Hybrid perovskites incorporating conjugated organic cations enable unusual charge carrier interactions among organic and inorganic structural components, but are difficult to prepare as films due to disparate component chemical/physical characteristics ( e.g. , solubility, thermal stability). Here we demonstrate that resonant infrared matrix-assisted pulsed laser evaporation (RIR-MAPLE) mitigates these challenges, enabling facile deposition of lead-halide-based perovskite films incorporating variable-length oligothiophene cations. Density functional theory (DFT) predicts suitable organic and inorganic moieties that form quantum-well-like structures with targeted luminescence or exciton separation/quenching. RIR-MAPLE-deposited films enable confirmation of these predictions by optical measurements, which further display excited state behavior transcending traditional quantum-well models— i.e. , with appropriate selection of specially synthesized organic/inorganic moieties, intercomponent carrier transfer efficiently converts excitons from singlet to triplet states in organics for which intersystem crossing cannot ordinarily compete with recombination. These observations demonstrate the uniquely versatile excited-state behavior in hybrid perovskite quantum wells, and the value of integrating DFT, organic synthesis, RIR-MAPLE and spectroscopy for screening/preparing rationally devised complex structures.
Unraveling luminescence mechanisms in zero-dimensional halide perovskites
Zero-dimensional (0D) halides perovskites, in which anionic metal-halide octahedra (MX 6 ) 4− are separated by organic or inorganic countercations, have recently shown promise as excellent luminescent materials. However, the origin of the photoluminescence (PL) and, in particular, the different photophysical properties in hybrid organic–inorganic and all inorganic halides are still poorly understood. In this work, first-principles calculations were performed to study the excitons and intrinsic defects in 0D hybrid organic–inorganic halides (C 4 N 2 H 14 X) 4 SnX 6 (X = Br, I), which exhibit a high photoluminescence quantum efficiency (PLQE) at room temperature (RT), and also in the 0D inorganic halide Cs 4 PbBr 6 , which suffers from strong thermal quenching when T > 100 K. We show that the excitons in all three 0D halides are strongly bound and cannot be detrapped or dissociated at RT, which leads to immobile excitons in (C 4 N 2 H 14 X) 4 SnX 6 . However, the excitons in Cs 4 PbBr 6 can still migrate by tunneling, enabled by the resonant transfer of excitation energy (Dexter energy transfer). The exciton migration in Cs 4 PbBr 6 leads to a higher probability of trapping and nonradiative more »
- Award ID(s):
- 1709116
- Publication Date:
- NSF-PAR ID:
- 10099111
- Journal Name:
- Journal of Materials Chemistry C
- Volume:
- 6
- Issue:
- 24
- Page Range or eLocation-ID:
- 6398 to 6405
- ISSN:
- 2050-7526
- Sponsoring Org:
- National Science Foundation
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Tunable optical properties and stability of lead free all inorganic perovskites (Cs 2 SnI x Cl 6−x )Organic–inorganic hybrid lead-based perovskites experience significant environmental instability under ambient moist air and are not environmentally benign due to the usage of toxic Pb. Here, we report a new approach to synthesize lead-free all inorganic perovskites (Cs 2 SnI x Cl 6−x ) using hydriodic acid (HI) demonstrating greatly enhanced environmental stability and tunable optical properties by controlling the I − /Cl − ratios. Single phase perovskites can be achieved with a low iodine or chlorine content, and a phase separation occurs in the binary system with closer iodine and chlorine dopings. UV-vis diffuse reflectance and photoluminescence measurements reveal tunable band gaps of Cs 2 SnI x Cl 6−x perovskites from the UV to the infrared region. The mixed halide perovskite with a lower chloride content shows significantly higher photoluminescence intensity. The thermal stability of mixed halide all-inorganic perovskites is continuously improved as the Cl content increases. The synthesis of Sn-based perovskites with tunable optical properties and environmental stability represents one step further toward the realization of the stable lead-free all inorganic perovskites.
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Hybrid materials comprised of inorganic quantum dots functionalized with small-molecule organic chromophores have emerged as promising materials for reshaping light's energy content. Quantum dots in these structures can serve as light harvesting antennas that absorb photons and pass their energy to molecules bound to their surface in the form of spin-triplet excitons. Energy passed in this manner can fuel upconversion schemes that use triplet fusion to convert infrared light into visible emission. Likewise, triplet excitons passed in the opposite direction, from molecules to quantum dots, can enable solar cells that use singlet fission to circumvent the Shockley–Queisser limit. Silicon QDs represent a key target for these hybrid materials due to silicon's biocompatibility and preeminence within the solar energy market. However, while triplet transfer from silicon QDs to molecules has been observed, no reports to date have shown evidence of energy moving in the reverse direction. Here, we address this gap by creating silicon QDs functionalized with perylene chromophores that exhibit bidirectional triplet exciton transfer. Using transient absorption, we find triplet transfer from silicon to perylene takes place over 4.2 μs while energy transfer in the reverse direction occurs two orders of magnitude faster, on a 22 ns timescale. To demonstratemore »
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- Publisher's Version of Record
- https://doi.org/10.1039/c8tc01291a
