Electrostatically Driven Polarization Flop and Strain-Induced Curvature in Free-Standing Ferroelectric Superlattices.

The combination of strain and electrostatic engineering in epitaxial heterostructures of ferroelectric oxides offers many possibilities for inducing new phases, complex polar topologies, and enhanced electrical properties. However, the dominant effect of substrate clamping can also limit the electromechanical response and often leaves electrostatics to play a secondary role. Releasing the mechanical constraint imposed by the substrate can not only dramatically alter the balance between elastic and electrostatic forces, enabling them to compete on par with each other, but also activates new mechanical degrees of freedom, such as the macroscopic curvature of the heterostructure. In this work, an electrostatically driven transition from a predominantly out-of-plane polarized to an in-plane polarized state is observed when a PbTiO3 /SrTiO3 superlattice with a SrRuO3 bottom electrode is released from its substrate. In turn, this polarization rotation modifies the lattice parameter mismatch between the superlattice and the thin SrRuO3 layer, causing the heterostructure to curl up into microtubes. Through a combination of synchrotron-based scanning X-ray diffraction imaging, Raman scattering, piezoresponse force microscopy, and scanning transmission electron microscopy, the crystalline structure and domain patterns of the curved superlattices are investigated, revealing a strong anisotropy in the domain structure and a complex mechanism for strain accommodation.

Spectrophotometric Determination of Ca2+ and Ca-Complex Formation Constants: Application to Chemical Enhanced Oil Recovery.

Chemicals such as anionic surfactants and polymers often contain groups that complex divalent ions such as Ca2+. The formation of divalent ion complexes can decrease emulsifying or viscosifying power and lead to adsorption or precipitation. This is particularly relevant in chemical enhanced oil recovery, where high viscosities and low interfacial tensions are required for mobility control and the formation of oil-water microemulsions, respectively. In this work, we use a Ca2+-sensitive dye to determine the Ca2+ concentration and Ca-complex formation constants in solutions containing complexing agents. This method can be used to rapidly screen the affinity of different chemicals to form Ca-complexes in low-salinity solutions. The complex formation constants can be implemented into chemical flooding simulators to investigate the interplay with mineral dissolution and cation exchange and model adsorption processes.

The Impact of Micelle Formation on Surfactant Adsorption-Desorption.

The monomer-micelle equilibrium is shown to be responsible for an asymmetry between surfactant adsorption and desorption rates. When a solution containing micelles is brought into contact with a solid surface, the micelles dissociate to supply monomers that adsorb to the surface. When the same surface is subsequently exposed to a surfactant-free solution, desorption occurs slowly because of the higher affinity of the monomers to remain to the surface than to form micelles. As a result, the number of monomers that desorb is limited by the critical micelle concentration (CMC) of the surfactant. This effect is particularly pronounced for surfactants with low CMC values and in systems with high surface-to-volume ratios, such as porous media. A generic model is developed and applied to simulate the Ca2+-mediated adsorption and desorption of surfactants in limestone cores.

Anisotropic magnetoresistance in spin-orbit semimetal SrIrO 3.

SrIrO 3 , the three-dimensional member of the Ruddlesden-Popper iridates, is a paramagnetic semimetal characterised by a the delicate interplay between spin-orbit coupling and Coulomb repulsion. In this work, we study the anisotropic magnetoresistance (AMR) of SrIrO 3 thin films, which is closely linked to spin-orbit coupling and probes correlations between electronic transport, magnetic order and orbital states. We show that the low-temperature negative magnetoresistance is anisotropic with respect to the magnetic field orientation, and its angular dependence reveals the appearance of a fourfold symmetric component above a critical magnetic field. We show that this AMR component is of magnetocrystalline origin, and attribute the observed transition to a field-induced magnetic state in SrIrO 3 .

Insulator-to-Metal Transition at Oxide Interfaces Induced by WO3 Overlayers.

Interfaces between complex oxides constitute a unique playground for two-dimensional electron systems (2DESs), where superconductivity and magnetism can arise from combinations of bulk insulators. The 2DES at the LaAlO3/SrTiO3 interface is one of the most studied in this regard, and its origin is determined by the polar field in LaAlO3 as well as by the presence of point defects, like oxygen vacancies and intermixed cations. These defects usually reside in the conduction channel and are responsible for a decrease of the electronic mobility. In this work, we use an amorphous WO3 overlayer to obtain a high-mobility 2DES in WO3/LaAlO3/SrTiO3 heterostructures. The studied system shows a sharp insulator-to-metal transition as a function of both LaAlO3 and WO3 layer thickness. Low-temperature magnetotransport reveals a strong magnetoresistance reaching 900% at 10 T and 1.5 K, the presence of multiple conduction channels with carrier mobility up to 80 000 cm2 V-1 s-1, and quantum oscillations of conductance.

Photocurrent generation with two-dimensional van der Waals semiconductors.

Two-dimensional (2D) materials have attracted a great deal of interest in recent years. This family of materials allows for the realization of versatile electronic devices and holds promise for next-generation (opto)electronics. Their electronic properties strongly depend on the number of layers, making them interesting from a fundamental standpoint. For electronic applications, semiconducting 2D materials benefit from sizable mobilities and large on/off ratios, due to the large modulation achievable via the gate field-effect. Moreover, being mechanically strong and flexible, these materials can withstand large strain (>10%) before rupture, making them interesting for strain engineering and flexible devices. Even in their single layer form, semiconducting 2D materials have demonstrated efficient light absorption, enabling large responsivity in photodetectors. Therefore, semiconducting layered 2D materials are strong candidates for optoelectronic applications, especially for photodetection. Here, we review the state-of-the-art in photodetectors based on semiconducting 2D materials, focusing on the transition metal dichalcogenides, novel van der Waals materials, black phosphorus, and heterostructures.

Entropy-driven formation of large icosahedral colloidal clusters by spherical confinement.

Icosahedral symmetry, which is not compatible with truly long-range order, can be found in many systems, such as liquids, glasses, atomic clusters, quasicrystals and virus-capsids. To obtain arrangements with a high degree of icosahedral order from tens of particles or more, interparticle attractive interactions are considered to be essential. Here, we report that entropy and spherical confinement suffice for the formation of icosahedral clusters consisting of up to 100,000 particles. Specifically, by using real-space measurements on nanometre- and micrometre-sized colloids, as well as computer simulations, we show that tens of thousands of hard spheres compressed under spherical confinement spontaneously crystallize into icosahedral clusters that are entropically favoured over the bulk face-centred cubic crystal structure. Our findings provide insights into the interplay between confinement and crystallization and into how these are connected to the formation of icosahedral structures.

Photovoltaic and photothermoelectric effect in a double-gated WSe2 device.

Tungsten diselenide (WSe2), a semiconducting transition metal dichalcogenide (TMDC), shows great potential as active material in optoelectronic devices due to its ambipolarity and direct bandgap in its single-layer form. Recently, different groups have exploited the ambipolarity of WSe2 to realize electrically tunable PN junctions, demonstrating its potential for digital electronics and solar cell applications. In this Letter, we focus on the different photocurrent generation mechanisms in a double-gated WSe2 device by measuring the photocurrent (and photovoltage) as the local gate voltages are varied independently in combination with above- and below-bandgap illumination. This enables us to distinguish between two main photocurrent generation mechanisms, the photovoltaic and photothermoelectric effect. We find that the dominant mechanism depends on the defined gate configuration. In the PN and NP configurations, photocurrent is mainly generated by the photovoltaic effect and the device displays a maximum responsivity of 0.70 mA/W at 532 nm illumination and rise and fall times close to 10 ms. Photocurrent generated by the photothermoelectric effect emerges in the PP configuration and is a factor of 2 larger than the current generated by the photovoltaic effect (in PN and NP configurations). This demonstrates that the photothermoelectric effect can play a significant role in devices based on WSe2 where a region of strong optical absorption, caused by, for example, an asymmetry in flake thickness or optical absorption of the electrodes, generates a sizable thermal gradient upon illumination.

Photovoltaic effect in few-layer black phosphorus PN junctions defined by local electrostatic gating.

In conventional photovoltaic solar cells, photogenerated carriers are extracted by the built-in electric field of a semiconductor PN junction, defined by ionic dopants. In atomically thin semiconductors, the doping level can be controlled by the field effect, enabling the implementation of electrically tunable PN junctions. However, most two-dimensional (2D) semiconductors do not show ambipolar transport, which is necessary to realize PN junctions. Few-layer black phosphorus (b-P) is a recently isolated 2D semiconductor with direct bandgap, high mobility, large current on/off ratios and ambipolar operation. Here we fabricate few-layer b-P field-effect transistors with split gates and hexagonal boron nitride dielectric. We demonstrate electrostatic control of the local charge carrier type and density in the device. Illuminating a gate-defined PN junction, we observe zero-bias photocurrents and significant open-circuit voltages due to the photovoltaic effect. The small bandgap of the material allows power generation for illumination wavelengths up to 940 nm, attractive for energy harvesting in the near-infrared.

Fast and broadband photoresponse of few-layer black phosphorus field-effect transistors.

Few-layer black phosphorus, a new elemental two-dimensional (2D) material recently isolated by mechanical exfoliation, is a high-mobility layered semiconductor with a direct bandgap that is predicted to strongly depend on the number of layers, from 0.35 eV (bulk) to 2.0 eV (single layer). Therefore, black phosphorus is an appealing candidate for tunable photodetection from the visible to the infrared part of the spectrum. We study the photoresponse of field-effect transistors (FETs) made of few-layer black phosphorus (3-8 nm thick), as a function of excitation wavelength, power, and frequency. In the dark state, the black phosphorus FETs can be tuned both in hole and electron doping regimes allowing for ambipolar operation. We measure mobilities in the order of 100 cm(2)/V s and a current ON/OFF ratio larger than 10(3). Upon illumination, the black phosphorus transistors show a response to excitation wavelengths from the visible region up to 940 nm and a rise time of about 1 ms, demonstrating broadband and fast detection. The responsivity reaches 4.8 mA/W, and it could be drastically enhanced by engineering a detector based on a PN junction. The ambipolar behavior coupled to the fast and broadband photodetection make few-layer black phosphorus a promising 2D material for photodetection across the visible and near-infrared part of the electromagnetic spectrum.