Interlayer excitons have been extensively studied in monolayer transition metal dichalcogenide (TMD) heterobilayers mainly due to the long lifetime, which is beneficial for a wide range of optoelectronic applications. To date, the majority of investigations of interlayer excitons in TMD heterobilayers have been focusing on the geometric arrangement of structures, spin–valley lifetime, and interlayer valley excitons with interlayer hopping rules. Nevertheless, interlayer excitons in TMD heterobilayers strongly depend on the local atomic registry and coupling strength, which increase the complexity of the device fabrication. Here, we report pronounced interlayer exciton emission in two-dimensional (2D) perovskite/monolayer TMD heterostructures without the need of thermal annealing or specific geometric arrangements, and the interlayer exciton emission is rather general among 2D perovskites and monolayer TMDs. Such interlayer exciton emission completely dominates the emission spectrum at 78 K regardless of the stacking sequence, suggesting the robust interlayer coupling in 2D perovskite/monolayer TMD heterostructures. Furthermore, the interlayer exciton emission shows a large blue-shift with increasing laser intensity due to the repulsive dipole–dipole interaction and can persist above 220 K. Importantly, the interlayer exciton emission also possesses robust circular polarization in chiral 2D perovskite/monolayer WSe2 heterostructures, which can be applied to manipulate the valley degree of freedom for valleytronic devices. Our findings would provide a favorable platform to explore interlayer coupling and related physical processes in 2D perovskites and TMDs and further provoke more investigations into the understanding and controlling of excitonic effects and associated optoelectronic applications in van der Waals heterostructures over a broad-range spectral response.

Monolayer two-dimensional (2D) transition metal dichalcogenides (TMDs) have attracted great interest in spintronics and valleytronics due to the spin− valley locking effect. To efficiently control and manipulate the valley pseudospin is of paramount importance for valley-based electronics and optoelectronics. A variety of strategies have been developed to address the valley pseudospin including optical, electrical, and magnetic methods; nonetheless, they involve either below liquid-nitrogen temperature or an external magnetic field, which increases the cost and complexity of the devices. Here, we report a straightforward way to manipulate valley polarization in monolayer TMDs via selective spin injection in chiral 2D perovskite/monolayer TMD (e.g., MoS 2 and WSe 2 ) van der Waals heterostructures without requiring an external magnetic field or specially designed device structures. We show the danglingbond-free vdW interface can allow an impressive average spin injection efficiency of 78% to produce persistent valley polarization in monolayer MoS 2 (WSe 2 ) over 10% from liquid-nitrogen temperature to above 200 K. We attribute the valley polarization of monolayer MoS 2 (WSe 2 ) to selective spin injection from chiral 2D perovskites, which can effectively introduce population imbalance between valleys in monolayer MoS 2 (WSe 2 ). Our findings provide an alternative strategy to manipulate the valley polarization in TMDs without requiring circularly polarized light excitation, below liquid-nitrogen temperature, or external magnetic field, and thus would promote the development of perovskite-based spintronic and valleytronic devices.

Two-dimensional (2D) perovskites show great potential for optoelectronic applications due to their bandgap tunability, extremely large excition binding energy, and large crystal anisotropy compared with their three-dimensional counterparts. To fully explore exciton-based applications and improve their performance, it is essential to understand the exciton behavior in 2D perovskites. Here, we investigate exciton anisotropy within the crystallographic plane and cross plane of (C4H9NH3)2PbI4 2D perovskite crystals by polarization-resolved photoluminescence, reflection, and photoconductivity studies. We observe a polarization-dependent emission evolution and an enhanced self-trapped exciton emission with an oblique incident excitation from the cross plane. Furthermore, the anisotropy of excitons in (C4H9NH3)2PbI4 2D perovskite crystals is identified by polarization-resolved photoluminescence and photoconductivity measurement, and a completely opposite polarization-dependent behavior was observed for free excitons and self-trapped excitons. We attribute this different anisotropy to the existence of out-of-plane excitons and different optical selection rule for free excitons and self-trapped excitons. Our findings will shed light on designing and improving the performance of exciton-based optoelectronic devices in 2D perovskites.

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.