Crystallize It before It Diffuses: Kinetic Stabilization of Thin-Film Phosphorus-Rich Semiconductor CuP2.

Numerous phosphorus-rich metal phosphides containing both P-P bonds and metal-P bonds are known from the solid-state chemistry literature. A method to grow these materials in thin-film form would be desirable, as thin films are required in many applications and they are an ideal platform for high-throughput studies. In addition, the high density and smooth surfaces achievable in thin films are a significant advantage for characterization of transport and optical properties. Despite these benefits, there is hardly any published work on even the simplest binary phosphorus-rich phosphide films. Here, we demonstrate growth of single-phase CuP2 films by a two-step process involving reactive sputtering of amorphous CuP2+x and rapid annealing in an inert atmosphere. At the crystallization temperature, CuP2 is thermodynamically unstable with respect to Cu3P and P4. However, CuP2 can be stabilized if the amorphous precursors are mixed on the atomic scale and are sufficiently close to the desired composition (neither too P poor nor too P rich). Fast formation of polycrystalline CuP2, combined with a short annealing time, makes it possible to bypass the diffusion processes responsible for decomposition. We find that thin-film CuP2 is a 1.5 eV band gap semiconductor with interesting properties, such as a high optical absorption coefficient (above 105 cm-1), low thermal conductivity (1.1 W/(K m)), and composition-insensitive electrical conductivity (around 1 S/cm). We anticipate that our processing route can be extended to other phosphorus-rich phosphides that are still awaiting thin-film synthesis and will lead to a more complete understanding of these materials and of their potential applications.

Characterization of the soft X-ray spectrometer PEAXIS at BESSY†II.

The performance of the recently commissioned spectrometer PEAXIS for resonant inelastic soft X-ray scattering (RIXS) and X-ray photoelectron spectroscopy and its hosting beamline U41-PEAXIS at the BESSY II synchrotron are characterized. The beamline provides linearly polarized light from 180 eV to 1600 eV allowing for RIXS measurements in the range 200-1200 eV. The monochromator optics can be operated in different configurations to provide either high flux with up to 1012 photons s-1 within the focal spot at the sample or high energy resolution with a full width at half maximum of <40 meV at an incident photon energy of ∼400 eV. The measured total energy resolution of the RIXS spectrometer is in very good agreement with theoretically predicted values obtained by ray-tracing simulations. PEAXIS features a 5 m-long RIXS spectrometer arm that can be continuously rotated about the sample position by 106° within the horizontal photon scattering plane, thus enabling the study of momentum-transfer-dependent excitations. Selected scientific examples are presented to demonstrate the instrument capabilities, including measurements of excitations in single-crystalline NiO and in liquid acetone employing a fluid cell sample manipulator. Planned upgrades of the beamline and the RIXS spectrometer to further increase the energy resolution to ∼100 meV at 1000 eV incident photon energy are discussed.

Water Adsorption Enhances Electrical Conductivity in Transparent P-Type CuI.

CuI has been recently rediscovered as a p-type transparent conductor with a high figure of merit. Even though many metal iodides are hygroscopic, the effect of moisture on the electrical properties of CuI has not been clarified. In this work, we observe a 2-fold increase in the conductivity of CuI after exposure to ambient humidity for 5 h, followed by slight long-term degradation. Simultaneously, the work function of CuI decreases by almost 1 eV, which can explain the large spread in the previously reported work function values. The conductivity increase is partially reversible and is maximized at intermediate humidity levels. On the basis of the large intragrain mobility measured by THz spectroscopy, we suggest that hydration of grain boundaries may be beneficial for the overall hole mobility.

MultiFLEXX - The new multi-analyzer at the cold triple-axis spectrometer FLEXX.

The first experimental characterization of a multiple energy analysis wide angle backend for a cold triple-axis spectrometer is reported. The multi-analyzer module MultiFLEXX employs 155 detection channels which simultaneously probe an extensive range in wavevector and energy transfer. Successful mapping of magnetic excitations in MnF2 and Ho demonstrate order of magnitude gains in data collection efficiency using this novel type backend. MultiFLEXX is competitive to standard triple-axis spectroscopy in terms of energy resolution and signal-to-noise ratio. A minority of the detector channels is affected by spurious signals inherent to this multiplexing concept. The characteristic signature of these spurious signals easily allows for their discrimination. The instrument concept focuses on detection efficiency in the horizontal scattering plane which makes it an ideal technique for fast mapping and parametric studies including extreme sample environment.

Wavelength-independent constant period spin-echo modulated small angle neutron scattering.

Spin-Echo Modulated Small Angle Neutron Scattering (SEMSANS) in Time-of-Flight (ToF) mode has been shown to be a promising technique for measuring (very) small angle neutron scattering (SANS) signals and performing quantitative Dark-Field Imaging (DFI), i.e., SANS with 2D spatial resolution. However, the wavelength dependence of the modulation period in the ToF spin-echo mode has so far limited the useful modulation periods to those resolvable with the limited spatial resolution of the detectors available. Here we present our results of an approach to keep the period of the induced modulation constant for the wavelengths utilised in ToF. This is achieved by ramping the magnetic fields in the coils responsible for creating the spatially modulated beam in synchronisation with the neutron pulse, thus keeping the modulation period constant for all wavelengths. Such a setup enables the decoupling of the spatial detector resolution from the resolution of the modulation period by the use of slits or gratings in analogy to the approach in grating-based neutron DFI.

Quantitative Neutron Dark-field Imaging through Spin-Echo Interferometry.

Neutron dark-field imaging constitutes a seminal progress in the field of neutron imaging as it combines real space resolution capability with information provided by one of the most significant neutron scattering techniques, namely small angle scattering. The success of structural characterizations bridging the gap between macroscopic and microscopic features has been enabled by the introduction of grating interferometers so far. The induced interference pattern, a spatial beam modulation, allows for mapping of small-angle scattering signals and hence addressing microstructures beyond direct spatial resolution of the imaging system with high efficiency. However, to date the quantification in the small angle scattering regime is severely limited by the monochromatic approach. To overcome such drawback we here introduce an alternative and more flexible method of interferometric beam modulation utilizing a spin-echo technique. This novel method facilitates straightforward quantitative dark-field neutron imaging, i.e. the required quantitative microstructural characterization combined with real space image resolution. For the first time quantitative microstructural reciprocal space information from small angle neutron scattering becomes available together with macroscopic image information creating the potential to quantify several orders of magnitude in structure sizes simultaneously.

Quantum spin correlations through the superconducting-to-normal phase transition in electron-doped superconducting Pr0.88LaCe0.12CuO4-delta.

The quantum spin fluctuations of the S = 1/2 Cu ions are important in determining the physical properties of high-transition-temperature (high T(c)) copper oxide superconductors, but their possible role in the electron pairing of superconductivity remains an open question. The principal feature of the spin fluctuations in optimally doped high-T(c) superconductors is a well defined magnetic resonance whose energy (E(R)) tracks T(c) (as the composition is varied) and whose intensity develops like an order parameter in the superconducting state. We show that the suppression of superconductivity and its associated condensation energy by a magnetic field in the electron-doped high-T(c) superconductor Pr(0.88)LaCe(0.12)CuO(4-delta) (T(c) = 24 K), is accompanied by the complete suppression of the resonance and the concomitant emergence of static antiferromagnetic order. Our results demonstrate that the resonance is intimately related to the superconducting condensation energy, and thus suggest that it plays a role in the electron pairing and superconductivity.