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Journal ArticleDOI

Ultrafast Zero-Bias Photocurrent in GeS Nanosheets: Promise for Photovoltaics

23 May 2017-ACS energy letters (American Chemical Society)-Vol. 2, Iss: 6, pp 1429-1434
TL;DR: In this article, the terahertz electromagnetic pulses emitted by photoexcited GeS nanosheets without external bias were used to confirm that shift currents are indeed responsible for the observed emission.
Abstract: Ferroelectric semiconductors have been predicted to exhibit strong zero-bias shift current, spurring the search for ferroelectric semiconductors with band gaps in the visible range as candidates for so-called shift current photovoltaics with efficiencies not constrained by the Schockley–Queisser limit Recent theoretical works have predicted that two-dimensional IV–VI monochalcogenides are multiferroic and capable of generating significant shift currents Here we present experimental validation of this prediction, observing ultrafast shift currents by detecting terahertz electromagnetic pulses emitted by the photoexcited GeS nanosheets without external bias We explore excitation fluence, orientation, and excitation polarization dependence of the terahertz emission to confirm that shift currents are indeed responsible for the observed emission Experimental observation of zero-bias photocurrents puts GeS nanosheets forth as a promising candidate material for applications in third-generation photovoltaics
Citations
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Journal ArticleDOI
TL;DR: The application of ferroelectric materials (i.e. solids that exhibit spontaneous electric polarisation) in solar cells has a long and controversial history as mentioned in this paper, and the recent successful application of inorganic and hybrid perovskite structured materials (e.g. BiFeO3, CsSnI3, CH3NH3PbI3) emphasises that polar semiconductors can be used in conventional photovoltaic architectures.
Abstract: The application of ferroelectric materials (i.e. solids that exhibit spontaneous electric polarisation) in solar cells has a long and controversial history. This includes the first observations of the anomalous photovoltaic effect (APE) and the bulk photovoltaic effect (BPE). The recent successful application of inorganic and hybrid perovskite structured materials (e.g. BiFeO3, CsSnI3, CH3NH3PbI3) in solar cells emphasises that polar semiconductors can be used in conventional photovoltaic architectures. We review developments in this field, with a particular emphasis on the materials known to display the APE/BPE (e.g. ZnS, CdTe, SbSI), and the theoretical explanation. Critical analysis is complemented with first-principles calculation of the underlying electronic structure. In addition to discussing the implications of a ferroelectric absorber layer, and the solid state theory of polarisation (Berry phase analysis), design principles and opportunities for high-efficiency ferroelectric photovoltaics are presented.

248 citations

Journal ArticleDOI
TL;DR: In this paper, the authors explain recent progress in the experimental characterization and theoretical understanding of group-IV monochalcogenides, as well as their potential for device applications.
Abstract: Monolayers of group-IV monochalcogenides, such as GeS, GeSe, SnS, SnSe, and SnTe, display interesting properties such as ferroelectricity, ferroelasticity, and unusual spin textures. This makes these materials interesting from both fundamental and applied perspectives. This Colloquium explains recent progress in the experimental characterization and theoretical understanding as well as their potential for device applications.

83 citations


Cites background from "Ultrafast Zero-Bias Photocurrent in..."

  • ...…studied in bulk ferroelectrics (Ivchenko and Ganichev, 2016; Sturman and Sturman, 1992), topological insulators (Hosur, 2011), 2D ferroelectrics (Kushnir et al., 2019, 2017; Panday et al., 2019; Rangel et al., 2017), Weyl semimetals (Chan et al., 2017; de Juan et al., 2017; Rees et al., 2019;…...

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Journal ArticleDOI
TL;DR: In this article, the gas sensing properties of single-layer GeS have been studied by performing density functional theory (DFT) calculations, and the present results demonstrate that monolayer GeS exhibits high selectivity and sensitivity toward NO2 molecules and short recovery time, coupled with a strong anisotropic transport feature.
Abstract: The gas sensing properties of single-layer GeS have been studied by performing density functional theory (DFT) calculations, and the present results demonstrate that monolayer GeS exhibits high selectivity and sensitivity toward NO2 molecules and short recovery time, coupled with a strong anisotropic transport feature. Moreover, applying biaxial strains and electric fields could effectively modulate the capture and release of gaseous NO2. Further calculations indicate that oxygen atoms and water molecules decorated on GeS hardly affect the superb selectivity toward NO2 against the other gases. The presence of an S-vacancy on the GeS monolayer greatly promotes the adsorption of NO2, facilitating molecular dissociation. The underlying mechanism is also elaborated at the level of electronic structures. The present findings make GeS monolayers potential materials for NO2 gas sensors and capturers in future applications.

81 citations

Journal ArticleDOI
TL;DR: In this paper, the authors observed the evolution of the shift current in a prototypical ferroelectric semiconductor antimony sulfur iodide (SbSI) by detecting emitted terahertz electromagnetic waves.
Abstract: 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 geometric phase of the constituting electronic bands: the Berry connection. This photocurrent, termed shift current, is expected to emerge on the timescale of primary photoexcitation process. We observe ultrafast evolution of the shift current in a prototypical ferroelectric semiconductor antimony sulfur iodide (SbSI) by detecting emitted terahertz electromagnetic waves. By sweeping the excitation photon energy across the bandgap, ultrafast electron dynamics as a source of terahertz emission abruptly changes its nature, reflecting a contribution of Berry connection on interband optical transition. The shift excitation carries a net charge flow and is followed by a swing over of the electron cloud on a subpicosecond timescale. Understanding these substantive characters of the shift current with the help of first-principles calculation will pave the way for its application to ultrafast sensors and solar cells.

76 citations

Journal ArticleDOI
TL;DR: A facile, direct-current, steady-state method for unambiguous determination of shift by means of the simultaneous measurements of linear and circular bulk photovoltaic currents under magnetic field, in a sillenite piezoelectric crystal is reported.
Abstract: The quantum phenomenon of shift photovoltaic current was predicted decades ago, but this effect was never observed directly because shift and ballistic currents coexist. The atomic-scale relaxation time of shift, along with the absence of a photo-Hall behavior, has made decisive measurement of shift elusive. Here, we report a facile, direct-current, steady-state method for unambiguous determination of shift by means of the simultaneous measurements of linear and circular bulk photovoltaic currents under magnetic field, in a sillenite piezoelectric crystal. Comparison with theoretical predictions permits estimation of the signature length scale for shift. Remarkably, shift and ballistic photovoltaic currents under monochromatic illumination simultaneously flow in opposite directions. Disentangling the shift and ballistic contributions opens the way for quantitative, fundamental insight into and practical understanding of these radically different photovoltaic current mechanisms and their relationship.

63 citations

References
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Journal ArticleDOI
28 Nov 2013-Nature
TL;DR: The ability of KBNNO to absorb three to six times more solar energy than the current ferroElectric materials suggests a route to viable ferroelectric semiconductor-based cells for solar energy conversion and other applications.
Abstract: Most known ferroelectric photovoltaic materials have very wide electronic bandgaps (that is, they absorb only high-energy photons) but here a family of perovskite oxides is described that have tunable bandgaps, allowing their use across the whole visible-light spectrum. The spontaneous electrical polarization that characterizes a ferroelectric material is attractive for solar-cell applications as the positive and negative charges generated by light absorption have a natural tendency to separate, making them easier to harvest efficiently. Unfortunately most known ferroelectrics have wide electronic bandgaps — that is they absorb only higher energy photons that make up a small fraction of the solar spectrum. Ilya Grinberg and colleagues now show that a classic ferroelectric can be chemically engineered to tune the bandgap over a broad range, achieving strong absorption and photocurrent generation across the solar spectrum. Ferroelectrics have recently attracted attention as a candidate class of materials for use in photovoltaic devices, and for the coupling of light absorption with other functional properties1,2,3,4,5,6,7. In these materials, the strong inversion symmetry breaking that is due to spontaneous electric polarization promotes the desirable separation of photo-excited carriers and allows voltages higher than the bandgap, which may enable efficiencies beyond the maximum possible in a conventional p–n junction solar cell2,6,8,9,10. Ferroelectric oxides are also stable in a wide range of mechanical, chemical and thermal conditions and can be fabricated using low-cost methods such as sol–gel thin-film deposition and sputtering3,5. Recent work3,5,11 has shown how a decrease in ferroelectric layer thickness and judicious engineering of domain structures and ferroelectric–electrode interfaces can greatly increase the current harvested from ferroelectric absorber materials, increasing the power conversion efficiency from about 10−4 to about 0.5 per cent. Further improvements in photovoltaic efficiency have been inhibited by the wide bandgaps (2.7–4 electronvolts) of ferroelectric oxides, which allow the use of only 8–20 per cent of the solar spectrum. Here we describe a family of single-phase solid oxide solutions made from low-cost and non-toxic elements using conventional solid-state methods: [KNbO3]1 − x[BaNi1/2Nb1/2O3 − δ]x (KBNNO). These oxides exhibit both ferroelectricity and a wide variation of direct bandgaps in the range 1.1–3.8 electronvolts. In particular, the x = 0.1 composition is polar at room temperature, has a direct bandgap of 1.39 electronvolts and has a photocurrent density approximately 50 times larger than that of the classic ferroelectric (Pb,La)(Zr,Ti)O3 material. The ability of KBNNO to absorb three to six times more solar energy than the current ferroelectric materials suggests a route to viable ferroelectric semiconductor-based cells for solar energy conversion and other applications.

1,041 citations

Journal ArticleDOI
TL;DR: In this paper, the authors predict anisotropic piezoelectric effects in intrinsic monolayer group IV monochalcogenides (MX, M=Sn or Ge, X=Se or S), including SnSe, SnS, GeSe, and GeS.
Abstract: We predict enormous, anisotropic piezoelectric effects in intrinsic monolayer group IV monochalcogenides (MX, M=Sn or Ge, X=Se or S), including SnSe, SnS, GeSe, and GeS. Using first-principle simulations based on the modern theory of polarization, we find that their piezoelectric coefficients are about one to two orders of magnitude larger than those of other 2D materials, such as MoS2 and GaSe, and bulk quartz and AlN which are widely used in industry. This enhancement is a result of the unique “puckered” C2v symmetry and electronic structure of monolayer group IV monochalcogenides. Given the achieved experimental advances in the fabrication of monolayers, their flexible character, and ability to withstand enormous strain, these 2D structures with giant piezoelectric effects may be promising for a broad range of applications such as nano-sized sensors, piezotronics, and energy harvesting in portable electronic devices.

571 citations

Journal ArticleDOI
TL;DR: The photovoltaic effect in epitaxial BFO thin films is studied and an open-circuit voltage Voc of 0.3 V is obtained, demonstrating that photocurrent direction can be switched by the polarization direction of the BFO film and that the ferroelectric polarization is the main driving force of the observed photov Holtaic effect.
Abstract: Adv. Mater. 2010, 22, 1763–1766 2010 WILEY-VCH Verlag G T IO N While silicon-based diodes have been the dominant solar cell type, novel photovoltaic mechanisms are being explored in pursuit of lower cost or improved efficiency. In a semiconductor photodiode, such as a Si solar cell, photons with energy higher than the band gap are absorbed to produce electron-hole pairs, which are separated by the internal field in the p–n junction and collected with the electrodes. However, a p–n junction is not a prerequisite for the photovoltaic effect. For exitonic solar cells, photon absorption creates excitons, which dissociate at a heterojunction. In materials without a center of symmetry, such as ferroelectric materials, steady-state photocurrent can exist in a homogeneous medium under uniform illumination, a phenomenon called bulk photovoltaic effect (BPVE). BPVE is a fascinating mechanism with many unique features such as extremely large photovoltage, a photocurrent proportional to the polarization magnitude, and charge-carrier separation in homogeneous media. Observed in bulk ferroelectrics in as early as 1950s, BPVE has seen a resurgent interest recently, especially in ferroelectric thin films. It has been proposed that remarkably higher photovoltaic efficiency can be achieved in thin films. On the other hand, open-circuit voltage much larger than the band gap has also been achieved with ferroelectric thin films with in-plane interdigital electrodes, which has led to the development of UV sensors and dosimeters. The ferroelectric thin-film materials under the previous study, such as BaTiO3 and Pb(ZrTi)O3, have wide band gaps (typically larger than 3.3 eV) corresponding to the UV region. BPVE in visible wavelength could lead to the development of new photovoltaic cells or other novel optoelectronic devices. BiFeO3 (BFO), a multiferroic material at room temperature with a band gap near 2.74 eV and a very large remnant ferroelectric polarization, offers a unique opportunity for such an investigation. Appreciable photoconductivity in visible light has been reported in BFO. Optical studies by absorption spectroscopy and spectroscopic ellipsometry have shown that BFO has a direct band gap with high absorption coefficient. Recently, a switchable-diode effect and a visible-light photovoltaic effect has been observed in BFO bulk crystals. However, no value of photovoltage has been reported for BFO single crystals and significant bulk photovoltaic response has not been demonstrated in BFO thin film. It is also unclear if the photovoltaic response in BFO is due to the diode effect. Here, we studied the photovoltaic effect in epitaxial BFO thin films and obtained an open-circuit voltage Voc of 0.3 V. We further demonstrated that photocurrent direction can be switched by the polarization direction of the BFO film and that the ferroelectric polarization is the main driving force of the observed photovoltaic effect. Moreover, the as-deposited BFO films were self-polarized and they could readily function as a photovoltaic cell without any poling. Epitaxial BFO thin films of 170 nm were grown by radiofrequency (RF) magnetron sputter deposition on a (001)c SrTiO3 (STO) substrate, with a 60-nm layer of SrRuO3 (SRO) as the bottom electrode. The resulting films show good epitaxy as determined by high-resolution X-ray diffraction (HRXRD; Supporting Information, Fig. S1). The polarization–electric field (P–E) hysteresis measurement shows a remnant polarization (Pr) of more than 65mCcm 2 with a Au top electrode (Fig. S2). Devices with an indium tin oxide (ITO) top electrode have a slightly smaller Pr. Figure 1a shows the spectral response of the short-circuit current (Jsc) of the BFO film. Highest current density is detected at 460 nm, closely corresponding to the measured BFO band gap of 2.72 eV (Fig. S3). Incident light at 435 nm, slightly above band gap, was used for the current-density–voltage (J–V) measurement (Fig. 1b). The as-deposited samples were electrically poled before measurement. The poling direction is termed positive if a positive bias voltage is applied to the top electrode with the bottom electrode grounded. In the J–Vmeasurement, the applied voltage is positive if a positive bias voltage is applied to the bottom electrode. Fig. 1b shows that for the positively poled samples the photocurrent is positive (i.e., it flows out of the top electrode). In contrast, after the negative poling, the photocurrent direction is reversed. The magnitudes of both the photocurrent and photovoltage are smaller in positively poled samples than in negatively poled ones. Jsc is observed to increase almost linearly with the illumination intensity (Fig. 1c), whileVoc saturates at high illumination intensity (Fig. 1d). At the highest illumination intensitymeasured,Voc in the negatively poled film of 170-nm thickness is 0.286V. The substantialVoc obtainedhere is probably a result of the low conductivity of our samples, which is on the order of 10V 1 cm , six orders of magnitude smaller than that reported by Basu et al. and also much smaller than that reported by Choi. The photovoltaic response for the as-deposited films without any poling was also measured. The results are surprisingly

505 citations

Journal ArticleDOI
TL;DR: First-principles calculation evidence is shown that the GeS and GeSe monolayers as well as bulk SnS and SnSe can maintain their ferroelasticity and ferroelectricity (anti-ferro electricity) beyond the room temperature, suggesting high potential for practical device application.
Abstract: Phosphorene and phosphorene analogues such as SnS and SnSe monolayers are promising nanoelectronic materials with desired bandgap, high carrier mobility, and anisotropic structures. Here, we show first-principles calculation evidence that these monolayers are potentially the long-sought two-dimensional (2D) materials that can combine electronic transistor characteristic with nonvolatile memory readable/writeable capability at ambient condition. Specifically, phosphorene is predicted to be a 2D intrinsic ferroelastic material with ultrahigh reversible strain, whereas SnS, SnSe, GeS, and GeSe monolayers are multiferroic with coupled ferroelectricity and ferroelasticity. Moreover, their low-switching barriers render room-temperature nonvolatile memory accessible, and their notable structural anisotropy enables ferroelastic or ferroelectric switching readily readable via electrical, thermal, optical, mechanical, or even spintronic detection upon the swapping of the zigzag and armchair direction. In addition, ...

487 citations

Journal ArticleDOI
TL;DR: In this paper, the authors predict enormous piezoelectric effects in intrinsic monolayer group IV monochalcogenides (MX, M=Sn or Ge, X=Se or S), including SnSe, SnS, GeSe and GeS.
Abstract: We predict enormous piezoelectric effects in intrinsic monolayer group IV monochalcogenides (MX, M=Sn or Ge, X=Se or S), including SnSe, SnS, GeSe and GeS. Using first-principle simulations based on the modern theory of polarization, we find that their characteristic piezoelectric coefficients are about two orders of magnitude larger than those of other 2D materials, such as MoS2 and GaSe, and bulk quartz and AlN which are widely used in industry. This enhancement is a result of the unique "puckered" C2v symmetry and weaker chemical bonds of monolayer group IV monochalcogenides. Given the achieved experimental advances in fabrication of monolayers, their flexible character and ability to withstand enormous strain, these 2D structures with giant piezoelectric effects may be promising for a broad range of applications, such as nano-sized sensors, piezotronics, and energy harvesting in portable electronic devices.

468 citations