Tailoring the Optical, Electronic, and Magnetic Properties of MAPbI₃ through Self-Assembled Fe Incorporation

Abstract

We have produced Fe-doped paramagnetic MAPbI 3 microwires by using a novel strategy involving a self-assembly growth process of [PbI 6 ] 4− octahedral chains in the presence of liquid water. Structural and morphological studies confirmed that after the dissociation and recrystallization process, the doped samples preserved both the perovskite structure with a tetragonal phase and a microwire shape, while X-ray photoelectron spectroscopy revealed the presence of mixed-valence Fe 3+ /Fe 2+ ions with negligible change in the PbI 6 cage environment and the maximum valence band position. From first-principles calculations, we determined that Fe 2+ ions are localized in the interstitial site while Fe 3+ ones are substitutional on Pb sites. The very high mobility and static dielectric constant, achieved by photogenerated charge carriers in MAPbI 3 , are suppressed for Fe-doped MAPbI 3 samples. These results are discussed based on a nonradiative recombination process assisted by phonons that is activated by the inclusion of the Fe ions. Our ab initio calculations support this model that can be also used to explain the quenching of the photoluminescence emission peaks. The successful insertion of dopants that can tune the perovskite's physical properties is important to the development of functional devices and is also able to open new potential applications such as in magnetic/semiconducting devices.

Magnetism in a 2D Hybrid Ruddlesden–Popper Perovskite through Charge Redistribution Driven by an Organic Functional Spacer

“…More recently, the range of applications of a hybrid perovskite has been expanding, and the phenomena related to spin-polarized electronic transport in spintronic or energy-related devices have been addressed including spin–orbit coupling. , In this type of approach, spin injection, accumulation, transport, and detection at room temperature by the manipulation of dopants are often reported. , A straightforward alternative approach to achieving magnetism is through magnetic ion doping such as Fe, Mn, and Co into the semiconducting perovskite structure. − This approach has played an important role to electronics and spintronics in conventional semiconductors, but the incorporation of extrinsic dopants introduces disorder and defects into the electronic structure. We have recently reported Fe ions incorporated into MAPbI 3 perovskite microwires introducing magnetic degrees of freedom into the system but at the cost of suppressing the mobility of charge carriers as well as photoluminescence quenching …”

“…We have recently reported Fe ions incorporated into MAPbI 3 perovskite microwires introducing magnetic degrees of freedom into the system but at the cost of suppressing the mobility of charge carriers as well as photoluminescence quenching. 20 On the other hand, 2D Ruddlesden−Popper (RP) perovskites with a layered crystal structure offer synthetic versatility, presenting more dedicated device implementation and new properties to be explored. 21,22 Several functionalities of the 2D perovskites can be easily adjusted by incorporating organic molecules into the 2D array.…”

Lattice-Distortion-Induced Change in the Magnetic Properties in Br-Defect Host CsPbBr3Perovskite Quantum Dots

“…Moreover, CsPbBr 3 PQDs and their related family materials may show defect (doped or intrinsic)-induced magnetic properties. − Mn-doped CH 3 NH 3 PbI 3 with weak magnetization has been reported by Náfrádi et al, indicating that halide perovskites could be a viable option for spintronics devices. However, before the achievement of ambient-temperature-driven spintronics, Mn:CH 3 NH 3 PbI 3 thin-film-based devices register spin splitting (<0.2 eV) and a low Curie temperature (25 K), which should be considerably improved. Investigations by Ren et al .…”

“…However, before the achievement of ambient-temperature-driven spintronics, Mn:CH 3 NH 3 PbI 3 thin-film-based devices register spin splitting (<0.2 eV) and a low Curie temperature (25 K), which should be considerably improved. Investigations by Ren et al . of Mn-doped hybrid perovskite CH 3 NH 3 PbI 3 films reveal substantial ferromagnetic (FM) characteristics at ambient temperature.…”

“…The CsPbBr 3 PQDs were synthesized by injecting cesium oleate (Cs oleate) into a PbBr 2 solution at 180 °C, and the mixture was stirred for 5 s, following a previously described hot-injection synthesis approach. , The reaction was quenched in an ice bath, and the yellow precipitate was collected by centrifugation. − Transmission electron microscopy (TEM) was used to examine the shape, structure, and size of CsPbBr 3 PQDs . The X-ray diffraction (XRD) pattern reveals the orthorhombic polymorph of the CsPbBr 3 PQDs .…”