Real-Time In Situ Observation of CsPbBr3 Perovskite Nanoplatelets Transforming into Nanosheets.

The manipulation of nano-objects through heating is an effective strategy for inducing structural modifications and therefore changing the optoelectronic properties of semiconducting materials. Despite its potential, the underlying mechanism of the structural transformations remains elusive, largely due to the challenges associated with their in situ observations. To address these issues, we synthesize temperature-sensitive CsPbBr3 perovskite nanoplatelets and investigate their structural evolution at the nanoscale using in situ heating transmission electron microscopy. We observe the morphological changes that start from the self-assembly of the nanoplatelets into ribbons on a substrate. We identify several paths of merging nanoplates within ribbons that ultimately lead to the formation of nanosheets dispersed randomly on the substrate. These observations are supported by molecular dynamics simulations. We correlate the various paths for merging to the random orientation of the initial ribbons along with the ligand mobility (especially from the edges of the nanoplatelets). This leads to the preferential growth of individual nanosheets and the merging of neighboring ones. These processes enable the creation of structures with tunable emission, ranging from blue to green, all from a single material. Our real-time observations of the transformation of perovskite 2D nanocrystals reveal a route to achieve large-area nanosheets by controlling the initial orientation of the self-assembled objects with potential for large-scale applications.

Stable Sn-Based Hybrid Perovskite-Related Structures with Tunable Color Coordinates via Organic Cations in Low-Temperature Synthesis.

Organic-inorganic Pb-free layered perovskites are efficient broadband emitters and thus are promising materials for lighting applications. However, their synthetic protocols require a controlled atmosphere, high temperature, and long preparation time. This hinders the potential tunability of their emission through organic cations, as is instead common practice in Pb-based structures. Here, we present a set of Sn-Br layered perovskite-related structures that display different chromaticity coordinates and photoluminescence quantum yield (PLQY) up to 80%, depending on the choice of the organic monocation. We first develop a synthetic protocol that is performed under air and at 4 °C, requiring only a few steps. X-ray and 3D electron diffraction analyses show that the structures exhibit diverse octahedra connectivity (disconnected and face-sharing) and thus optical properties, while preserving the organic-inorganic layer intercalation. These results provide key insight into a previously underexplored strategy to tune the color coordinates of Pb-free layered perovskites through organic cations with complex molecular configurations.

Boosting Photocatalytic Activity Using Reduced Graphene Oxide (RGO)/Semiconductor Nanocomposites: Issues and Future Scope.

Semiconductor nanoparticles are promising materials for light-driven processes such as solar-fuel generation, photocatalytic pollutant remediation, and solar-to-electricity conversion. Effective application of these materials alongside light can assist in reducing the dependence on fossil-fuel driven processes and aid in resolving critical environmental issues. However, severe recombination of the photogenerated charge-carriers is a persistent bottleneck in several semiconductors, particularly those that contain multiple cations. This issue typically manifests in the form of reduced lifetime of the photoexcited electrons-holes leading to a decrease in the quantum efficiency of various light-driven applications. On the other hand, semiconducting oxides or sulfides, coupled with reduced graphene oxide (RGO), have drawn a considerable interest recently, partly because of the RGO enhancing charge separation and transportation through its honeycomb sp2 network structure. High electron mobility, conductivity, surface area, and cost-effectiveness are the hallmark of the RGO. This Mini-Review focuses on (1) examining the approach to the integration of RGO with semiconductors to produce binary nanocomposites; (2) insights into the microstructure interface, which plays a critical role in leveraging charge transport; (3) key examples of RGO composites with oxide and sulfide semiconductors with photocatalysis as application; and (4) strategies that have to be pursued to fully leverage the benefit of RGO in RGO/semiconductors to attain high photocatalytic activity for a sustainable future. This Mini-Review focuses on areas requiring additional exploration to fully understand the interfacial science of RGO and semiconductor, for clarity regarding the interfacial stability between RGO and the semiconductor, electronic coupling at the heterojunction, and morphological properties of the nanocomposites. We believe that this Mini-Review will assist with streamlining new directions toward the fabrication of RGO/semiconductor nanocomposites with higher photocatalytic activity for solar-driven multifunctional applications.

Charge Coupling Enhanced Photocatalytic Activity of BaTiO3/MoO3 Heterostructures.

In this work, we proposed an efficient heterostructure photocatalyst by integrating the ferroelectric BaTiO3 (BTO) layer with the semiconductor MoO3 layer, availing the ferroelectric polarization of BaTiO3 and high generation of photoinduced charge carriers in the MoO3 layer. The effect of MoO3 layer thickness (tMoO3) on the photocatalytic efficiency of the BTO/MoO3 heterostructures is found to be optimum at tMoO3 = 67 nm as tMoO3 varies from 40 to 800 nm. The BTO/MoO3 heterostructure with tMoO3 = 67 nm exhibits a high efficiency of 86% for the degradation of rhodamine B (RhB) under the exposure of UV-visible light for 60 min. The photocatalysis rate kinetics analysis reveals that the rate constant in the heterostructure is 1.7 times of pure BTO and 3.2 times of pure MoO3 films. The enhanced photocatalytic activity in the heterostructures is attributed to the electric field-driven carrier separation due to the ferroelectric polarization and the heterojunction band bending. The charge coupling effect between BaTiO3 and MoO3 is evident from the current-voltage characteristics. The maximum lattice strain in the heterostructure with tMoO3 = 67 nm as evident from X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and photoluminescence (PL) analysis further confirms the charge transfer between the layers. The degradation as well as decolorization efficiency of the BTO/MoO3 heterostructure is higher than that of pure BTO and MoO3 films. Radical trapping experiments reveal that electrons are the major contributors to the photocatalytic activity of the BTO/MoO3 heterostructure. The reusability test shows only a reduction of 5% in the efficiency of the heterostructure after five photocatalysis cycles. The heterostructure can also efficiently decompose the other dyes such as rose bengal and methyl violet. Thus, our findings prove that an efficient and reusable photocatalyst can be designed through the integration of the ferroelectrics with the semiconductor layers.