominantly resides on interstitial sites, its ionization probability is extremely low, rendering P unsuitable for introducing electrons into SiNCs embedded in SiO2. Increased sample conductivity and photoluminescence (PL) quenching previously assigned to ionized P donors originate from deep defect levels due to P.

We report on integrated geomorphological, mineralogical, geochemical and biological investigations of the hydrothermal vent field located on the floor of the density-stratified acidic (pH ~ 5) crater of the Kolumbo shallow-submarine arc-volcano, near Santorini. Kolumbo features rare geodynamic setting at convergent boundaries, where arc-volcanism and seafloor hydrothermal activity are occurring in thinned continental crust. Special focus is given to unique enrichments of polymetallic spires in Sb and Tl (±Hg, As, Au, Ag, Zn) indicating a new hybrid seafloor analogue of epithermal-to-volcanic-hosted-massive-sulphide deposits. Iron microbial-mat analyses reveal dominating ferrihydrite-type phases, and high-proportion of microbial sequences akin to "Nitrosopumilus maritimus", a mesophilic Thaumarchaeota strain capable of chemoautotrophic growth on hydrothermal ammonia and CO2. Our findings highlight that acidic shallow-submarine hydrothermal vents nourish marine ecosystems in which nitrifying Archaea are important and suggest ferrihydrite-type Fe(3+)-(hydrated)-oxyhydroxides in associated low-temperature iron mats are formed by anaerobic Fe(2+)-oxidation, dependent on microbially produced nitrate.

We report on integrated geomorphological, mineralogical, geochemical and biological investigations of the hydrothermal vent field located on the floor of the density-stratified acidic (pH , 5) crater of the Kolumbo shallow-submarine arc-volcano, near Santorini. Kolumbo features rare geodynamic setting at convergent boundaries, where arc-volcanism and seafloor hydrothermal activity are occurring in thinned continental crust. Special focus is given to unique enrichments of polymetallic spires in Sb and Tl (6Hg, As, Au, Ag, Zn) indicating a new hybrid seafloor analogue of epithermal-to-volcanic-hosted-massive-sulphide deposits. Iron microbial-mat analyses reveal dominating ferrihydrite-type phases, and high-proportion of microbial sequences akin to "Nitrosopumilus maritimus", a mesophilic Thaumarchaeota strain capable of chemoautotrophic growth on hydrothermal ammonia and CO2. Our findings highlight that acidic shallow-submarine hydrothermal vents nourish marine ecosystems in which nitrifying Archaea are important and suggest ferrihydrite-type Fe31-(hydrated)-oxyhydroxides in associated low-temperature iron mats are formed by anaerobic Fe21-oxidation, dependent on microbially produced nitrate.

Sulphur plays a vital role in every human organism. It is known, that sulphur-bearing compounds, such as for example cysteine and glutathione, play critical roles in development and progression of many diseases. Any alteration in sulphur's biochemistry could become a precursor of serious pathological conditions. One of such condition is prostate cancer, the most frequently diagnosed malignancy in the western world and the second leading cause of cancer related death in men. The purpose of presented studies was to examine what changes occur in the nearest chemical environment of sulphur in prostate cancer cell lines in comparison to healthy cells. The Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy was used, followed by theoretical calculations. The results of preliminary analysis is presented.

The study presented here was initiated by a discussion to investigate the possibility of using synchrotron radiation as a source for the Next Generation Lithography (NGL) based on the EUV-concept (Extreme Ultra-Violet; here 13.5 nm or 11.3 nm radiation, respectively). The requirements are: 50 W, 2% bandwidth and minimal power outside this bandwidth. Three options were investigated. The first two deal with radiation from bending magnets and undulators. The results confirm the earlier work by Oxfords Instrument and others that these light-sources lack in-band power while emitting excessive out-of-band radiation. The third approach is a FEL (Free Electron Laser) driven by a 500 MeV linear accelerator with a superconducting mini-undulator as radiation emitting device. Such a device would produce in-band EUV-power in excess of 50 W with negligible out-of-band power., Submitted to Nuclear Instruments and Methods A

Al2O3 on Si is known to form an ultrathin interfacial SiO2 during deposition and subsequent annealing, which creates a negative fixed charge ( Qfix) that enables field-effect passivation and low surface recombination velocities in Si solar cells. Various concepts were suggested to explain the origin of this negative Qfix. In this study, we investigate Al-O monolayers (MLs) from atomic layer deposition (ALD) sandwiched between deliberately grown/deposited SiO2 films. We show that the Al atoms have an ultralow diffusion coefficient (∼4 × 10-18 cm2/s at 1000 °C), are deposited at a constant rate of ∼5 × 1014 Al atoms/(cm2 cycle) from the first ALD cycle, and are tetrahedral O-coordinated because the adjacent SiO2 imprints its tetrahedral near-order and bond length into the Al-O MLs. By variation in the tunnel-SiO2 thickness and the number of Al-O MLs, we demonstrate that the tetrahedral coordination alone is not sufficient for the formation of Qfix but that a SiO2/Al2O3 interface within a tunneling distance from the substrate must be present. The Al-induced acceptor states at these interfaces have energy levels slightly below the Si valence band edge and require charging by electrons from either the Si substrate or from Si/SiO2 dangling bonds to create a negative Qfix. Hence, tunneling imposes limitations for the SiO2 and Al2O3 layer thicknesses. In addition, Coulomb repulsion between the charged acceptor states results in an optimum number of Al-O MLs, i.e., separation of both interfaces. We achieve maximum negative Qfix of ∼5 × 1012 cm-2 (comparable to thick ALD-Al2O3 on Si) with ∼1.7 nm tunnel-SiO2 and just seven ALD-Al2O3 cycles (∼8 Å) after optimized annealing at 850 °C for 30 s. The findings are discussed in the context of a passivating, hole-selective tunnel contact for high-efficiency Si solar cells. ispartof: ACS APPLIED MATERIALS & INTERFACES vol:10 issue:36 pages:30495-30505 ispartof: location:United States status: published