New State-Diagram of Aqueous Solutions Unveiling Ionic Hydration, Antiplasticization, and Structural Heterogeneities in LiTFSI–H₂O

Here, we report a new state-diagram for aqueous solutions based on concentration-dependent glass-transition temperatures of concentrated and ice freeze-concentrated solutions. Different from the equilibrium phase diagram, this new state-diagram can provide comprehensive information about the hydration numbers of solutes, nonequilibrium vitrification/cold-crystallization, and vitrification/devitrification processes of aqueous solutions in three distinct concentration zones separated by two critical water-content points of only functions of the hydration number. Based on this new state-diagram, we observe the comparable hydration ability of LiTFSI to LiCl and an atypical concentration-dependent cold-crystallization behavior of the LiTFSI–H2O system. These results unveil the negligible hydration ability of TFSI– in a water-rich solution, characterize the antiplasticizing effect of water induced by the strengthened Li+–TFSI––H2O interaction when only hydration water and confined water are present, and confirm the increasing fraction of water-rich domains with the decrease in water content when the cation and anion become incompletely hydrated on average. These results highlight the novel water-content-mediated interactions among the anion, cation, and H2O for LiTFSI–H2O

Diffusions in Aqueous Solutions with Multivalent Cations and Especially in Cationic First Hydration Shell

Compared with univalent cationic diffusion, little is known about the diffusion behavior of multivalent cations let alone the diffusion of water in their first hydration shell. Here, we show that all published translational diffusion coefficients of multivalent cations and water measured at room temperature exhibit the same concentration dependence when plotted as a function of the mass fraction of free water or of hydrated solute. This behavior is held until only hydration and confined water remain in solutions, wherein their concentration dependences become cationic charge number-dependent. We also found that the iceberg model can well describe the diffusions of multivalent cations with decreasing water content until only hydration water is present. However, 1H-pulsed-field-gradient nuclear magnetic resonance measurements confirmed that 1H in the first hydration shell diffuses faster than Al3+ at room temperature and they have the same diffusion coefficient only with decreasing the temperature down to about 243 K. Therefore, iceberg model only equivalently describes the effect of strong ion–water interaction on multivalent cationic diffusion. These results will also help us reconceive our current understanding of the pathway for hydration water affecting the diffusion behavior of solutes with relatively weak solute–water interactions

Freestanding Crystalline β‑Ga₂O₃ Flexible Membrane Obtained via Lattice Epitaxy Engineering for High-Performance Optoelectronic Device

Wearable and flexible β-Ga2O3-based semiconductor devices have attracted considerable attention, due to their outstanding performance and potential application in real-time optoelectronic monitoring and sensing. However, the unavailability of high-quality crystalline and flexible β-Ga2O3 membranes limits the fabrication of relevant devices. Here, through lattice epitaxy engineering together with the freestanding method, we demonstrate the preparation of a robust bending-resistant and crystalline β-Ga2O3 (−201) membrane. Based on this, we fabricate a flexible β-Ga2O3 photodetector device that shows comparable performance in photocurrent responsivity and spectral selectivity to conventional rigid β-Ga2O3 film-based devices. Moreover, based on the transferred β-Ga2O3 membrane on a silicon wafer, the PEDOT:PSS/β-Ga2O3 p–n heterojunction device with self-powered characteristic was constructed, further demonstrating its superior heterogeneous integration ability with other functional materials. Our results not only demonstrate the feasibility of obtaining a high-quality crystalline and flexible β-Ga2O3 membrane for an integrated device but also provide a pathway to realize flexible optical and electronic applications for other semiconducting materials