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Impact of electrodes on the extraction of shift current from a ferroelectric semiconductor SbSI

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 Added by Masao Nakamura Dr
 Publication date 2018
  fields Physics
and research's language is English




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Noncentrosymmetric bulk crystals generate photocurrent without any bias voltage. One of the dominant mechanisms, shift current, comes from a quantum interference of electron wave functions being distinct from classical current caused by electrons drift or diffusion. The dissipation-less nature of shift current, however, has not been fully verified presumably due to the premature understanding on the role of electrodes. Here we show that the photocurrent dramatically enhances by choosing electrodes with large work function for a $p$-type ferroelectric semiconductor SbSI. An optimized device shows a nearly constant zero-bias photocurrent despite significant variation in photocarrier mobility dependent on temperature, which could be a clear hallmark for the dissipation-less nature of shift current. Distinct from conventional photovoltaic devices, the shift current generator operates as a majority carrier device. The present study provides fundamental design principles for energy-harvesting and photo-detecting devices with novel architectures optimal for the shift current photovoltaic effect.



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80 - M. Sotome 2018
Photoexcitation in solids brings about transitions of electrons/holes between different electronic bands. If the solid lacks an inversion symmetry, these electronic transitions support spontaneous photocurrent due to the topological character of the constituting electronic bands; the Berry connection. This photocurrent, termed shift current, is expected to emerge on the time-scale of primary photoexcitation process. We observed ultrafast time evolution of the shift current in a prototypical ferroelectric semiconductor by detecting emitted terahertz electromagnetic waves. By sweeping the excitation photon energy across the band gap, ultrafast electron dynamics as a source of terahertz emission abruptly changes its nature, reflecting a contribution of Berry connection upon interband optical transition. The shift excitation carries a net charge flow, and is followed by a swing-over of the electron cloud on the sub-picosecond time-scale of electron-phonon interaction. Understanding these substantive characters of the shift current will pave the way for its application to ultrafast sensors and solar cells.
The bulk photovoltaic effect generates intrinsic photocurrents in materials without inversion symmetry. Shift current is one of the bulk photovoltaic phenomena related to the Berry phase of the constituting electronic bands: photo-excited carriers coherently shift in real space due to the difference in the Berry connection between the valence and conduction bands. Ferroelectric semiconductors and Weyl semimetals are known to exhibit such nonlinear optical phenomena. Here we consider chalcopyrite semiconductor ZnSnP$_2$ which lacks inversion symmetry and calculate the shift current conductivity. We find that the magnitude of the shift current is comparable to the recently measured values on other ferroelectric semiconductors and an order of magnitude larger than bismuth ferrite. The peak response for both optical and shift current conductivity, which mainly comes from P-3$p$ and Sn-5$p$ orbitals, is several eV above the bandgap.
It is thought that the proposed new family of multi-functional materials namely the ferroelectric thermoelectrics may exhibit enhanced functionalities due to the coupling of the thermoelectric parameters with ferroelectric polarization in solids. Therefore, the ferroelectric thermoelectrics are expected to be of immense technological and fundamental significance. As a first step towards this direction, it is most important to identify the existing high performance thermoelectric materials exhibiting ferroelectricity. Herein, through the direct measurement of local polarization switching we show that the recently discovered thermoelectric semiconductor $AgSbSe_{2}$ has local ferroelectric ordering. Using piezo-response force microscopy, we demonstrate the existence of nanometer scale ferroelectric domains that can be switched by external electric field. These observations are intriguing as $AgSbSe_{2}$ crystalizes in cubic rock salt structure with centro-symmetric space group (Fm-3m) and therefore no ferroelectricity is expected. However, from high resolution transmission electron microscopy (HRTEM) measurement we found the evidence of local superstructure formation which, we believe, leads to local distortion of the centro-symmetric arrangement in $AgSbSe_{2}$ and gives rise to the observed ferroelectricity. Stereochemically active $5s^{2}$ lone pair of Sb can also give rise to local structural distortion, which creates ferroelectricity in $AgSbSe_{2}$.
365 - H. Kohlstedt 2005
We present the concept of ferroelectric tunnel junctions (FTJs). These junctions consist of two metal electrodes separated by a nanometer-thick ferroelectric barrier. The current-voltage characteristics of FTJs are analyzed under the assumption that the direct electron tunneling represents the dominant conduction mechanism. First, the influence of converse piezoelectric effect inherent in ferroelectric materials on the tunnel current is described. The calculations show that the lattice strains of piezoelectric origin modify the current-voltage relationship owing to strain-induced changes of the barrier thickness, electron effective mass, and position of the conduction-band edge. Remarkably, the conductance minimum becomes shifted from zero voltage due to the piezoelectric effect, and a strain-related resistive switching takes place after the polarization reversal in a ferroelectric barrier. Second, we analyze the influence of the internal electric field arising due to imperfect screening of polarization charges by electrons in metal electrodes. It is shown that, for asymmetric FTJs, this depolarizing-field effect also leads to a considerable change of the barrier resistance after the polarization reversal. However, the symmetry of the resulting current-voltage loop is different from that characteristic of the strain-related resistive switching. The crossover from one to another type of the hysteretic curve, which accompanies the increase of FTJ asymmetry, is described taking into account both the strain and depolarizing-field effects. It is noted that asymmetric FTJs with dissimilar top and bottom electrodes are preferable for the non-volatile memory applications because of a larger resistance on/off ratio.
We report the current-perpendicular-to-plane giant magnetoresistance of a spin valve with Co2MnSi (CMS) Heusler alloy ferromagnetic electrodes. A multilayer stack of Cr/Ag/Cr/CMS/Cu/CMS/Fe25Co75/Ir28Mn72/Ru was deposited on a MgO (001) single crystal substrate. The bottom CMS layer was epitaxially grown on the Cr/Ag/Cr buffer layers and was ordered to the L21 structure after annealing at 673 K. The upper CMS layer was found to grow epitaxially on the Cu spacer layer despite the large lattice mismatch between Cu and CMS. The highest MR ratios of 8.6% and 30.7% for CPP-GMR were recorded at room temperature and 6 K, respectively. The high spin polarization of the epitaxial CMS layers is the most likely origin of the high MR ratio.
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