The mathematical field of topology has become a framework to describe the low-energy electronic structure of crystalline solids. A typical feature of a bulk insulating three-dimensional topological crystal are conducting two-dimensional surface states. This constitutes the topological bulk-boundary correspondence. Here, we establish that the electronic structure of bismuth, an element consistently described as bulk topologically trivial, is in fact topological and follows a generalized bulk-boundary correspondence of higher-order: not the surfaces of the crystal, but its hinges host topologically protected conducting modes. These hinge modes are protected against localization by time-reversal symmetry locally, and globally by the three-fold rotational symmetry and inversion symmetry of the bismuth crystal. We support our claim theoretically and experimentally. Our theoretical analysis is based on symmetry arguments, topological indices, first-principle calculations, and the recently introduced framework of topological quantum chemistry. We provide supporting evidence from two complementary experimental techniques. With scanning-tunneling spectroscopy, we probe the unique signatures of the rotational symmetry of the one-dimensional states located at step edges of the crystal surface. With Josephson interferometry, we demonstrate their universal topological contribution to the electronic transport. Our work establishes bismuth as a higher-order topological insulator.
While the basic principles of conventional solar cells are well understood, little attention has gone towards maximizing the efficiency of photovoltaic devices based on shift currents. By analysing effective models, here we outline simple design principles for the optimization of shift currents for frequencies near the band gap. Our method allows us to express the band edge shift current in terms of a few model parameters and to show it depends explicitly on wavefunctions in addition to standard band structure. We use our approach to identify two classes of shift current photovoltaics, ferroelectric polymer films and single-layer orthorhombic monochalcogenides such as GeS, which display the largest band edge responsivities reported so far. Moreover, exploring the parameter space of the tight-binding models that describe them we find photoresponsivities that can exceed 100 mA W−1. Our results illustrate the great potential of shift current photovoltaics to compete with conventional solar cells.
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