Cumulative polarization in conductive interfacial ferroelectrics.

Ferroelectricity in atomically thin bilayer structures has been recently predicted1 and measured2-4 in two-dimensional materials with hexagonal non-centrosymmetric unit-cells. The crystal symmetry translates lateral shifts between parallel two-dimensional layers to sign changes in their out-of-plane electric polarization, a mechanism termed 'slide-tronics'4. These observations have been restricted to switching between only two polarization states under low charge carrier densities5-12, limiting the practical application of the revealed phenomena13. To overcome these issues, one should explore the nature of polarization in multi-layered van der Waals stacks, how it is governed by intra- and interlayer charge redistribution and to what extent it survives the addition of mobile charge carriers14. To explore these questions, we conduct surface potential measurements of parallel WSe2 and MoS2 multi-layers with aligned and anti-aligned configurations of the polar interfaces. We find evenly spaced, nearly decoupled potential steps, indicating highly confined interfacial electric fields that provide a means to design multi-state 'ladder-ferroelectrics'. Furthermore, we find that the internal polarization remains notable on electrostatic doping of mobile charge carrier densities as high as 1013 cm-2, with substantial in-plane conductivity. Using density functional theory calculations, we trace the extra charge redistribution in real and momentum spaces and identify an eventual doping-induced depolarization mechanism.

Polarization Saturation in Multilayered Interfacial Ferroelectrics.

Van der Waals polytypes of broken inversion and mirror symmetries  have been recently shown to exhibit switchable electric polarization even at the ultimate two-layer thin limit. Their out-of-plane polarization has been found to accumulate in a ladder-like fashion with each successive layer, offering 2D building blocks for the bottom-up construction of 3D ferroelectrics. Here, it is demonstrated experimentally that beyond a critical stack thickness, the accumulated polarization in rhombohedral polytypes of molybdenum disulfide saturates. The underlying saturation mechanism, deciphered via density functional theory and self-consistent Poisson-Schrödinger calculations, point to a purely electronic redistribution involving: 1. Polarization-induced bandgap closure that allows for cross-stack charge transfer and the emergence of free surface charge; 2. Reduction of the polarization saturation value, as well as the critical thickness at which it is obtained, by the presence of free carriers. The resilience of polar layered structures to atomic surface reconstruction, which is essentially unavoidable in polar 3D crystals, potentially allows for the design of new devices with mobile surface charges. The findings, which are of general nature, should be accounted for when designing switching and/or conductive devices based on ferroelectric layered materials.

Excitonic signatures of ferroelectric order in parallel-stacked MoS2.

Interfacial ferroelectricity, prevalent in various parallel-stacked layered materials, allows switching of out-of-plane ferroelectric order by in-plane sliding of adjacent layers. Its resilience against doping potentially enables next-generation storage and logic devices. However, studies have been limited to indirect sensing or visualization of ferroelectricity. For transition metal dichalcogenides, there is little knowledge about the influence of ferroelectric order on their intrinsic valley and excitonic properties. Here, we report direct probing of ferroelectricity in few-layer 3R-MoS2 using reflectance contrast spectroscopy. Contrary to a simple electrostatic perception, layer-hybridized excitons with out-of-plane electric dipole moment remain decoupled from ferroelectric ordering, while intralayer excitons with in-plane dipole orientation are sensitive to it. Ab initio calculations identify stacking-specific interlayer hybridization leading to this asymmetric response. Exploiting this sensitivity, we demonstrate optical readout and control of multi-state polarization with hysteretic switching in a field-effect device. Time-resolved Kerr ellipticity reveals direct correspondence between spin-valley dynamics and stacking order.

Rapid Spin Depolarization in the Layered 2D Ruddlesden-Popper Perovskite (BA)(MA)PbI.

We report temperature-dependent spectroscopy on the layered (n = 4) two-dimensional (2D) Ruddlesden-Popper perovskite (BA)(MA)PbI. Helicity-resolved steady-state photoluminescence (PL) reveals no optical degree of polarization. Time-resolved PL shows a photocarrier lifetime on the order of nanoseconds. From simultaneously recorded time-resolved differential reflectivity (TRΔR) and time-resolved Kerr ellipticity (TRKE), a photocarrier lifetime of a few nanoseconds and a spin relaxation time on the order of picoseconds was found. This stark contrast in lifetimes clearly explains the lack of spin polarization in steady-state PL. While we observe clear temperature-dependent effects on the PL dynamics that can be related to structural dynamics, spin relaxation is nearly T-independent. Our results highlight that spin relaxation in 2D (BA)(MA)PbI occurs at time scales faster than the exciton recombination time, which poses a bottleneck for applications aiming to utilize this degree of freedom.

Spin transport in polarization induced two-dimensional electron gas channel in c-GaN nano-wedges.

A two-dimensional electron gas (2DEG), which has recently been shown to develop in the central vertical plane of a wedge-shaped c-oriented GaN nanowall due to spontaneous polarization effect, offers a unique scenario, where the symmetry between the conduction and valence band is preserved over the entire confining potential. This results in the suppression of Rashba coupling even when the shape of the wedge is not symmetric. Here, for such a 2DEG channel, relaxation time for different spin projections is calculated as a function of donor concentration and gate bias. Our study reveals a strong dependence of the relaxation rate on the spin-orientation and density of carriers in the channel. Most interestingly, relaxation of spin oriented along the direction of confinement has been found to be completely switched off. Upon applying a suitable bias at the gate, the process can be switched on again. Exploiting this fascinating effect, an electrically driven spin-transistor has been proposed.

Photocurrent modulation under dual excitation in individual GaN nanowires.

The photo-response properties of vapor-liquid-solid (VLS) grown [101[combining macron]0] oriented individual GaN nanowires of the diameter ranging from 30 to 100 nm are investigated under the joint illumination of above and sub-bandgap lights. When illuminated with above-bandgap light, these wires show persistent photoconductivity (PPC) effects with long build-up and decay times. The study reveals the quenching of photoconductivity (PC) upon illumination with an additional sub-bandgap light. PC recovers when the sub-bandgap illumination is withdrawn. A rate equation model attributing the PPC effect to the entrapment of photo-generated holes in the surface states and the PC quenching effect on the sub-bandgap light driven release of the holes from the trapped states has been proposed. The average height of the capture barrier has been found to be about 400 meV. The study also suggests that the capture barrier has a broad distribution with an upper cut-off energy of ∼2 eV.