Halide Ion Mixing across Colloidal 2D Ruddlesden-Popper Perovskites: Implication of Spacer Ligand on Mixing Kinetics.

Halide ion exchange seen in metal halide perovskites provide a substantial opportunity to control their halide composition and corresponding optoelectronic properties. Halide ion mixing across colloidal 3D perovskite nanocrystals have been extensively studied while the mixing within colloidal 2D counterparts remain underexplored. In this study, the halide ion exchange kinetics across colloidally stable 2D Ruddlesden-Popper layered bromide (Br) and iodide (I) perovskites using two different spacer ligands such as aromatic phenethylammonium (PEA) versus linear butyammonium (BA) is demonstrated. The halide exchange kinetic rate constant (k), as determined by tracking time-dependent absorbance changes, indicates that Br/I halide mixing in 2D PEA-based perovskites (2.7 × 10-3 min-1 ) occurs at an order of magnitude slower than in 2D BA-based perovskites (3.3 × 10-2 min-1 ). Concentration (≈1 mM to 100 mM) and temperature-dependent (50 to 80 °C) kinetic studies further allow for the determination of activation barrier for halide ion mixing across the 2D layered perovskites with 75.2 ± 4.4 kJ mol-1 (2D PEA) and 57.8 ± 7.8 kJ mol-1 (2D BA), respectively. The activation energy reveals that the type of spacer cations plays a crucial role in controlling the halide ion mobility and halide stability due mainly to the internal ligand chemical interaction within 2D structures.

How Chemical Bonding Impacts Halide Perovskite Nanocrystals Growth to Bulk Films: Implication of Pb-X Bond on Growth Kinetics.

Lead halide perovskites nanocrystals have emerged as a leading candidate in perovskite solar cells and light-emitting diodes. Given their favorable, tunable optoelectronic properties through modifying the size of nanocrystals, it is imperative to understand and control the growth of lead halide perovskite nanocrystals. However, during the nanocrystal growth into bulk films, the effect of halide bonding on growth kinetics remains elusive. To understand how a chemical bonding of Pb-X (covalency and ionicity) impact on growth of nanocrystals, we have examined two different halide perovskite nanocrystals of CsPbCl3 (more ionic) and CsPbI3 (more covalent) derived from the same parent CsPbBr3 nanocrystals. Tracking the growth of nanocrystals by monitoring the spectral features of bulk peaks (at 445 nm for Cl and at 650 nm for I) enables us to determine the growth activation energy to be 92 kJ/mol (for CsPbCl3 ) versus 71 kJ/mol (for CsPbI3 ). The electronegativity of halides in Pb-X bonds governs the bond strength (150-240 kJ/mol), characteristics of bonding (ionic versus covalent), and growth kinetics and resulting activation energies. A fundamental understanding of Pb-X bonding provides a significant insight into controlling the size of the perovskite nanocrystals with more desired optoelectronic properties.

Dual-Emissive Mn-Doped Lead Halide Perovskite Nanocrystals as Background-Suppressed Latent Fingerprint Detection Probes.

Diverse strategies have been developed to visualize latent fingerprints (LFPs) that are undetectable by the naked eye. Among them, fluorescence-based approaches have emerged as an attractive method for enabling high-resolution LFP imaging. However, the use of fluorescent probes for LFP detection remains challenging due to cumbersome processing, low selectivity, and high background interference. Here, we demonstrate highly efficient, sensitive, and background-free LFP detection with dual-color emission arising from manganese (Mn)-doped lead halide perovskite (CsPb(Cl1-yBry)3) nanocrystals (NCs). The resulting bright, fluorescent, solid-state nanopowder (NP) permits the visualization of LFP ridge structures and the resolution of level 1-3 LFP features. The dual-color emission of the Mn-doped perovskite NP provides a simple, robust, and effective route to overcome background interference, thereby increasing the resolution and sensitivity of the LFP detection. The combination of the high quantum efficiency and dual emission of Mn-doped perovskite NP offers great potential for forensic science.

Mixed or Segregated: Toward Efficient and Stable Mixed Halide Perovskite-Based Devices.

Convenient modulation of bandgap for the mixed halide perovskites (MHPs) (e.g., CsPbBr x I1-x ) through varying the halide composition (i.e., the ratio of bromide to iodide) allows for optimizing the light-harvesting properties in perovskite solar cells (PSCs) and emission color in perovskite light-emitting diodes (PeLEDs). Such MHPs, yet, severely suffered from the instability under light irradiation and electrical bias as a result of an intrinsic soft, ionic lattice and a high halide ion mobility. Understanding the halide ion migration (mediated through halide vacancies) and suppressing the halide ion segregation, thus, remain a significant challenge both in the field of PSCs and PeLEDs since it is directly linked to the long-term stability and performances of the corresponding devices. In this Mini-Review, we discuss the intrinsic instability of the MHPs arising from the ionic nature of perovskites. The liquid crystalline properties with the low formation energy of halide ion defects facilitate the defect-mediated halide ion migration. Several different mechanistic models are provided to explain the fundamental origin of the photo- or electric field-driven halide ion segregation based upon thermodynamics and kinetics. These reflect that lattice strains (internal or polaron-induced) and bandgap energy differences between parent mixed halide and iodide-rich domain serve as the thermodynamic driving forces for halide segregation. On the basis of the deeper understanding of the underpinning segregation mechanism mediated through hole trapping and accumulation at the iodide-rich sites, we further discuss the strategies to mitigate the detrimental halide segregation through composition-, defect-, dimension-, and interface-engineering. Finally, we provide a fundamental insight into designing perovskite-based photovoltaic and optoelectronic devices for the long-term operational stability.