Low-dimensional multiferroic materials hold great promises in miniaturized device applications such as nanoscale transducers, actuators, sensors, photovoltaics, and nonvolatile memories. Here, using first-principles theory we predict that two-dimensional (2D) monolayer group IV monochalcogenides including GeS, GeSe, SnS, and SnSe are a class of 2D semiconducting multiferroics with giant strongly-coupled in-plane spontaneous ferroelectric polarization and spontaneous ferroelastic lattice strain that are thermodynamically stable at room temperature and beyond, and can be effectively modulated by elastic strain engineering. Their optical absorption spectra exhibit strong in-plane anisotropy with visible-spectrum excitonic gaps and sizable exciton binding energies, rendering the unique characteristics of low-dimensional semiconductors. More importantly, the predicted low domain wall energy and small migration barrier together with the coupled multiferroic order and anisotropic electronic structures suggest their great potentials for tunable multiferroic functional devices by manipulating external electrical, mechanical, and optical field to control the internal responses, and enable the development of four device concepts including 2D ferroelectric memory, 2D ferroelastic memory, and 2D ferroelastoelectric nonvolatile photonic memory as well as 2D ferroelectric excitonic photovoltaics.

Magnesium rechargeable batteries potentially offer high-energy density, safety, and low cost due to the ability to employ divalent, dendrite-free, and earth-abundant magnesium metal anode. Despite recent progress, further development remains stagnated mainly due to the sluggish scission of magnesium-chloride bond and slow diffusion of divalent magnesium cations in cathodes. Here we report a battery chemistry that utilizes magnesium monochloride cations in expanded titanium disulfide. Combined theoretical modeling, spectroscopic analysis, and electrochemical study reveal fast diffusion kinetics of magnesium monochloride cations without scission of magnesium-chloride bond. The battery demonstrates the reversible intercalation of 1 and 1.7 magnesium monochloride cations per titanium at 25 and 60 °C, respectively, corresponding to up to 400 mAh g−1 capacity based on the mass of titanium disulfide. The large capacity accompanies with excellent rate and cycling performances even at room temperature, opening up possibilities for a variety of effective intercalation hosts for multivalent-ion batteries.

Nonlinear optical properties of materials such as second and higher order harmonic generation and electro-optic effect play pivotal roles in lasers, frequency conversion, electro-optic modulators, switches, and so forth. The strength of nonlinear optical responses highly depends on intrinsic crystal symmetry, transition dipole moments, specific optical excitation, and local environment. Using first-principles electronic structure theory, here we predict giant second harmonic generation (SHG) in recently discovered two-dimensional (2D) ferroelectric-ferroelastic multiferroics-group IV monochalcogenides (i.e., GeSe, GeS, SnSe, and SnS). Remarkably, the strength of SHG susceptibility in GeSe and SnSe monolayers is more than 1 order of magnitude higher than that in monolayer MoS, and 2 orders of magnitude higher than that in monolayer hexagonal BN. Their extraordinary SHG is dominated by the large residual of two opposite intraband contributions in the SHG susceptibility. More importantly, the SHG polarization anisotropy is strongly correlated with the intrinsic ferroelastic and ferroelectric orders in group IV monochalcogenide monolayers. Our present findings provide a microscopic understanding of the large SHG susceptibility in 2D group IV monochalcogenide multiferroics from first-principles theory and open up a variety of new avenues for 2D ferroelectrics, multiferroics, and nonlinear optoelectronics, for example, realizing active electrical/optical/mechanical switching of ferroic orders in 2D multiferroics and in situ ultrafast optical characterization of local atomistic and electronic structures using noncontact noninvasive optical SHG techniques.

We report the strong light-induced activation of forbidden exciton transition in CsPbBr 3 perovskite quantum dots mediated by the symmetry-breaking polaron that modifies the optical selection rule of the confined exciton transition. The activated forbidden transition results in an intense pump-induced absorption in the transient absorption spectra above the bandgap, where the original parity-forbidden transition was located. In contrast to many other semiconductor quantum dots, photoexcitation of an exciton in CsPbBr 3 quantum dots creates a sufficiently large perturbation via a lattice-distorting polaron, which turns on the formally forbidden transition. Compared to the bulk or weakly confined CsPbBr 3 , the activation of the forbidden transition in strongly confined quantum dots is much more prominent due to the stronger influence of the polaron on exciton transitions in the confined space. This nonlinear optical property highlights the intimate coupling of the photoexcited charge carriers with the lattice in the CsPbBr 3 quantum dots, allowing access to the forbidden exciton transitions with light.

Low-dimensional multiferroicity, though highly scarce in nature, has attracted great attention due to both fundamental and technological interests. Using first-principles density functional theory, we show that ferromagnetism and ferroelectricity can coexist in monolayer transition metal phosphorus chalcogenides (TMPCs) -CuMP 2 X 6 (M=Cr, V; X=S, Se). These van der Waals layered materials represent a class of 2D multiferroic semiconductors that simultaneously possess ferroelectric and ferromagnetic orders. In these monolayer materials, Cu atoms spontaneously move away from the center atomic plane, giving rise to nontrivial electric dipole moment along the plane normal. In addition, their ferromagnetism originates from indirect exchange interaction between Cr/V atoms, while their out-of-plane ferroelectricity suggests the possibility of controlling electric polarization by external vertical electric field. Monolayer semiconducting TMPCs thus provide a solid-state 2D materials platform for realizing 2D nanoscale switches and memory devices patterned with top and bottom electrodes. a)

Novel materials with nontrivial electronic and photonic band topology are crucial for realizing novel devices with low power consumption and heat dissipation, and quantum computing free of decoherence. Here using first-principles approach, we predict a class of ternary transition metal chalcogenides (TTMC) MM'Te 4 exhibits dual topological characteristics: quantum spin Hall (QSH) insulators in their 2D monolayers and topological Weyl semimetals in their 3D noncentrosymmetric crystals upon van der Waals (vdW) stacking.Remarkably, we find that one can create and annihilate Weyl fermions, and realize the transition between Type-I and Type-II Weyl fermions by tuning vdW interlayer spacing. Our calculations show that they possess excellent thermodynamic stability and weak interlayer binding, implying their great potentials for experimental synthesis, direct exfoliation and vdW heterostacking.Moreover, their ternary nature will offer more tunability for electronic structure by controlling different stoichiometry and valence charges. Our findings provide an ideal materials platform for realizing QSH effect and exploring topological phase transition, and will open up a variety of new opportunities for two-dimensional materials and topological materials research.

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Nonlinear optical responses to external electromagnetic field, characterized by second- and higher-order susceptibilities, play crucial roles in nonlinear optics and optoelectronics. Here, we demonstrate the possibility to achieve ferroicity-driven nonlinear photocurrent switching in time-reversal invariant multiferroics. It is enabled by the second-order current response to electromagnetic field whose direction can be controlled by both internal ferroic orders and external light polarization. Second-order direct photocurrent consists of shift current and circular photocurrent under linearly and circularly polarized light irradiation, respectively. We elucidate the microscopic mechanism in a representative class of two-dimensional multiferroic materials using group theoretical analyses and first-principles theory. The complex interplay of symmetries, shift vector, and Berry curvature governs the fundamental properties and switching behavior of shift current and circular photocurrent. Ferroicity-driven nonlinear photocurrent switching will open avenues for realizing nonlinear optoelectronics, nonlinear multiferroics, etc., using the coupled ferroic orders and nonlinear responses of ferroic materials under external field.