Polarization-Controlled Surface Defect Formation in a Hybrid Perovskite.

Hybrid perovskites have two properties that are absent in traditional inorganic photovoltaic materials, namely, polarization and mobile ionic defects, the interaction between which may introduce new features into the materials. By using the first-principles calculations, we find that the formation energies of the vacancy defects at a tetragonal MAPbI3(110) surface are highly related to the surface polarization. The positive total polarization and local polarization of MA facilitate the formation of surface MA vacancies, whereas the negative total polarization and local polarization of MAI are favorable for the formation of surface iodine vacancies. The phenomena can be explained quantitatively on the basis of the two kinds of Coulomb interactions between the charged defect and the polarization-induced electrostatic field. The comprehensive insights into the interaction between the polarization and the ionic defects in hybrid perovskites can provide a new avenue for defect control for high-performance perovskite solar cells via surface polarization.

Intrinsic interaction between in-plane ferroelectric polarization and surface adsorption.

The chemical properties of a ferroelectric surface are polarization dependent, the underlying nature of which is, however, far from being completely understood. One of the reasons is that when the polarization direction is perpendicular to the surface, the depolarization field may induce electronic or atomic reconstruction and thus change the chemistry of the ferroelectric surface in complicated ways. Instead, the in-plane polarization results in no depolarization field. Therefore, the chemical properties of a ferroelectric surface can be more intrinsically reflected by the interplay between the in-plane polarization and the surface adsorption. By using first-principles calculations, we study the effect of the strain-induced in-plane polarization on the adsorption of a series of molecules on the reduced rutile TiO2(110) surface. We reveal that it is the surface doping caused by the charge transfer between the adsorbates and the TiO2(110) surface that dominates the polarization-induced change of the adsorption energy, as a result of screening long-range Coulomb interactions. The electrostatic interaction between the polarization of the substrate and the polar molecule is of relatively less importance. We propose that charge transfer effects generally occur for ferroelectric surfaces with no localized surface states.

Influence of strain on water adsorption and dissociation on rutile TiO2(110) surface.

The influence of externally applied strain on water adsorption and dissociation on a defect-free rutile TiO2(110) surface is studied by using first-principles calculations. We found that while compressive strain makes water adsorption and dissociation less favorable, tensile strain increases the energy gain of water adsorption, and decreases the energy cost of water dissociation. Specifically, dissociative water becomes more stable than molecular water when an 8% tensile in-plane strain is applied. Moreover, the dissociation barrier decreases with increasing strain more rapidly for more isolated water. The rate of decrease of this barrier for nearly isolated water is 0.017 eV per 1% biaxial strain. This demonstrates that applying strain is a possible way to engineer the surface adsorption and dissociation of water on a TiO2(110) surface, and therefore engineer the relevant surface reactivity.

Active sites and mechanisms for oxygen reduction reaction on nitrogen-doped carbon alloy catalysts: Stone-Wales defect and curvature effect.

Carbon alloy catalysts (CACs) are promising oxygen reduction reaction (ORR) catalysts to substitute platinum. However, despite extensive studies on CACs, the reaction sites and mechanisms for ORR are still in controversy. Herein, we present rather general consideration on possible ORR mechanisms for various structures in nitrogen doped CACs based on the first-principles calculations. Our study indicates that only a particular structure of a nitrogen pair doped Stone-Wales defect provides a good active site. The ORR activity of this structure can be tuned by the curvature around the active site, which makes its limiting potential approaching the maximum limiting potential (0.80 V) in the volcano plot for the ORR activity of CACs. The calculated results can be compared with the recent experimental ones of the half-wave potential for CAC systems that range from 0.60 to 0.80 V in the reversible-hydrogen-electrode (RHE) scale.

Tuning the area percentage of reactive surface of TiO2 by strain engineering.

Surfaces with high reactivity usually have a low area percentage, which greatly limits the efficiency of surface reactivity. In this Letter we demonstrate a generic way of increasing the percentage of the highly reactive surface by using external strain. Bulk and surface elastic properties of TiO2 are studied via density functional theory calculations. The equilibrium shape of anatase TiO2 under applied strain is discussed based on the elastic properties. We find that when 5% compressive strain is applied biaxially along [100] and [010]; directions, the area percentage of the anatase (001) surface can be increased by ~5 times in comparison with the case when no strain is applied. Since the moderate strain does not introduce extrinsic defects into the material, we propose that it is an ideal way to increase the reactivity of titanium dioxide crystallites by applying biaxial compressive external strain along the a axis.

Self-templating growth of copper nanopearl-chain arrays in electrodeposition.

We report here a unique in-plane self-templating electrochemical growth of arrays of copper nanopearl chains from an ultrathin layer of CuSO4 electrolyte. Scanning electron microscopy indicates that the electrodeposit filaments form equally spaced bundles, which consist of long, straight, pearl-chain-like copper filaments with corrugated periodic structure. The bundle separation can be tuned by changing the applied electric current in electrodeposition. Experiments show that the periodic morphology on the nanopearl chain corresponds to the periodic distribution of copper and cuprous oxide. The mechanism for the bundle formation is discussed.

Interplay between external strain and oxygen vacancies on a rutile TiO2(110) Surface.

Comprehensive first-principle calculations on strained rutile TiO2(110) indicate that the formation energy of different types of oxygen vacancies depends on the external strain. For the unstrained state, the energetically favorable oxygen vacancy (EFOV) appears on the bridging site of the first layer; when 3% tensile strain along [11[over ]0] is applied, EFOV moves to the in-plane site, while 2% compressive strain along either [001] or [11[over ]0] shifts EFOV to the subbridging site. We therefore suggest that the distribution of oxygen vacancies can be engineered by external strain, which may help to improve the applications of a TiO2 surface where oxygen vacancy plays an important role.

Role of interference between localized and propagating surface waves on the extraordinary optical transmission through a subwavelength-aperture array.

We report in this Letter that when radiation is incident on a metal surface perforated with an array of ring-shaped subwavelength apertures, the phase difference between the propagating surface Bloch wave and the localized surface wave can be tailored by the geometrical parameters of the array so as to affect the shape of the transmission spectrum. Above the resonant frequency of the aperture, interference between the two kinds of surface waves leads to a minimum in the transmission spectrum, whereas below it, the interference leads to a maximum. We suggest that this feature provides flexibility in engineering surface-wave-based all-optical devices.

Consecutive rotation of crystallographic orientation in lateral growth.

A consecutive rotation of crystallographic orientation has been observed in lateral crystallization of NH4Cl on a glass substrate, which induces a periodic distribution of faceted and roughened regions on the surface of a crystallite aggregate. Experimental observation indicates that this phenomenon derives from the asymmetric surface energies at the growth front, which deform the nascent nucleus and tilt the crystallographic orientation in the nucleation-mediated layered growth. We suggest that this effect is significant for a class of lateral growth where nucleation plays a dominate role.