Supercritical fluid in deep subduction zones as revealed by multiphase fluid inclusions in an ultrahigh-pressure metamorphic vein.

Due to their low viscosity, high mobility, and high element contents, supercritical fluids are important agents in the cycling of elements. However, the chemical composition of supercritical fluids in natural rocks is poorly understood. Here, we investigate well-preserved primary multiphase fluid inclusions (MFIs) from an ultrahigh-pressure (UHP) metamorphic vein of the Bixiling eclogite in Dabieshan, China, thus providing direct evidence for the components of supercritical fluid occurring in a natural system. Via the 3D modeling of MFIs by Raman scanning, we quantitatively determined the major composition of the fluid trapped in the MFIs. Combined with the peak-metamorphic pressure-temperature conditions and the cooccurrence of coesite, rutile, and garnet, we suggest that the trapped fluids in the MFIs represent supercritical fluids in a deep subduction zone. The strong mobility of the supercritical fluids with respect to carbon and sulfur suggests that such fluids have profound effects on global carbon and sulfur cycling.

Thermally Assisted Rashba Splitting and Circular Photogalvanic Effect in Aqueously Synthesized 2D Dion-Jacobson Perovskite Crystals.

Recently, a two-dimensional Dion-Jacobson (DJ) perovskite (AMP)PbI4 (AMP = 4-(aminomethyl)piperidinium) is emerging with remarkable Rashba effect and ferroelectricity. However, the origin of the giant Rashba splitting remains elusive and the current synthetic strategy via slow cooling is time- and power-consuming, hindering its future applications. Here, we report on an economical aqueous method to obtain (AMP)PbI4 crystals and clarify the origin of the giant Rashba effect by temperature- and polarization-dependent photoluminescence (PL) spectroscopy. The strong temperature-dependent PL helicity indicates the thermally assisted structural distortion as the main origin of the Rashba effect, suggesting that valley polarization still preserves at high temperatures. The Rashba effect was further confirmed by the circular photogalvanic effect near the indirect bandgap. Our study not only optimizes the synthetic strategies of this DJ perovskite but also sheds light on its potential applications in room/high-temperature spintronics and valleytronics.

Circularly polarized light emission and detection by chiral inorganic semiconductors.

Chiral inorganic semiconductors with high dissymmetric factor are highly desirable, but it is generally difficult to induce chiral structure in inorganic semiconductors because of their structure rigidity and symmetry. In this study, we introduced chiral ZnO film as hard template to transfer chirality to CsPbBr3 film and PbS quantum dots (QDs) for circularly polarized light (CPL) emission and detection, respectively. The prepared CsPbBr3/ZnO thin film exhibited CPL emission at 520 nm and the PbS QDs/ZnO film realized CPL detection at 780 nm, featuring high dissymmetric factor up to around 0.4. The electron transition based mechanism is responsible for chirality transfer.

The strain effects in 2D hybrid organic-inorganic perovskite microplates: bandgap, anisotropy and stability.

Strain engineering provides an efficient strategy to modulate the fundamental properties of semiconducting structures for use in functional electronic and optoelectronic devices. Here, we report on how the strain affects the bandgap, optical anisotropy and stability of two-dimensional (2D) perovskite (BA)2(MA)n-1PbnI3n+1 (n = 1-3) microplates, using photoluminescence spectroscopy. Upon applying external strain, the bandgap decreases at a rate of -5.60/-2.74/-1.38 meV per % for n = 1, 2, and 3 2D perovskites, respectively. This change of the bandgap can be ascribed to the distortion of the octahedra (Pb-I bond contraction) in 2D perovskites, supported by a study on emission anisotropy, which increases with the increase of strain. In addition, the external strain can significantly deteriorate the stability of 2D perovskites due to the strain induced distortion which would make the penetration of moisture and oxygen into the perovskite microplates easier, resulting in much faster degradation rates. Our findings not only provide insights into the design and optimization of functional devices, but also provide a new approach to improve the stability of 2D perovskite based devices.

The Role of Chloride Incorporation in Lead-Free 2D Perovskite (BA)2SnI4: Morphology, Photoluminescence, Phase Transition, and Charge Transport.

The incorporation of chloride (Cl) into methylammonium lead iodide (MAPbI3) perovskites has attracted much attention because of the significantly improved performance of the MAPbI3-based optoelectronic devices with a negligible small amount of Cl incorporation. It is expected that the Cl incorporation in 2D perovskites with layered nature would be much more efficient and thus can greatly alter the morphology, optical properties, phase transition, and charge transport; however, studies on those aspects in 2D perovskites remain elusive up to date. Here, a one-pot solution method to synthesize the Cl-doped lead-free 2D perovskite (BA)2SnI4 with various Cl incorporation concentrations is reported and how the Cl incorporation affects the morphology change, photoluminescence, phase transition, and charge transport is investigated. The Cl element is successfully incorporated into the crystal lattice in the solution-processed perovskite materials, confirmed by X-ray photoelectron spectroscopy and energy dispersive X-ray spectroscopy measurements. The temperature-dependent photoluminescence studies indicate that the emission properties and phase transition behavior in (BA)2SnI4- x Cl x can be tuned by varying the Cl incorporation concentration. Electrical measurement suggests that the charge transport behavior can also be greatly altered by the Cl doping concentration and the electrical conductivity can be significantly improved under a higher Cl incorporation concentration.

Aqueous Synthesis of Low-Dimensional Lead Halide Perovskites for Room-Temperature Circularly Polarized Light Emission and Detection.

Low-dimensional lead halide perovskite materials are an emerging class of solution-processable semiconductors with promising potential applications in optoelectronic devices. Unfortunately, it is impossible to synthesize high-crystalline-quality low-dimensional perovskite single crystals without using chemotoxic solutions such as dimethylformamide/dimethyl sulfoxide or applying heating. Herein we report an economical and universal aqueous method to synthesize 2D layered and 1D chain perovskite single crystals at room temperature. The resultant chiral 2D perovskites can efficiently and selectively emit and detect circularly polarized light at room temperature. The as-synthesized 1D perovskite single crystals exhibit strong quantum confinement and enhanced self-trapped states that give efficient warm circularly polarized white-light emission. This aqueous synthetic method is general for other high-quality low-dimensional lead halide perovskite single crystals, and thus our findings would motivate more fundamental investigations on low-dimensional perovskites for potential optoelectronic applications.

Temperature-Dependent Band Gap in Two-Dimensional Perovskites: Thermal Expansion Interaction and Electron-Phonon Interaction.

Two-dimensional organic-inorganic perovskites have attracted considerable interest recently. Here, we present a systematic study of the temperature-dependent photoluminescence on phase pure (n-BA)2(MA) n-1Pb nI3 n+1 ( n = 1-5) and (iso-BA)2(MA) n-1Pb nI3 n+1 ( n = 1-3) microplates obtained by mechanical exfoliation. The photoluminescence peak position gradually changes from a red-shift for n = 1 to a blue-shift for n = 5 with an increase in temperature in the (n-BA)2(MA) n-1Pb nI3 n+1 ( n = 1-5) series, while only a monotonous blue-shift has been observed for the (iso-BA)2(MA) n-1Pb nI3 n+1 ( n = 1-3) series, which can be attributed to the competition between the thermal expansion interaction and electron-phonon interaction. In the (n-BA)2(MA) n-1Pb nI3 n+1 ( n = 1-5) series, the thermal expansion interaction and electron-phonon interaction are both gradually enhanced and the former progressively dominates the latter from n = 1 to n = 5, resulting in the band gap versus temperature changing from a red-shift to a blue-shift. In contrast, both of these factors show a weaker layer thickness dependence, leading to the monotonous blue-shift in the (iso-BA)2(MA) n-1Pb nI3 n+1 ( n = 1-3) series.