2D/3D Halide Perovskites for Optoelectronic Devices

The traditional three-dimensional (3D) halide perovskites (HPs) have experienced rapid development due to their highly power conversion efficiency (PCE). However, the instability of 3D perovskite on humidity and UV irradiation blocks their commercialization. In the past few years, two-dimensional (2D) halide perovskites attract much attention because they behave better stability due to the water resistance of the aliphatic carbon chains in the 2D perovskite lattice. In this review, we categorize the 2D/3D perovskites based on the applications [i.e., solar cells (SCs), light-emitting diodes (LEDs) and photodetectors (PDs)]. We further discuss the recent efforts in the performance enhancement of the 2D/3D perovskite-based devices. However, there are still some difficulties before 2D/3D HPs is fully commercialized. We will provide some scientific and technical challenges and prospects in the article to point out the future direction.

Significantly suppressing ion migration in metal halide perovskites via trace of multivalent interstitial doping

Cations with suitable sizes to occupy an interstitial site of perovskite crystals have been widely used to inhibit ion migration and promote performance and stability of perovskite optoelectronics. However, the interstitial doping accompanies inevitable lattice strain to impair long-range ordering and stability of the crystals to cause a sacrificial trade-off. Here, we unravel the evident influence of the valence states of the interstitial cations on their efficacy to suppress the ion migration. Incorporation of a trivalent neodymium cation (Nd3+) effectively mitigates the ion migration in the perovskite lattice with significantly reduced dosage (0.08%) compared to a widely used monovalent cation dopant (Na+, 0.45%). Less but better, the prototypical perovskite solar cells incorporated with Nd3+ exhibits significantly enhanced photovoltaic performance and operational stability.

Structural Transitions and Stability of FAPbI3 and MAPbI3: The Role of Interstitial Water

We studied the influence of water on the structural stability and transformations of MAPI and FAPI by anelastic and dielectric spectroscopies under various temperature and H2O partial pressure protocols. Before discussing the new results in terms of interstitial water in MAPI and FAPI, the literature is briefly reviewed, in search of other studies and evidences on interstitial water in hybrid halide perovskites. In hydrated MAPI, the elastic anomaly between the cubic α and tetragonal β phases may be depressed by more than 50%, demonstrating that there are H2O molecules dispersed in the perovskite lattice in interstitial form, that hinder the long range tilting of the PbI6 octahedra. Instead, in FAPI, interstitial water accelerates in both senses the reconstructive transformations between 3D α and 1D δ phases, which is useful during the crystallization of the α phase. On the other hand, the interstitial H2O molecules increase the effective size of the MA and FA cations to which are bonded, shifting the thermodynamic equilibrium from the compact perovskite structure to the open δ and hydrated phases of loosely bonded chains of PbI6 octahedra. For this reason, when fabricating devices based on hybrid metal-organic halide perovskites, it is important to reduce the content of interstitial water as much as possible before encapsulation.

Vibrational relaxation dynamics in layered perovskite quantum wells

Organic–inorganic layered perovskites, or Ruddlesden–Popper perovskites, are two-dimensional quantum wells with layers of lead-halide octahedra stacked between organic ligand barriers. The combination of their dielectric confinement and ionic sublattice results in excitonic excitations with substantial binding energies that are strongly coupled to the surrounding soft, polar lattice. However, the ligand environment in layered perovskites can significantly alter their optical properties due to the complex dynamic disorder of the soft perovskite lattice. Here, we infer dynamic disorder through phonon dephasing lifetimes initiated by resonant impulsive stimulated Raman photoexcitation followed by transient absorption probing for a variety of ligand substitutions. We demonstrate that vibrational relaxation in layered perovskite formed from flexible alkyl-amines as organic barriers is fast and relatively independent of the lattice temperature. Relaxation in layered perovskites spaced by aromatic amines is slower, although still fast relative to bulk inorganic lead bromide lattices, with a rate that is temperature dependent. Using molecular dynamics simulations, we explain the fast rates of relaxation by quantifying the large anharmonic coupling of the optical modes with the ligand layers and rationalize the temperature independence due to their amorphous packing. This work provides a molecular and time-domain depiction of the relaxation of nascent optical excitations and opens opportunities to understand how they couple to the complex layered perovskite lattice, elucidating design principles for optoelectronic devices.

Polymerized hybrid perovskites with enhanced stability, flexibility and lattice rigidity

The intrinsic soft lattice nature of organometal halide perovskites (OHPs) makes them very tolerant to defects and ideal candidates for solution-processed optoelectronic devices. However, the soft lattice results in low stability towards external stresses such as heating and humidity, and induces high density of phonons, causing strong electron-phonon coupling. Here, we report solid-state polymerization of OHPs using unsaturated 4-vinylbenzylammonium as organoammonium cations without damaging perovskite structure and its tolerance to defects. The polymerized perovskites show enhanced stability and flexibility. Furthermore, the polymerized 4-vinylbenzylammonium group improves perovskite lattice rigidity substantially, resulting in reduced electron-phonon coupling and non-radiative recombination rate, and enhanced carrier mobility because of suppressed phonon scattering. We finally demonstrate efficient polymerized perovskite based light-emitting diodes with an external quantum efficiency of 23.2% and enhanced operation stability.

Influence of ZnO addition and milling process on structure and conductivity of BaCe0.2Zr0.7Y0.1O3-δ ceramics

Precursor powders for BaCe0.2Zr0.7Y0.1O3-?(BCZY27) ceramics were synthesized by a modified Pechinimethod and calcined at 900?C for 12 h. The calcined BCZY27 powders were milled in eccentric and in high energy mill with the addition of 2 and 4mol% ZnO as sintering aid. The effects of milling and sintering aids on the sinterability and electrical conductivity were studied. The linear shrinkage in thermomechanical analyses started at 1050?C for the BCZY27 with 4mol% ZnO processed in eccentric mill. Theoretical density above of 90%TD was obtained for the BCZY27 milled with 4mol% ZnO and sintered at 1400?C for 4h. X-ray diffraction analysis of the BCZY27 ceramics sintered at 1400?C confirmed the presence of BaCe0.2Zr0.7Y0.1O3-? and Y0.4Ce0.6O1.8 phases. The incorporation of Zn into perovskite lattice leads to the secondary phase formation. SEM and EDS analyses confirmed the presence of Y0.4Ce0.6O1.8 phase. The sintering was assisted by BaO-ZnO eutectic, which was reflected by the increase of activation energy values for grain boundary conduction. The milling processing did not affect the conductivity properties. The obtained BCZY27 dense sample has conductivity of 7.60 ? 10?3 S/cm at 500?C.

Origins of the long-range exciton diffusion in perovskite nanocrystal films: photon recycling vs exciton hopping

The outstanding optoelectronic performance of lead halide perovskites lies in their exceptional carrier diffusion properties. As the perovskite material dimensionality is reduced to exploit the quantum confinement effects, the disruption to the perovskite lattice, often with insulating organic ligands, raises new questions on the charge diffusion properties. Herein, we report direct imaging of >1 μm exciton diffusion lengths in CH3NH3PbBr3 perovskite nanocrystal (PNC) films. Surprisingly, the resulting exciton mobilities in these PNC films can reach 10 ± 2 cm2 V−1 s−1, which is counterintuitively several times higher than the carrier mobility in 3D perovskite films. We show that this ultralong exciton diffusion originates from both efficient inter-NC exciton hopping (via Förster energy transfer) and the photon recycling process with a smaller yet significant contribution. Importantly, our study not only sheds new light on the highly debated origins of the excellent exciton diffusion in PNC films but also highlights the potential of PNCs for optoelectronic applications.

Atomic-scale microstructure of metal halide perovskite

Hybrid organic-inorganic perovskites have high potential as materials for solar energy applications, but their microscopic properties are still not well understood. Atomic-resolution scanning transmission electron microscopy has provided invaluable insights for many crystalline solar cell materials, and we used this method to successfully image formamidinium lead triiodide [CH(NH2)2PbI3] thin films with a low dose of electron irradiation. Such images reveal a highly ordered atomic arrangement of sharp grain boundaries and coherent perovskite/PbI2 interfaces, with a striking absence of long-range disorder in the crystal. We found that beam-induced degradation of the perovskite leads to an initial loss of formamidinium [CH(NH2)2+] ions, leaving behind a partially unoccupied perovskite lattice, which explains the unusual regenerative properties of these materials. We further observed aligned point defects and climb-dissociated dislocations. Our findings thus provide an atomic-level understanding of technologically important lead halide perovskites.

Understanding electrochemical switchability of perovskite-type exsolution catalysts

Exsolution of metal nanoparticles from perovskite-type oxides is a very promising approach to obtain catalysts with superior properties. One particularly interesting property of exsolution catalysts is the possibility of electrochemical switching between different activity states. In this work, synchrotron-based in-situ X-ray diffraction experiments on electrochemically polarized La0.6Sr0.4FeO3-δ thin film electrodes are performed, in order to simultaneously obtain insights into the phase composition and the catalytic activity of the electrode surface. This shows that reversible electrochemical switching between a high and low activity state is accompanied by a phase change of exsolved particles between metallic α-­Fe and Fe-oxides. Reintegration of iron into the perovskite lattice is thus not required for obtaining a switchable catalyst, making this process especially interesting for intermediate temperature applications. These measurements also reveal how metallic particles on La0.6Sr0.4FeO3-δ electrodes affect the H2 oxidation and H2O splitting mechanism and why the particle size plays a minor role.