Two-dimensional (2D) organic–inorganic hybrid halide perovskites exhibit unique properties, such as long charge carrier lifetimes, high photoluminescence quantum efficiencies, and great tolerance to defects. Over the last several decades tremendous progress has occurred in the development of 2D layered halide perovskite semiconductor materials and devices. Chemical functionalization of 2D halide perovskites is an effective approach for tuning their electronic properties. A large amount of effort has been made in compositional engineering of the cations and anions in the perovskite lattice. However, few efforts have incorporated rationally designed semiconducting organic moieties into these systems to alter the overall chemical and optoelectronic properties of 2D perovskites. In fact, incorporation of large conjugated organic groups in the spatially confined inorganic perovskite matrix was found to be challenging, and this synthetic challenge hinders a deeper understanding of the materials’ structure–property relationships. Recently, exciting progress has been made regarding the molecular design, optical characterization, and device fabrication of novel 2D halide perovskite materials that incorporate functional organic semiconducting building blocks. In this article, we provide a timely review regarding this recent progress. Moreover, we discuss successes and current challenges regarding the synthesis, characterization, and device applications of such hybrid materials and provide a perspective on the true future promise of these advanced nanomaterials.
more »
« less
Pressure induced semiconductor to metal phase transition of a charge-ordered indium halide perovskite.
Phase transitions in halide perovskites triggered by external stimuli generate significantly different material properties, providing a great opportunity for broad applications. Here, we demonstrate an In-based, charge-ordered (In+/In3+) inorganic halide perovskite with the composition of Cs2In(I)In(III)Cl6 in which a pressure-driven semiconductor-to-metal phase transition exists. The single crystals, synthesized via a solid-state reaction method, crystallize in a distorted perovskite structure with space group I4/m with a = 17.2604(12) Å, c = 11.0113(16) Å if both the strong reflections and superstructures are considered. The supercell was further confirmed by rotation electron diffraction measurement. The pressure-induced semiconductor-to-metal phase transition was demonstrated by high-pressure Raman and absorbance spectroscopies and was consistent with theoretical modeling. This type of charge-ordered inorganic halide perovskite with a pressure-induced semiconductor-to-metal phase transition may inspire a range of potential applications.
more »
« less
- Award ID(s):
- 1708448
- PAR ID:
- 10192170
- Date Published:
- Journal Name:
- Proceedings of the National Academy of Sciences of the United States of America
- ISSN:
- 0027-8424
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
more » « less
Wide–band gap metal halide perovskites are promising semiconductors to pair with silicon in tandem solar cells to pursue the goal of achieving power conversion efficiency (PCE) greater than 30% at low cost. However, wide–band gap perovskite solar cells have been fundamentally limited by photoinduced phase segregation and low open-circuit voltage. We report efficient 1.67–electron volt wide–band gap perovskite top cells using triple-halide alloys (chlorine, bromine, iodine) to tailor the band gap and stabilize the semiconductor under illumination. We show a factor of 2 increase in photocarrier lifetime and charge-carrier mobility that resulted from enhancing the solubility of chlorine by replacing some of the iodine with bromine to shrink the lattice parameter. We observed a suppression of light-induced phase segregation in films even at 100-sun illumination intensity and less than 4% degradation in semitransparent top cells after 1000 hours of maximum power point (MPP) operation at 60°C. By integrating these top cells with silicon bottom cells, we achieved a PCE of 27% in two-terminal monolithic tandems with an area of 1 square centimeter.
-
more » « less
Abstract Ferroelectricity is typically suppressed under hydrostatic compression because the short-range repulsions, which favor the nonpolar phase, increase more rapidly than the long-range interactions, which prefer the ferroelectric phase. Here, based on single-crystal X-ray diffraction and density-functional theory, we provide evidence of a ferroelectric-like transition from phase
I 213 toR 3 induced by pressure in two isostructural defect antiperovskites Hg3Te2Cl2(15.5 GPa) and Hg3Te2Br2(17.5 GPa). First-principles calculations show that this transition is attributed to pressure-induced softening of the infrared phonon mode Γ4, similar to the archetypal ferroelectric material BaTiO3at ambient pressure. Additionally, we observe a gradual band-gap closing from ~2.5 eV to metallic-like state of Hg3Te2Br2with an unexpectedly stableR 3 phase even after semiconductor-to-metal transition. This study demonstrates the possibility of emergence of polar metal under pressure in this class of materials and establishes the possibility of pressure-induced ferroelectric-like transition in perovskite-related systems. -
more » « less
Abstract Three‐dimensional (3D) organic–inorganic metal halide perovskite materials possess great potential applications for approaching efficient optoelectronics due to the unique optoelectronic properties of perovskite materials and cost‐effective manufacturing possibilities of optoelectronics. However, the scientific and technical challenges of 3D perovskite materials were their inferior long‐term stability, which hampered their practical applications. The low‐dimensional perovskite materials composed of alternating organic and inorganic layers are one of the most credible paths toward stable perovskite photovoltaics and optoelectronics. In this short review, we first present a discussion of the crystal structure and nontrivial optoelectronic properties of the low‐dimensional halide perovskites. The synthetic methods for the preparation of the low‐dimensional halide perovskites are reviewed. After that, we focus on the recent development of perovskite photovoltaics, light‐emitting diodes, and lasers by the low‐dimensional halide perovskites. Finally, we outline the challenges of the low‐dimensional halide perovskites and their applications.
image -
more » « less
Abstract In two-dimensional chiral metal-halide perovskites, chiral organic spacers endow structural and optical chirality to the metal-halide sublattice, enabling exquisite control of light, charge, and electron spin. The chiroptical properties of metal-halide perovskites have been measured by transmissive circular dichroism spectroscopy, which necessitates thin-film samples. Here, by developing a reflection-based approach, we characterize the intrinsic, circular polarization-dependent complex refractive index for a prototypical two-dimensional chiral lead-bromide perovskite and report large circular dichroism for single crystals. Comparison with ab initio theory reveals the large circular dichroism arises from the inorganic sublattice rather than the chiral ligand and is an excitonic phenomenon driven by electron-hole exchange interactions, which breaks the degeneracy of transitions between Rashba-Dresselhaus-split bands, resulting in a Cotton effect. Our study suggests that previous data for spin-coated films largely underestimate the optical chirality and provides quantitative insights into the intrinsic optical properties of chiral perovskites for chiroptical and spintronic applications.
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1073/pnas.1907576116
