Photophysics of lead-free tin halide perovskite films and solar cells

The last five years have seen very active research in the field of environmentally friendly lead-free perovskite solar cells. Tin halide perovskites are certainly one of the most promising alternatives to lead-based perovskites, while the performance of present tin-based perovskite solar cells is still relatively low. Nevertheless, recent experiments on thin films with improved quality have indicated that tin halide perovskites can, in principle, provide a high device performance. In this Perspective, we summarize recent progress in the understanding of the fundamental photophysics of tin halide perovskite thin films. To identify the reason for the low performance of present devices, we discuss the energy loss mechanisms in solar cell structures from the viewpoint of photocarrier dynamics

Large thermal expansion leads to negative thermo-optic coefficient of halide perovskite CH₃NH₃PbCl₃

Lead halide perovskites have emerged as new optoelectronic materials owing to their outstanding optical properties. There has been increased interest in their temperature-sensitive optical properties and new optical applications have been proposed thereby. Here, we report the origin of the unusual negative thermo-optic coefficient of the halide perovskite CH₃NH₃PbCl₃, i.e., a decrease in the refractive index by an increase in temperature. From the temperature dependences of the absorption spectrum and the lattice constant and using the Lorentz oscillator model, we conclude that the negative thermo-optic coefficient below the absorption edge is predominantly determined by the large thermal expansion coefficient inherent to this soft material system. This work demonstrates that the negative thermo-optic coefficient is a distinctive phenomenon reflecting the unique electronic and lattice properties of halide perovskites

Smectic Pair Density Wave Order in EuRbFe4As4

The pair density wave (PDW) is a novel superconducting state in which Cooper pairs carry center-of-mass momentum in equilibrium, leading to the breaking of translational symmetry. Experimental evidence for such a state exists in high magnetic field and in some materials that feature density wave orders that explicitly break translational symmetry. However, evidence for a zero-field PDW state that exists independent of other spatially ordered states has so far been elusive. Here, we show that such a state exists in the iron pnictide superconductor EuRbFe4As4 (Eu-1144), a material that features coexisting superconductivity (Tc ~ 37K) and magnetism (Tm ~ 15 K). We show from the Spectroscopic Imaging Scanning Tunneling Microscopy (SI-STM) measurements that the superconducting gap at low temperature has long-range, unidirectional spatial modulations with an incommensurate period of ~8 unit cells. Upon raising the temperature above Tm, the modulated superconductor disappears, but a uniform superconducting gap survives to Tc. When an external magnetic field is applied, gap modulations disappear inside the vortex halo. The SI-STM and bulk measurements show the absence of other density wave orders, showing that the PDW state is a primary, zero-field superconducting state in this compound. Both four-fold rotational symmetry and translation symmetry are recovered above Tm, indicating that the PDW is a smectic order

Bilayer Indium Tin Oxide Electrodes for Deformation-Free Ultrathin Flexible Perovskite Solar Cells

The superior electrical conductivity and optical transparency of indium tin oxide (ITO) make it an ideal electrode material for use in optoelectronic devices such as solar cells. When ITO electrodes are fabricated on very thin plastic substrates, however, the internal stress of the ITO layer causes the substrate to deform, severely limiting the device's performance. Herein, it is shown that ITO bilayers composed of an amorphous base layer and a crystalline overlayer lead to deformation-free ITO electrodes. It is shown that an optimized bilayer structure is achieved when the internal stresses of the amorphous and crystalline layers approximately cancel. With this approach, mixed composition metal halide perovskite solar cells with ITO electrodes are successfully fabricated on 4 μm polyethylene naphthalate films. A power conversion efficiency (PCE) of 18.2% is obtained for the reference cell design, corresponding to a power-to-weight ratio of 24 W g−1 before encapsulation. The devices retain 95% of the original PCE after 1000 bend cycles, while under simulated indoor lighting (white LED, 200 lux, 5000 K) the PCE reaches 28.3%. A 3-cell module with a designated area of 2.3 cm² is realized with a power output of 28.1 mW and an open-circuit voltage of 3.17 V

Photophysics of lead-free tin halide perovskite films and solar cells

The last five years have seen very active research in the field of environmentally friendly lead-free perovskite solar cells. Tin halide perovskites are certainly one of the most promising alternatives to lead-based perovskites, while the performance of present tin-based perovskite solar cells is still relatively low. Nevertheless, recent experiments on thin films with improved quality have indicated that tin halide perovskites can, in principle, provide a high device performance. In this Perspective, we summarize recent progress in the understanding of the fundamental photophysics of tin halide perovskite thin films. To identify the reason for the low performance of present devices, we discuss the energy loss mechanisms in solar cell structures from the viewpoint of photocarrier dynamics

Metal-free ferroelectric halide perovskite exhibits visible photoluminescence correlated with local ferroelectricity

メタルフリーペロブスカイト物質が示す強誘電性と可視光発光の協奏 --多機能デバイスへの応用に期待--. 京都大学プレスリリース. 2022-06-23.Perovskite materials with tunable electronic and structural characteristics can realize various physical properties including electrical/ionic conduction, ferroelectricity, and luminescence. Integrating and coupling these properties in a single perovskite material offer new possibilities for fundamental research and applications. In particular, coupling ferroelectricity and luminescence would enable novel applications. Here, we report that the metal-free ferroelectric perovskite MDABCO (N-methyl-N′-diazabicyclo[2.2.2]octonium)–ammonium triiodide exhibits coupled superior ferroelectricity and visible photoluminescence (PL). Besides strong second-harmonic generation (SHG) associated with its ferroelectricity, MDABCO–ammonium triiodide shows long-lifetime PL at room temperature. Remarkably, the PL intensity depends strongly on the polarization of the excitation light. We found that this anisotropy is coupled to the local crystal orientation that was determined by polarization-resolved SHG. Our results suggest that the anisotropic PL property can be tuned in response to its ferroelectric state via an external field and, thereby, presents a previosuly unobserved functionality in perovskites

Large negative thermo-optic coefficients of a lead halide perovskite

負の屈折率温度係数を示す新しい半導体を発見 --ハロゲン化金属ペロブスカイトを用いた光学温度補償に成功--. 京都大学プレスリリース. 2019-07-22.Lead halide perovskites are promising semiconductors for high-performance photonic devices. Because the refractive index determines the optimal design and performance limit of the semiconductor devices, the refractive index and its change upon external modulations are the most critical properties for advanced photonic applications. Here, we report that the refractive index of halide perovskite CH3NH3PbCl3 shows a distinct decrease with increasing temperature, i.e., a large negative thermo-optic coefficient, which is opposite to those of conventional inorganic semiconductors. By using this negative coefficient, we demonstrate the compensation of thermally induced optical phase shifts occurring in conventional semiconductors. Furthermore, we observe a large and slow refractive index change in CH3NH3PbCl3 during photoirradiation and clarify its origin to be a very low thermal conductivity supported by theoretical analysis. The giant thermo-optic response of CH3NH3PbCl3 facilitates efficient phase modulation of visible light

One-step solution synthesis of white-light-emitting films via dimensionality control of the Cs-Cu-I system

Low-dimensional lead-free luminescent halides have emerged as highly promising phosphors for white-light emission. Recently, we reported a broadband blue-emitting copper(I) iodide-based material, Cs3Cu2I5, with a high photoluminescence quantum yield (PLQY) (similar to 90%) and a zero-dimensional nature, providing significant dimensionality for the photoactive site. However, this material is insufficient as a white-light emitter owing to the deficient yellow emission. In this paper, we report a novel yellow luminescent phosphor, CsCu2I3, with a 1D structure for the photoactive site. This material exhibits a broadband emission centered at similar to 560 nm with a PLQY of similar to 8%. We demonstrate a thin film with white-light emission that can be fabricated using one-step spin-coating of a mixed precursor solution of 1D CsCu2I3 (yellow) and 0D Cs3Cu2I5 (blue). (C) 2019 Author(s)

One-step solution synthesis of white-light-emitting films via dimensionality control of the Cs–Cu–I system

Low-dimensional lead-free luminescent halides have emerged as highly promising phosphors for white-light emission. Recently, we reported a broadband blue-emitting copper(I) iodide-based material, Cs3Cu2I5, with a high photoluminescence quantum yield (PLQY) (similar to 90%) and a zero-dimensional nature, providing significant dimensionality for the photoactive site. However, this material is insufficient as a white-light emitter owing to the deficient yellow emission. In this paper, we report a novel yellow luminescent phosphor, CsCu2I3, with a 1D structure for the photoactive site. This material exhibits a broadband emission centered at similar to 560 nm with a PLQY of similar to 8%. We demonstrate a thin film with white-light emission that can be fabricated using one-step spin-coating of a mixed precursor solution of 1D CsCu2I3 (yellow) and 0D Cs3Cu2I5 (blue). (C) 2019 Author(s)

Charge Injection Mechanism at Heterointerfaces in CH₃NH₃PbI₃ Perovskite Solar Cells Revealed by Simultaneous Time-Resolved Photoluminescence and Photocurrent Measurements

Organic–inorganic hybrid perovskite solar cells are attracting much attention due to their excellent photovoltaic properties. In these multilayered structures, the device performance is determined by complicated carrier dynamics. Here, we studied photocarrier recombination and injection dynamics in CH₃NH₃PbI₃ perovskite solar cells using time-resolved photoluminescence (PL) and photocurrent (PC) measurements. It is found that a peculiar slowdown in the PL decay time constants of the perovskite layer occurs for higher excitation powers, followed by a decrease of the external quantum efficiency for PC. This indicates that a carrier-injection bottleneck exists at the heterojunction interfaces, which limits the photovoltaic performance of the device in concentrator applications. We conclude that the carrier-injection rate is sensitive to the photogenerated carrier density, and the carrier-injection bottleneck strongly enhances recombination losses of photocarriers in the perovskite layer at high excitation conditions. The physical origin of the bottleneck is discussed based on the result of numerical simulations