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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.

In this study, we concentrate on the seismic signature of subducted sediments and suggest the formation of the L‐discontinuity beneath the ancient craton related to migrated sediment dehydration. We first determined the single‐crystal elasticity of topaz, the product of sediment dehydration, at high pressures and temperatures by Brillouin scattering. Using the derived elastic parameters, we establish the velocity and density profiles of subducted sediments in the upper mantle. According to our modeling results, 8.5–17.5 vol.% sediments intruding into the upper mantle will induce a 2%–4% low‐VS anomaly at 210–260 km. Meanwhile, continuous heating will lead to the dehydration of phengite in sediments. The dehydration of this amount sediments can generate a 3%–6% ISS with negative Clapeyron slopes, satisfying the observed L‐discontinuity in northern Finland and northern America without the anisotropy changes but accompanied by low‐velocity anomalies. Our study thus provides new insights into the origin of the L‐discontinuity. Plain Language Summary The origin of the global seismic discontinuities in the Earth's mantle has been well understood, but the formation mechanism of some local seismic discontinuities is still vague. Lehmann discontinuity (L‐discontinuity) is one of the regional discontinuities in the upper mantle with a 2%–6% impendence contrast (ISS) and negative Clapeyron slope. However, the deformation mechanism changes of olivine cannot explain the formation of the L‐discontinuity without the anisotropy changes. Here, we emphasize the significance of the migration and dehydration of the subducted sediments in the origin of the L‐discontinuity beneath the ancient craton. We determined the single‐crystal elasticity of topaz, the product of the sediment dehydration, and then investigated the seismic signature of subducted sediments. Our modeling results indicated that ∼17.5 vol.% sediments intruding into the upper mantle would lead to ∼4% low‐VS anomalies at 210–260 km. After the continuous heating, these intruding sediments would dehydrate by the reaction with the negative Clapeyron slopes, thus producing significant ISS. Therefore, the migration and dehydration of the subducted sediments can reasonably interpret the seismic characteristics of the L‐discontinuity beneath the cratonic regions such as northern Finland and northern America. Our results deepen the understanding of the origin of the L‐discontinuity. Key Points Single‐crystal elasticity of topaz under high pressure and temperature has been investigated by Brillouin scattering The obtained elasticity parameters are used to model the density and velocity profiles of the subducted sediments We suggest the formation of the L‐discontinuity beneath the ancient craton related to migrated sediment dehydration

Small‐scale scatterers observed in the mid‐lower mantle beneath the subduction zones are thought to result from the phase transition of stishovite within subducted oceanic crusts. Here we investigate the phase transition of (Al, H)‐bearing stishovite with four compositions at simultaneously high P‐T conditions combining Raman spectroscopy and X‐ray diffraction. These experimental results reveal that the incorporation of 0.01 a.p.f.u Al into stishovite with H/Al ratio of ∼1/3 lowers the transition pressure by 6.7(3) GPa. However, the Clapeyron slope of this transition is nearly unaffected by changes in the Al content and has a value of 12.2–12.5(3) MPa/K. According to our results, Al content variation ranging from 0 to 0.07 a.p.f.u in SiO2 can reasonably explain the depth distribution from 800 to 1,900 km of the seismic scatterers observed in the circum‐Pacific region. These results deepen our understanding on the complex features of mid‐lower mantle seismic scatterers and corresponding dynamic processes.

To better understand the transport of Mo and W in granitic melts and the formation mechanism of porphyry ore deposits, we have investigated the diffusivities of Mo and W in granitic melts with 0.04-5.1 wt% H2O at 1000-1600°C and 1 GPa using a diffusion couple approach and a Mo saturation approach with Mo sheet serving as the source. The Mo and W diffusivities obtained from diffusion profiles measured by LA-ICP-MS can be described as: DMo,anhy=10-1.47±0.73 exp[-(387±25)/RT], DW,anhy=10-1.28±1.05 exp[-(396±35)/RT], DMo,2.7wt%H2O=10-5.37±0.52 exp [-(211±18)/RT], DMo,5.1wt%H2O= 10-6.87±0.69 exp[-133±20)/RT], where D is diffusivity in m2/s (with the subscripts denoting water contents and \"anhy\" representing nominally anhydrous melt), R is the gas constant, T is the temperature in K, and the activation energies in the exponential are in kJ/mol. When the influence of H2O is incorporated, Mo diffusivity in granitic melts with <5.1 wt% H2O can be modeled as: log DMo=-(1.94±1.58) - (0.87±0.36)ω - [(19341±2784)-(2312±620)w]/T where w is H2O content in the melt in wt%. The diffusion behavior (low diffusivities, high activation energies, and strong H2O effects) of Mo and W indicates that they exist and diffuse in the melt in the form of hexavalent cations. Their low diffusivities imply that the bulk concentrations of Mo and W in exsolved hydrothermal fluid and those in the melt are probably not in equilibrium. However, because of the large fluid-melt partition coefficients of Mo and W, they can still be enriched in the hydrothermal fluid, although to a lesser extent than equilibrium partitioning would allow. Slow Mo and W diffusion can be a significant rate-limiting step for the formation of porphyry Mo/W deposits.

Subducting oceanic slabs undergo metamorphic dehydration with the increase of temperature and pressure during subduction. Dehydration is an essential step for element recycling, and slab fluids are critical agents for mediating slab-mantle interaction. Dehydration is mainly controlled by the thermal structure of subduction zones and the stability of hydrous minerals. At fore-arc depths, slab dehydration produces aqueous fluid with dissolved salts such as NaCl. As subduction proceeds deeper, the content of silicate components increases. At sub-arc and post-arc depths, a hydrous silicate melt is likely to form, or a supercritical fluid could arise from complete miscibility between silicates and H 2 O. The partitioning of elements between slab fluid and the residual solid rock is controlled by the type of fluid, and generally it is the supercritical fluid that is the most capable of mobilizing trace elements, being an effective carrier even for high field strength elements. Understanding the chemistry of slab fluids relies on sophisticated integration of experiments, theoretical computation and investigation of natural rock samples. This contribution focuses on the content and speciation of key volatiles, including carbon, nitrogen and sulfur, in slab fluids as well as important fluid properties such as oxygen fugacity and acidity. The properties of slab fluids show complicated variation under the control of mineral assemblages and T-P conditions. Slab fluids at great depths of subductions have been inferred to be modestly alkaline and not necessarily very oxidizing as often assumed. Further progress in the research of slab dehydration and the chemistry and properties of slab fluids demands urgently the development of innovative experimental and computational technology including in situ analytical methods at high T-P .

Two-dimensional (2D) organic-inorganic hybrid perovskites have attracted growing attention recently due to their naturally formed quantum-well structure, unique photoelectric properties and better environmental stability compared to three-dimensional perovskites. The reduced screening and enhanced Coulomb interaction in 2D perovskites result in the formation of excitonic complexes. While the properties of free excitons have been well investigated, studies on biexcitons remain elusive. Here, we report on the biexcitons in 2D (iso-BA) PbI (BA=C NH ) crystals. The biexciton emission can be observed under a very low excitation power density of 6.4 W/cm at 78 K. The biexciton exhibits a large biexciton binding energy of 46 meV due to the large exciton binding energy of (iso-BA) PbI . Furthermore, the biexcitons exhibit a favorable polarization orientation, resulting in different anisotropy between biexcitons and excitons. Our findings would motivate more studies on biexcitons in 2D perovskites and pave the way for exploiting the many-body physics for biexciton lasing and optical storage devices.

The optoelectronic performances of the layered materials are strongly dependent on the thickness of the samples due to the surface effect. As the size of the samples decreases to few nanometers, the surface depletion field and surface defect density are prominent arising from the large surface to volume ratio. For instance, thin two-dimensional (2D) organic-inorganic hybrid perovskite microplates usually exhibit a rather low photoluminescence quantum yield (PLQY), owning to the strong surface effect. Here, we report that the PLQY can be enhanced as large as 28 times in (iso-BA) 2 Pbl 4 (BA = C 4 H 9 NH 3 ) 2D perovskite thin microplates encapsulated by graphene, resulting in that the PLQY is more than 18% for the microplate with a thickness of 6.7 nm at 78 K. As the thickness of the 2D perovskite microplate increases, the enhancement is gradually reduced and finally vanishes. This observation is in striking contrast to that in monolayer transition metal dichalcogenides (TMDs), when the PLQY is quenched by covering a layer of graphene due to the efficient charge transfer. The enhancement of PLQY in 2D perovskites can be mainly ascribed to the reduced quantum confined Stark effect (QCSE) due to the reduced surface depletion field after covering graphene flake, resulting in the enhanced radiative recombination efficiency. Our findings provide a cost-effective approach to enhance the luminescence, which may pave the way toward high performance light emitting devices based on 2D perovskites.

The incorporation of chloride (Cl) into methylammonium lead iodide (MAPbI 3 ) perovskites has attracted much attention because of the significantly improved performance of the MAPbI 3 ‐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) 2 SnI 4 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) 2 SnI 4− 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.

Surface depletion field would introduce the depletion region near surface and thus could significantly alter the optical, electronic and optoelectronic properties of the materials, especially low-dimensional materials. Two-dimensional (2D) organic—inorganic hybrid perovskites with van der Waals bonds in the out-of-plane direction are expected to have less influence from the surface depletion field; nevertheless, studies on this remain elusive. Here we report on how the surface depletion field affects the structural phase transition, quantum confinement and Stark effect in 2D (BA) 2 PbI 4 perovskite microplates by the thickness-, temperature- and power-dependent photoluminescence (PL) spectroscopy. Power dependent PL studies suggest that high-temperature phase (HTP) and low-temperature phase (LTP) can coexist in a wider temperature range depending on the thickness of the 2D perovskite microplates. With the decrease of the microplate thickness, the structural phase transition temperature first gradually decreases and then increases below 25 nm, in striking contrast to the conventional size dependent structural phase transition. Based on the thickness evolution of the emission peaks for both high-temperature phase and low-temperature phase, the anomalous size dependent phase transition could probably be ascribed to the surface depletion field and the surface energy difference between polymorphs. This explanation was further supported by the temperature dependent PL studies of the suspended microplates and encapsulated microplates with graphene and boron nitride flakes. Along with the thickness dependent phase transition, the emission energies of free excitons for both HTP and LTP with thickness can be ascribed to the surface depletion induced confinement and Stark effect.

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−xClx 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. A one‐pot solution method to synthesize lead‐free 2D perovskite (BA)2SnI4−xClx crystals with various Cl incorporation concentrations is reported. The Cl element is successfully incorporated into the crystal lattice. The Cl incorporation greatly alters the morphology, optical properties, phase transition temperature, and charge transport behavior of the as‐synthesized crystals.