Tunable band gap in hydrogenated quasi-free-standing graphene.

We show by angle-resolved photoemission spectroscopy that a tunable gap in quasi-free-standing monolayer graphene on Au can be induced by hydrogenation. The size of the gap can be controlled via hydrogen loading and reaches approximately 1.0 eV for a hydrogen coverage of 8%. The local rehybridization from sp(2) to sp(3) in the chemical bonding is observed by X-ray photoelectron spectroscopy and X-ray absorption and allows for a determination of the amount of chemisorbed hydrogen. The hydrogen induced gap formation is completely reversible by annealing without damaging the graphene. Calculations of the hydrogen loading dependent core level binding energies and the spectral function of graphene are in excellent agreement with photoemission experiments. Hydrogenation of graphene gives access to tunable electronic and optical properties and thereby provides a model system to study hydrogen storage in carbon materials.

Spectroscopic characterization of N-doped single-walled carbon nanotube strands: an X-ray photoelectron spectroscopy and Raman study.

We have studied in detail the carbon and nitrogen bonding environments in nitrogen-doped single-walled carbon nanotubes (SWCNTs). The samples consisting of long strands of N-doped SWCNTs were synthesized using an aerosol assisted chemical vapor deposition method involving benzylamine-ethanol-ferrocene solutions. The studied samples were produced using different benzylamine concentrations in the solutions, and exhibited a maximum concentration of ca. 0.3%at of N, determined by X-ray photoelectron spectroscopy (XPS). In general, we observed that the ratio between substitutional nitrogen and the pyridine-like bonded nitrogen varied upon the precursor composition. Moreover, we have observed that the sp2-like substitutional configuration of the C-N bond does not exceed the 50% of the total N atomic incorporation. In addition, we have characterized all these samples using Raman spectroscopy and electron microscopy.

Incidence of Quantum Confinement on Dark Triplet Excitons in Carbon Nanotubes.

The photophysics of single-wall carbon nanotubes (SWCNTs) is intensively studied due to their potential application in light harvesting and optoelectronics. Excited states of SWCNTs form strongly bound electron-hole pairs, excitons, of which only singlet excitons participate in application relevant optical transitions. Long-living spin-triplet states hinder applications, but they emerge as candidates for quantum information storage. Therefore, knowledge of the triplet exciton energy structure, in particular in a SWCNT chirality dependent manner, is greatly desired. We report the observation of light emission from triplet state recombination, i.e., phosphorescence, for several SWCNT chiralities using a purpose-built spectrometer. This yields the singlet-triplet gap as a function of the SWCNT diameter, and it follows predictions based on quantum confinement effects. Saturation under high microwave power (up to 10 W) irradiation allows the spin-relaxation time for triplet states to be determined. Our study sensitively discriminates whether the lowest optically active state is populated from an excited state on the same nanotube or through Förster exciton energy transfer from a neighboring nanotube.

Ultralong Spin Lifetime in Light Alkali Atom Doped Graphene.

Today's great challenges of energy and informational technologies are addressed with a singular compound, Li- and Na-doped few-layer graphene. All that is impossible for graphite (homogeneous and high-level Na doping) and unstable for single-layer graphene works very well for this structure. The transformation of the Raman G line to a Fano line shape and the emergence of strong, metallic-like electron spin resonance (ESR) modes attest the high level of graphene doping in liquid ammonia for both kinds of alkali atoms. The spin-relaxation time in our materials, deduced from the ESR line width, is 6-8 ns, which is comparable to the longest values found in spin-transport experiments on ultrahigh-mobility graphene flakes. This could qualify our material as a promising candidate in spintronics devices. On the other hand, the successful sodium doping, this being a highly abundant metal, could be an encouraging alternative to lithium batteries.

Suitability of the shallow water hydrothermal system at Ambitle Island (Papua New Guinea) to study the effect of high pCO2 on coral reefs.

Volcanic CO2 seeps were successfully used to predict coral reef response to ocean acidification, although toxic elements, often characteristic of hydrothermal vents were rarely reported. We measured the physicochemical conditions, seawater carbonate chemistry and trace elements in Tutum Bay, Papua New Guinea. There, intense emission of hydrothermal fluids and CO2 expose the coral reef to a seawater pHT between 7.6 and 7.7. Arsenic and silica were enriched by up to six times in surface seawater, while bottom concentrations were lower and thus similar to coral reefs worldwide. Manganese, cesium, iron and zinc concentrations fell into the range of other coastal environments. Our measurements suggest that Tutum Bay is a suitable site to study the response of coral reefs to high pCO2. Considering that arsenic is a common metal in hydrothermal fluids, its characterization should be included in any study that uses volcanic CO2 seeps as natural laboratories for ocean acidification.

Single-walled carbon nanotubes synthesis: a direct comparison of laser ablation and carbon arc routes.

Carbon arc and chemical vapor deposition are at present the most efficient methods for mass production of single-walled carbon nanotubes. However, laser ablation is renowned for high quality nanotubes with narrow diameter distributions and hence is also of great interest. The aim of this work was to compare both the carbon arc and laser ablation techniques with respect to the quality--and relative yield of the produced SWCNTs. For this comparative study we used Fe as the catalyst, which is known not to be very active in laser ablation. However, we show this is not the case when H2 is included in the reaction. The reactions for both synthesis routes were carried out in a N2-H2 (95-5% vol.) atmosphere. The same homogenous carbon rods with different iron contents, between 1 and 5 at.% were used as the carbon feedstock and catalyst supply in both synthesis routes. Additionally, two types of carbon rods containing 1 at.% Fe with different graphitization degrees were also investigated. In the arc-discharge case, the low-graphitized electrode produced a web-like product rich in SWCNTs, while the high-graphitized carbon rods yielded soot containing carbon-encapsulated iron nanocrystallites, amorphous carbon nanoparticles, and surprisingly a small fraction of SWCNTs. With laser ablation synthesis, the Fe content and the reactor temperature significantly influenced the SWCNTs yield. Carbon arc plasma diagnostics were also performed. By using optical emission and Absorption spectroscopy the plasma temperature, C2 and CN radical content in the arc zone were determined.

An optically detected magnetic resonance spectrometer with tunable laser excitation and wavelength resolved infrared detection.

We present the development and performance of an optically detected magnetic resonance (ODMR) spectrometer. The spectrometer represents advances over similar instruments in three areas: (i) the exciting light is a tunable laser source which covers much of the visible light range, (ii) the optical signal is analyzed with a spectrograph, (iii) the emitted light is detected in the near-infrared domain. The need to perform ODMR experiments on single-walled carbon nanotubes motivated the present development and we demonstrate the utility of the spectrometer on this material. The performance of the spectrometer is critically compared to similar instruments. The present development opens the way to perform ODMR studies on various new materials such as molecules and luminescent quantum dots where the emission is in the near-infrared range and requires a well-defined excitation wavelength and analysis of the scattered light.

Radiation Protection Clothing in X-Ray Diagnostics - Influence of the Different Methods of Measurement on the Lead Equivalent and the Required Mass.

PURPOSE: The determination of attenuation compared to lead for lead-free and lead-reduced protective clothing depends strongly on the different methods of measurement. The standards EN 61331-1 (2002), DIN 6857-1 und IEC 61331-1 (2014) are now available for the testing of protective clothing. These standards define methods in the narrow beam and in the inverse broad beam geometry with partially different radiation qualities. In the narrow beam the scattered radiation and fluorescence are not considered due to the arrangement. Therefore, the protective effect of lead-free materials will be incorrectly estimated compared to lead material. The influence of the different methods of measurement on the lead equivalent and the required mass of radiation protection clothing was examined. MATERIALS AND METHODS: The lead equivalents for material samples for commercially available protective clothing were determined. These samples were made of lead and lead-reduced and lead-free materials. For determination of the attenuation equivalents, certified lead foils with high purity and a precise thickness of 0.05 to 1.25 mm were used. RESULTS: The measurements indicate that the lead equivalent depends on the method of measurement and the radiation quality. For X-ray tube voltages below 110 kV, lead-free or lead-reduced materials show a higher lead equivalent compared to lead material in some cases. Significant mass reductions of more than 10 % compared to lead material are only achievable with a limited range of use up to 100 kV. CONCLUSION: The implementation of an internationally accepted measuring standard for radiation protection clothing is reasonable and necessary. If standard IEC 61331-1 (2014) can fill this role is unknown. Key points • The attenuation factor and the lead equivalent depend strongly on the method of measurement.• The used X-ray spectra are only partially comparable with the spectra of scattered radiation.• Mass reductions for protective clothing are only achievable with a limited range of use. Citation Format: • Schöpf T, Pichler T. Radiation Protection Clothing in X-Ray Diagnostics - Influence of the Different Methods of Measurement on the Lead Equivalent and the Required Mass. Fortschr Röntgenstr 2016; 188: 768 - 775.

Optimal control of complex atomic quantum systems.

Quantum technologies will ultimately require manipulating many-body quantum systems with high precision. Cold atom experiments represent a stepping stone in that direction: a high degree of control has been achieved on systems of increasing complexity. However, this control is still sub-optimal. In many scenarios, achieving a fast transformation is crucial to fight against decoherence and imperfection effects. Optimal control theory is believed to be the ideal candidate to bridge the gap between early stage proof-of-principle demonstrations and experimental protocols suitable for practical applications. Indeed, it can engineer protocols at the quantum speed limit - the fastest achievable timescale of the transformation. Here, we demonstrate such potential by computing theoretically and verifying experimentally the optimal transformations in two very different interacting systems: the coherent manipulation of motional states of an atomic Bose-Einstein condensate and the crossing of a quantum phase transition in small systems of cold atoms in optical lattices. We also show that such processes are robust with respect to perturbations, including temperature and atom number fluctuations.

Atomically precise semiconductor--graphene and hBN interfaces by Ge intercalation.

The full exploration of the potential, which graphene offers to nanoelectronics requires its integration into semiconductor technology. So far the real-world applications are limited by the ability to concomitantly achieve large single-crystalline domains on dielectrics and semiconductors and to tailor the interfaces between them. Here we show a new direct bottom-up method for the fabrication of high-quality atomically precise interfaces between 2D materials, like graphene and hexagonal boron nitride (hBN), and classical semiconductor via Ge intercalation. Using angle-resolved photoemission spectroscopy and complementary DFT modelling we observed for the first time that epitaxially grown graphene with the Ge monolayer underneath demonstrates Dirac Fermions unaffected by the substrate as well as an unperturbed electronic band structure of hBN. This approach provides the intrinsic relativistic 2D electron gas towards integration in semiconductor technology. Hence, these new interfaces are a promising path for the integration of graphene and hBN into state-of-the-art semiconductor technology.

Joys and pitfalls of fermi surface mapping in Bi(2)Sr(2)CaCu(2)O(8+delta) using angle resolved photoemission

On the basis of angle-scanned photoemission data recorded using unpolarized radiation, with high (E,k) resolution, and an extremely dense sampling of k space, we resolve the current controversy regarding the normal state Fermi surface (FS) in Bi(2)Sr(2)CaCu(2)O(8+delta). The true picture is simple, self-consistent, and robust: the FS is holelike, with the form of rounded tubes centered on the corners of the Brillouin zone. Two further types of features are also clearly observed: shadow FSs, which are most likely to be due to short range antiferromagnetic spin correlations, and diffraction replicas of the main FS caused by passage of the photoelectrons through the modulated Bi-O planes.

Diameter selective charge transfer in p- and n-doped single wall carbon nanotubes synthesized by the HiPCO method.

The unusually broad diameter distribution of single wall carbon nanotubes (SWCNTs) in a HiPCO derived sample made it possible to observe for the first time a selective loss of Raman resonances corresponding to large diameter tubes upon both p- (FeCl3) and n-type (K) doping.

Infrared response of multiwalled boron nitride nanotubes.

We report the infrared (IR) response of bulk samples of multiwalled boron nitride nanotubes, produced by a substitution reaction from single walled carbon nanotubes, which is dominated by two characteristic BN-vibrations at 800 and 1372 cm-1.

[Radiation protection clothing in X-ray diagnostics - comparison of attenuation equivalents in narrow beam and inverse broad-beam geometry]. / Strahlenschutzkleidung in der Röntgendiagnostik - Vergleich der Schwächungsgleichwerte im schmalen Strahlenbündel und in inverser Breitstrahlgeometrie.

PURPOSE: Standard DIN EN 61 331-1 for attenuation measurements in the narrow and broad beam as well as DIN 6857-1 for the determination of shielding properties in the inverse broad-beam geometry are available for testing the attenuation of protection clothing. The attenuation measurements in the narrow beam don't consider scattered radiation and fluorescence due to the arrangement. This leads to the fact that the protective effect of lead-free materials will be misestimated when compared to lead. Therefore, the differences in attenuation equivalents, determined by both test methods for topical radiation protection aprons, were examined. MATERIALS AND METHODS: The attenuations in inverse broad-beam geometry according to DIN 6857-1 and in the narrow beam according to DIN EN 61 331-1 were measured using commercially available aprons. They were made of lead, lead-reduced and lead-free materials. For determination of the attenuation equivalents, certificated lead-foils with high purity and a precise thickness of 0.1 to 1.25 mm were used. RESULTS: The measurements in the narrow beam according to DIN EN 61 331-1 showed that nearly all aprons reach the required lead equivalent at mid-range tube voltages of 100 kV. At higher and lower tube voltages, the requirements of DIN EN 61 331-3 were largely not met. In contrast, the testing of the same aprons in inverse broad-beam geometry according to DIN 6857-1 showed that only a few aprons meet the requirements for being classified in the nominal protection class. CONCLUSION: The measurements suggest that testing method DIN 6857-1 has yet to prevail and that manufacturers are just beginning to develop the appropriate protective materials.

Energy sources for chemolithotrophs in an arsenic- and iron-rich shallow-sea hydrothermal system.

The hydrothermally influenced sediments of Tutum Bay, Ambitle Island, Papua New Guinea, are ideal for investigating the chemolithotrophic activities of micro-organisms involved in arsenic cycling because hydrothermal vents there expel fluids with arsenite (As(III)) concentrations as high as 950 µg L(-1) . These hot (99 °C), slightly acidic (pH ~6), chemically reduced, shallow-sea vent fluids mix with colder, oxidized seawater to create steep gradients in temperature, pH, and concentrations of As, N, Fe, and S redox species. Near the vents, iron oxyhydroxides precipitate with up to 6.2 wt% arsenate (As(V)). Here, chemical analyses of sediment porewaters from 10 sites along a 300-m transect were combined with standard Gibbs energies to evaluate the energy yields (-ΔG(r)) from 19 potential chemolithotrophic metabolisms, including As(V) reduction, As(III) oxidation, Fe(III) reduction, and Fe(II) oxidation reactions. The 19 reactions yielded 2-94 kJ mol(-1) e(-) , with aerobic oxidation of sulphide and arsenite the two most exergonic reactions. Although anaerobic As(V) reduction and Fe(III) reduction were among the least exergonic reactions investigated, they are still potential net metabolisms. Gibbs energies of the arsenic redox reactions generally correlate linearly with pH, increasing with increasing pH for As(III) oxidation and decreasing with increasing pH for As(V) reduction. The calculated exergonic energy yields suggest that micro-organisms could exploit diverse energy sources in Tutum Bay, and examples of micro-organisms known to use these chemolithotrophic metabolic strategies are discussed. Energy modeling of redox reactions can help target sampling sites for future microbial collection and cultivation studies.

Screening the missing electron: nanochemistry in action.

The excitement of nano-test-tube chemistry in a single-walled carbon nanotube is exemplified in our study on electron doping in carbon nanotubes. Electron doping through the 1D van Hove singularity of single-walled carbon nanotubes is realized via a chemical reaction of an encapsulated organocerium compound, CeCp3. The decomposition of CeCp3 inside the carbon nanotubes increases the doping level and greatly enhances the density of conduction electrons. The transition of the cerium encapsulating semiconducting tubes to metallic results in enhanced screening of the photoexcited core hole potential. This fact illustrates the importance of many body effects in understanding core-level excitation process in carbon nanotubes.

Electron-electron correlation in graphite: a combined angle-resolved photoemission and first-principles study.

The full three-dimensional dispersion of the pi bands, Fermi velocities, and effective masses are measured with angle-resolved photoemission spectroscopy and compared to first-principles calculations. The band structure by density-functional theory underestimates the slope of the bands and the trigonal warping effect. Including electron-electron correlation on the level of the GW approximation, however, yields remarkable improvement in the vicinity of the Fermi level. This demonstrates the breakdown of the independent electron picture in semimetallic graphite and points toward a pronounced role of electron correlation for the interpretation of transport experiments and double-resonant Raman scattering for a wide range of carbon based materials.