Rashba Spin Splitting Limiting the Application of 2D Halide Perovskites for UV-Emitting Devices.

Layered lead halide perovskites have attracted much attention as promising materials for a new generation of optoelectronic devices. To make progress in applications, a full understanding of the basic properties is essential. Here, we study 2D-layered (BA)2PbX4 by using different halide anions (X = I, Br, and Cl) along with quantum confinement. The obtained cell parameter evolution, supported by experimental measurements and theoretical calculations, indicates strong lattice distortions of the metal halide octahedra, breaking the local inversion symmetry in (BA)2PbCl4, which strongly correlates with a pronounced Rashba spin-splitting effect. Optical measurements reveal strong photoluminescence quenching and a drastic reduction in the PL quantum yield in this larger band gap compound. We suggest that these optical results are closely related to the appearance of the Rashba effect due to the existence of a local electric dipole. The results obtained in ab initio calculations showed that the (BA)2PbCl4 possesses electrical polarization of 0.13 µC/cm2 and spin-splitting energy of about 40 meV. Our work establishes that local octahedra distortions induce Rashba spin splitting, which explains why obtaining UV-emitting materials with high PLQY is a big challenge.

Comparing the Cubic and Tetragonal Phases of MAPbI3 at Room Temperature.

Stability and maintenance of the crystal structure are the main drawbacks of the application of organic-inorganic perovskites in photovoltaic devices. The ΔT = 62 K robust shift of the structural phase transition observed here allows us to conduct a comprehensive study at room temperature of the tetragonal versus cubic phase on MAPbI3. The absence of the shift in the cubic transition for all-inorganic CsPbI3 samples confirms the importance of both orientation and dynamics of the organic cations. Our results provide a unique opportunity to evaluate the physical properties of both cubic and tetragonal phases of MAPbI3 at the same temperature, eliminating different phonon effects as possible causes for different properties. Besides higher electrical resistivity, the perovskite cubic phase presents a faster charge carrier lifetime than the tetragonal phase and partial PL quenching, pointing toward increased trap-assisted nonradiative recombination. The light absorption coefficient in the cubic phase is larger than the absorption in the tetragonal phase in the green region.

High-throughput inverse design and Bayesian optimization of functionalities: spin splitting in two-dimensional compounds.

The development of spintronic devices demands the existence of materials with some kind of spin splitting (SS). In this Data Descriptor, we build a database of ab initio calculated SS in 2D materials. More than that, we propose a workflow for materials design integrating an inverse design approach and a Bayesian inference optimization. We use the prediction of SS prototypes for spintronic applications as an illustrative example of the proposed workflow. The prediction process starts with the establishment of the design principles (the physical mechanism behind the target properties), that are used as filters for materials screening, and followed by density functional theory (DFT) calculations. Applying this process to the C2DB database, we identify and classify 358 2D materials according to SS type at the valence and/or conduction bands. The Bayesian optimization captures trends that are used for the rationalized design of 2D materials with the ideal conditions of band gap and SS for potential spintronics applications. Our workflow can be applied to any other material property.

Machine Learning Study of the Magnetic Ordering in 2D Materials.

Magnetic materials have been applied in a large variety of technologies, from data storage to quantum devices. The development of two-dimensional (2D) materials has opened new arenas for magnetic compounds, even when classical theories discourage their examination. Here we propose a machine-learning-based strategy to predict and understand magnetic ordering in 2D materials. This strategy couples the prediction of the existence of magnetism in 2D materials using a random forest and the Shapley additive explanations method with material maps defined by atomic features predicting the magnetic ordering (ferromagnetic or antiferromagnetic). While the random forest model predicts magnetism with an accuracy of 86%, the material maps obtained by the sure independence screening and sparsifying method have an accuracy of ∼90% in predicting the magnetic ordering. Our model indicates that 3d transition metals, halides, and structural clusters with regular transition-metal sublattices have a positive contribution in the total weight deciding the existence of magnetism in 2D compounds. This behavior is associated with the competition between crystal field and exchange splitting. The machine learning model also indicates that the atomic spin orbit coupling (SOC) is a determinant feature for the identification of the patterns separating ferro- from antiferromagnetic order. The proposed strategy is used to identify novel 2D magnetic compounds that, together with the fundamental trends in the chemical and structural space, pave novel routes for experimental exploration.

Intrinsic doping limitations in inorganic lead halide perovskites.

Inorganic halide perovskites (HP's) of the CsPbX3 (X = I, Br, Cl) type have reached prominence in photovoltaic solar cell efficiencies, leading to the expectation that they are a new class of semiconductors relative to the traditional ones. Peculiarly, they have shown an asymmetry in their ability to be doped by holes vs. electrons. Indeed, both structural defect-induced doping as well as extrinsic impurity-induced doping strangely often result in HP's in a unipolar doping (dominantly p-type) with low free carriers' concentration. This raises the question whether such doping limitations presents just a temporary setback due to insufficient optimization of the doping process, or perhaps this represents an intrinsic, physically-mandated bottleneck. In this paper we study three fundamental Design Principles (DP's) for ideal doping, applying them via density functional doping theory to these HP's, thus identifying the violated DP that explains the doping limitations and asymmetry in these HP's. Here, the target DP are: (i) requires that the thermodynamic transition level between different charge states induced by the dopants must ideally be energetically shallow both for donors (n-type) or acceptors (p-type); DP-(ii) requires that the 'Fermi level pinning energies' for electrons E(n)pin and holes E(p)pin (being the limiting value of the Fermi level before a structural defect that compensate the doping forms spontaneously) should ideally be located inside the conduction band for n-type doping and inside the valence band for p-type doping. DP-(iii) requires that the doping-induced shift in equilibrium Fermi energy ΔE(n)F towards the conduction band for n-type doping (shift of ΔE(p)F towards the valence band, for p-type doping) to be sufficiently large. We find that, even though in HP's based on Br and Cl there are numerous shallow level dopants that satisfy DP-(i), in contrast DP-(ii) is satisfied only for holes and DP-(iii) fails for both holes and electrons, being the ultimate bottleneck for the n-type doping in Iodide HP's. This suggests an intrinsic mechanism for doping limitations in this class of semiconductors in terms of recognized physical mechanisms.

Controlling the Activation Energy for Single-Ion Diffusion through a Hybrid Polyelectrolyte Matrix by Manipulating the Central Coordinate Semimetal Atom.

The diffusion of lithium ions decoupled from a solid polymer electrolyte matrix is the key for high-energy electrochemical devices with the safety needed for commercial use. This Letter reports how the ion mobility in a single-phase hybrid polyelectrolyte (SPHP) matrix can be tuned by changing an inorganic coordinating atom from silicon (Si) to germanium (Ge). Nuclear Magnetic Resonance (NMR) results show that the lithium ion activation barrier in the polyelectrolyte with Si can be modulated from 0.26 eV to the unprecedented value of 0.12 eV in the polyelectrolyte with Ge. Density functional theory is used to show that the electronic structures of both polymers are very different, although their chemical structures are very similar, except for the coordinating atom. This simple chemical substitution route will certainly increase the interest in these polymers for applications in electrochemical devices.

Antidoping in Insulators and Semiconductors Having Intermediate Bands with Trapped Carriers.

Ordinary doping by electrons (holes) generally means that the Fermi level shifts towards the conduction band (valence band) and that the conductivity of free carriers increases. Recently, however, some peculiar doping characteristics were sporadically recorded in different materials without noting the mechanism: electron doping was observed to cause a portion of the lowest unoccupied band to merge into the valance band, leading to a decrease in conductivity. This behavior, that we dub as "antidoping," was seen in rare-earth nickel oxides SmNiO_{3}, cobalt oxides SrCoO_{2.5}, Li-ion battery materials, and even MgO with metal vacancies. We describe the physical origin of antidoping as well as its inverse problem-the "design principles" that would enable an intelligent search of materials. We find that electron antidoping is expected in materials having preexisting trapped holes and is caused by the annihilation of such "hole polarons" via electron doping. This may offer an unconventional way of controlling conductivity.

Interaction of Water with the Gypsum (010) Surface: Structure and Dynamics from Nonlinear Vibrational Spectroscopy and Ab Initio Molecular Dynamics.

Water-mineral interfaces are important for several environmental, industrial, biological, and geological processes. Gypsum, CaSO4·2H2O, is a widespread mineral of high technological, medical, and environmental relevance, but little is known about its surface structure and its interaction with water. A molecular-level understanding of gypsum/water interface is given here by a combined experimental/theoretical study. We investigate the structure and dynamics of water adsorbed from vapor on the gypsum (010) single-crystal surface at room temperature, combining sum-frequency generation (SFG) vibrational spectroscopy experiments and ab initio molecular dynamics (AIMD) simulations. The SFG spectra of gypsum at low relative humidity (RH) show an anisotropic arrangement of structural water molecules and the presence of dangling OH groups. The AIMD simulations allow a detailed assignment of the SFG spectra and show that the cleaved (010) surface rearranges to have only 25% of the OH groups pointing away from the surface. At higher RHs, the first adsorbed water layer binds to these OH groups and forms an anisotropic arrangement, but with the amount of free OH groups significantly suppressed and without any significant diffusion. Upon adsorption of a second water layer, although the topmost layer of molecules is more disordered and dynamic than the previous one, its structure is still influenced by the gypsum surface underneath because it has a much reduced amount of free OH groups with respect to the free surface of water, and a slower surface diffusion with respect to bulk water. The theoretical results corroborate the experimental ones and provide an accurate atomic characterization of the surface structure.

Cobalt-doped ZnO nanocrystals: quantum confinement and surface effects from ab initio methods.

Cobalt-doped ZnO nanocrystals were studied through ab initio methods based on the Density Functional Theory. Both quantum confinement and surface effects were explicitly taken into account. When only quantum confinement effects are considered, Co atoms interact through a superexchange mechanism, stabilizing an antiferromagnetic ground state. Usually, this is the case for high quality nanoparticles with perfect surface saturation. When the surfaces were considered, a strong hybridization between the Co atoms and surfaces was observed, strongly changing their electronic and magnetic properties. Our results indicated that the surfaces might qualitatively change the properties of impurities in semiconductor nanocrystals.

Origin of FM ordering in pristine micro- and nanostructured ZnO.

An unexpected presence of ferromagnetic (FM) ordering in nanostructured nonmagnetic metal oxides has been reported previously. Though this property was attributed to the presence of defects, systematic experimental and theoretical studies to pinpoint its origin and mechanism are lacking. While it is widely believed that oxygen vacancies are responsible for FM ordering, surprisingly we find that annealing as-prepared samples at low temperature (high temperature) in flowing oxygen actually enhances (diminishes) the FM ordering. For these reasons, we have prepared, annealed in different environments, and measured the ensuing magnetization in micrometer and nanoscale ZnO with varying crystallinity. We further find from our magnetization measurements and ab initio calculations that a range of magnetic properties in ZnO can result, depending on the sample preparation and annealing conditions. For example, within the same ZnO sample we have observed ferro- to para- and diamagnetic responses depending on the annealing conditions. We also explored the effects of surface states on the magnetic behavior of nanoscale ZnO through detailed calculations.

Role of confinement on diffusion barriers in semiconductor nanocrystals.

We find that quantum size effects not only play an important role in the electronic properties of defects in semiconductor nanocrystals, but also strongly affect the incorporation of defect atoms into the nanocrystals. In particular, using ab initio methods based on density functional theory, we predict that Mn defects will be energetically driven towards the surface of CdSe and ZnSe nanocrystals, and that the diffusion barrier of a Mn interstitial defect in a CdSe nanocrystal will be significantly lower than that in the bulk.

Energetic pinning of magnetic impurity levels in quantum-confined semiconductors.

Donor- and acceptor-type (D/A) impurities play central roles in controlling the physical properties of semiconductors. With continued miniaturization of information processing devices, the relationship between quantum confinement and D/A ionization energies becomes increasingly important. Here, we provide direct spectroscopic evidence that impurity D/A levels in doped semiconductor nanostructures are energetically pinned, resulting in variations in D/A binding energies with increasing quantum confinement. Using magnetic circular dichroism spectroscopy, the donor binding energies of Co2+ ions in colloidal ZnSe quantum dots have been measured as a function of quantum confinement and analyzed in conjunction with ab initio density functional theory calculations. The resulting experimental demonstration of pinned impurity levels in quantum dots has far-reaching implications for physical phenomena involving impurity-carrier interactions in doped semiconductor nanostructures, including in the emerging field of semiconductor spintronics where magnetic-dopant-carrier exchange interactions define the functionally relevant properties of diluted magnetic semiconductors.

Self-purification in semiconductor nanocrystals.

Doping of nanocrystals is an important and very difficult task. "Self-purification" mechanisms are often claimed to make this task even more difficult, as the distance a defect or impurity must move to reach the surface of a nanocrystal is very small. We show that self-purification can be explained through energetic arguments and is an intrinsic property of defects in semiconductor nanocrystals. We find the formation energies of defects increases as the size of the nanocrystal decreases. We analyze the case of Mn-doped CdSe nanocrystals and compare our results to experimental findings.

Symmetry considerations in CdSe nanocrystals.

Semiconductor nanocrystals or quantum dots show a wide range of physical properties depending on their size or shape. In this paper, we show that symmetry is also an important characteristic that can lead to different electronic and optical properties. We use pseudopotential density-functional theory, within a real space approach, and address the sensitivity of electronic and optical properties with respect to the symmetry point groups associated to CdSe nanocrystals.

Hole-mediated stabilization of cubic GaN.

We propose here a new approach to stabilize the cubic zinc-blende (ZB) phase by incorporation of impurities into a compound that has a hexagonal wurtzite (WZ) ground state. For GaN, we suggest that this can be achieved by adding 3d acceptors such as Zn, Mn, or Cu because the p-d repulsion between the 3d impurity levels and the valence band maximum is larger in the ZB phase than in the WZ phase. This makes the top of the valence states of the ZB structure higher than that of the WZ structure. As holes are created at the top of the valence states by the impurities, it will cost less energy for the holes to be created in the ZB structure, thus stabilizing this phase. Our first-principles total energy calculations confirm this novel idea.