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The transport and magnetic properties of the Magnéli phase tungsten oxide WO2.90, prepared via spark plasma sintering, were investigated across a broad temperature range of 4–550 K, including the previously unexplored low-temperature region below 300 K. Microstructure analysis shows that obtained pellets are fully dense, enabling reliable measurement of transport properties. Resistivity measurements reveal typical metallic behavior of WO2.90 at low temperatures. Above room temperature, resistivity tends to saturate by reaching a maximum value near 430 K. The resistivity saturation indicates that Mott-Ioffe-Regel limit is approached, where the charge carrier mean free path becomes comparable to the interatomic spacing. The temperature dependence of the resistivity can be well described by the phenomenological parallel resistor model. Significant positive magnetoresistance was observed at low temperatures, with an unusual linear dependence on the magnetic field. Despite its metallic conductivity, WO2.90 displays weak diamagnetism, likely due to the substantial core diamagnetism of tungsten and the bipolaronic pairing of charge carriers. [ABSTRACT FROM AUTHOR]

It has been proposed by Müller and Shengelaya that underdoped ultrathin layers of copper-oxide high-temperature superconductors (HTSs) sandwiched between high-dielectric-constant insulator layers could manifest increased superconducting critical temperature T c . To check this hypothesis, we investigated structural and transport properties of YBa 2 Cu 3 O 7 - δ (YBCO) thin films sandwiched between SrTiO 3 (STO) layers. Scanning transmission electron microscopy (STEM) showed that a high-quality interface is formed between YBCO and the top STO layers. An increase of T c up to Δ T ≈ 20 K was observed at these interfaces in case of underdoped YBCO films. [ABSTRACT FROM AUTHOR]

Metal–insulator–metal (M–I–M) structures involving transition-metal oxides and, more recently, also perovskite oxides with resistive switching effects have attracted substantial interest in research aimed at nonvolatile memories of nanometer dimensions. Although some models are presently under discussion, it is still not clear whether the fundamental switching mechanism is an interface or a bulk property, or a combination of both. Extended defects, such as dislocation lines and changes in the oxygen vacancy concentration, are considered responsible for the conducting state, and local reduction/oxidation processes have been proposed to be responsible for the resistive switching. In addition, the role of dopants has not been discussed in depth. Here we report on an electric-field-controlled electron trapping/detrapping process involved in the resistive switching in Cr-doped SrTiO3. Electroluminescence (EL) measurements reveal that during resistive switching, light emission is observed only in the switching transition from high to low conductivity. The EL spectrum is typical for Cr3+ in an octahedral ligand field, indicating that the switching process involves trapping/detrapping of electrons at the Cr site. With increasing conductivity of SrTiO3, we observe a change from the predominant $^{2}{E}\to^{4}{A}_{2g}$ (R-line) to the vibronically red-shifted $^{4}{T}_{2}\to^{4}{A}_{2g}$ transition, which points to a modification of the Cr-occupied lattice sites. [ABSTRACT FROM AUTHOR]

An insulator-to-metal transition is observed in Cr-doped SrTiO3 single crystals upon extended exposure to a high electric field, namely, electroconditioning (EC). Electron paramagnetic resonance (EPR) and transport measurements under laser irradiation show anticorrelation between the Cr3+ EPR signal and the electrical current. This proves that the Cr3+ ions are responsible for the photocurrent that initiates the EC process. We observe the presence of Cr3+/Cr4+ mixed valencies in the bulk in the conducting state. The EPR characterization of the spectra in the conducting state excludes the possibility of a Cr3+-oxygen vacancy complex in the bulk as a result of the EC. [ABSTRACT FROM AUTHOR]

We provide a status report on the development of perovskite-based transition-metal-oxide resistance-change memories. We focus on bipolar resistance switching observed in Cr-doped SrTiO3 memory cells with dimensions ranging from bulk single crystals to CMOS integrated nanoscale devices. We also discuss electronic and ionic processes during electroforming and resistance switching, as evidenced from electron-parametric resonance (EPR), x-ray absorption spectroscopy, electroluminescence spectroscopy, thermal imaging, and transport experiments. EPR in combination with electroluminescence reveals electron trapping and detrapping processes at the Cr site. Results of x-ray absorption experiments prove that the microscopic origin of the electroforming, that is, the insulator-to-metal transition, is the creation of oxygen vacancies. Cr-doped SrTiO3 memory cells exhibit short programming times (≤100 ns) and low programming currents (<100 µA) with up to 105 write and erase cycles. [ABSTRACT FROM AUTHOR]

Colloidal quantum dots (cQDs), semiconductor materials with widely tunable properties, can be printed in submicrometer patterns through electrohydrodynamic printing, avoiding aggressive photolithography steps. Postprinting ligand exchange determines the final optoelectronic properties of the cQD structures. However, achieving a complete bulk exchange is challenging, and the conventional vibrational analysis lacks the required spatial resolution. Infrared nanospectroscopy enables quantitative analysis of vibrational signals and structural topography on the nanometer scale upon ligand substitution on lead sulfide cQDs. A solution of ethanedithiol led to rapid (∼60 s) exchange of ≤90% of the ligands, in structures up to ∼750 nm thick. Prolonged exposures (>1 h) caused the degradation of the microstructures, with a systematic removal of cQDs regulated by surface:bulk ratios and solvent interactions. This study establishes a method for the development of devices through a combination of tunable photoactive materials, additive manufacturing of microstructures, and their quantitative nanometer-scale analysis.

MXenes are 2D transition metal carbides, nitrides, and/or carbonitrides that can be intercalated with cations through chemical or electrochemical pathways. While the insertion of alkali and alkaline earth cations into Ti 3 C 2 T x MXenes is well studied, understanding of the intercalation of redox-active transition metal ions into MXenes and its impact on their electronic and electrochemical properties is lacking. In this work, we investigate the intercalation of Cu ions into Ti 3 C 2 T x MXene and its effect on its electronic and electrochemical properties. Using X-ray absorption spectroscopy (XAS) and ab initio molecular dynamics (AIMD), we observe an unusual phenomenon whereby Cu 2+ ions undergo partial reduction upon intercalation from the solution into the MXene. Furthermore, using in situ XAS, we reveal changes in the oxidation states of intercalated Cu ions and Ti atoms during charging. We show that the pseudocapacitive response of Cu-MXene originates from the redox of both the Cu intercalant and Ti 3 C 2 T x host. Despite highly reducing potentials, Cu ions inside the MXene show an excellent stability against full reduction upon charging. Our findings demonstrate how electronic coupling between Cu ions and Ti 3 C 2 T x modifies electrochemical and electronic properties of the latter, providing the framework for the rational design and utilization of transition metal intercalants for tuning the properties of MXenes for various electrochemical systems.

Within the emerging field of proton-conducting fuel cells, BaZr 0.9 Y 0.1 O 3-δ (BZY10) is an attractive material due to its high conductivity and stability. The fundamentals of conduction in sintered pellets and thin films heterostructures have been explored in several studies; however, the role of crystallographic orientation, grains, and grain boundaries is poorly understood for proton conduction. This article reports proton conduction in a self-assembled multi-oriented BZY10 thin film grown on top of a (110) NdGaO 3 substrate. The multiple orientations are composed of different lattices, which provide a platform to study the lattice-dependent conductivity through different orientations in the vicinity of grain boundary between them and the substrate. The crystalline stacking of each orientation is confirmed by X-ray diffraction analysis and scanning transmission electron microscopy. The transport measurements are carried out under different gas atmospheres. The highest conductivity of 3.08 × 10 -3 S cm -1 at 400 °C is found under a wet H 2 environment together with an increased lattice parameter of 4.208 Å, while under O 2 and Ar environments, the film shows lower conductivity and lattice parameter. Our findings not only demonstrate the role of crystal lattice for conduction properties but also illustrate the importance of self-assembled strategies to achieve high proton conduction in BZY10 thin films.

The role of epitaxial strain and chemical termination in selected interfaces of perovskite oxide heterostructures is under intensive investigation because of emerging novel electronic properties. SrTiO   3 (STO) is one of the most used substrates for these compounds, and along its < 001 > direction allows for two nonpolar chemical terminations: TiO 2 and SrO. In this paper, we investigate the surface morphology and crystal structure of SrO epitaxial ultrathin films: from 1 to about 25 layers grown onto TiO   2 -terminated STO substrates. X-ray diffraction and transmission electron microscopy analysis reveal that SrO grows along its [ 111 ] direction with a 4% out-of-plane elongation. This large strain may underlay the mechanism of the formation of self-organized pattern of stripes that we observed in the initial growth. We found that the distance between the TiO   2 plane and the first deposited SrO layer is 0.27 ( 3 ) nm, a value which is about 40% bigger than in the STO bulk. We demonstrate that a single SrO-deposited layer has a different morphology compared to an ideal atomically flat chemical termination.

Quantum efficiency measurements of state of the art Cu(In,Ga)Se 2 (CIGS) thin film solar cells reveal current losses in the near infrared spectral region. These losses can be ascribed to inadequate optical absorption or poor collection of photogenerated charge carriers. Insight on the limiting mechanism is crucial for the development of more efficient devices. The electron beam induced current measurement technique applied on device cross-sections promises an experimental access to depth resolved information about the charge carrier collection probability. Here, this technique is used to show that charge carrier collection in CIGS deposited by multistage co-evaporation at low temperature is efficient over the optically active region and collection losses are minor as compared to the optical ones. Implications on the favorable absorber design are discussed. Furthermore, it is observed that the measurement is strongly affected by cross-section surface recombination and an accurate determination of the collection efficiency is not possible. Therefore it is proposed and shown that the use of an Al 2 O 3 layer deposited onto the cleaved cross-section significantly improves the accuracy of the measurement by reducing the surface recombination. A model for the passivation mechanism is presented and the passivation concept is extended to other solar cell technologies such as CdTe and Cu 2 (Zn,Sn)(S,Se) 4 ., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Solution processing of Cu2ZnSn(S,Se)4 (CZTSSe)-kesterite solar cells is attractive because of easy manufacturing using readily available metal salts. The solution-processed CZTSSe absorbers, however, often suffer from poor morphology with a bilayer structure, exhibiting a dense top crust and a porous bottom layer, albeit yielding efficiencies of over 10%. To understand whether the cell performance is limited by this porous layer, a systematic compositional study using (scanning) transmission electron microscopy ((S)TEM) and energy-dispersive X-ray spectroscopy of the dimethyl sulfoxide processed CZTSSe absorbers is presented. TEM investigation revealed a thin layer of CdS that is formed around the small CZTSSe grains in the porous bottom layer during the chemical bath deposition step. This CdS passivation is found to be beneficial for the cell performance as it increases the carrier collection and facilitates the electron transport. Electron-beam-induced current measurements reveal an enhanced carrier collection for this buried region as compared to reference cells with evaporated CdS.

Roll-to-roll manufacturing of CdTe solar cells on flexible metal foil substrates is one of the most attractive options for low-cost photovoltaic module production. However, various efforts to grow CdTe solar cells on metal foil have resulted in low efficiencies. This is caused by the fact that the conventional device structure must be inverted, which imposes severe restrictions on device processing and consequently limits the electronic quality of the CdTe layer. Here we introduce an innovative concept for the controlled doping of the CdTe layer in the inverted device structure by means of evaporation of sub-monolayer amounts of Cu and subsequent annealing, which enables breakthrough efficiencies up to 13.6%. For the first time, CdTe solar cells on metal foil exceed the 10% efficiency threshold for industrialization. The controlled doping of CdTe with Cu leads to increased hole density, enhanced carrier lifetime and improved carrier collection in the solar cell. Our results offer new research directions for solving persistent challenges of CdTe photovoltaics.