Lead halide perovskites are promising materials for a range of applications owing to their unique crystal structure and optoelectronic properties. Understanding the relationship between the atomic/mesostructures and the associated properties of perovskite materials is crucial to their application performances. Herein, the detailed pressure processing of CsPbBr3perovskite nanocube superlattices (NC‐SLs) is reported for the first time. By using in situ synchrotron‐based small/wide angle X‐ray scattering and photoluminescence (PL) probes, the NC‐SL structural transformations are correlated at both atomic and mesoscale levels with the band‐gap evolution through a pressure cycle of 0 ↔ 17.5 GPa. After the pressurization, the individual CsPbBr3NCs fuse into 2D nanoplatelets (NPLs) with a uniform thickness. The pressure‐synthesized perovskite NPLs exhibit a single cubic crystal structure, a 1.6‐fold enhanced photoluminescence quantum yield, and a longer emission lifetime than the starting NCs. This study demonstrates that pressure processing can serve as a novel approach for the rapid conversion of lead halide perovskites into structures with enhanced properties.
2D freestanding nanocrystal superlattices represent a new class of advanced metamaterials in that they can integrate mechanical flexibility with novel optical, electrical, plasmonic, and magnetic properties into one multifunctional system. The freestanding 2D superlattices reported to date are typically constructed from symmetrical constituent building blocks, which have identical structural and functional properties on both sides. Here, a general ligand symmetry‐breaking strategy is reported to grow 2D Janus gold nanocrystal superlattice sheets with nanocube morphology on one side yet with nanostar on the opposite side. Such asymmetric metallic structures lead to distinct wetting and optical properties as well as surface‐enhanced Raman scattering (SERS) effects. In particular, the SERS enhancement of the nanocube side is about 20‐fold of that of the nanostar side, likely due to the combined “hot spot + lightening‐rod” effects. This is nearly 700‐fold of SERS enhancement as compared with the symmetric nanocube superlattices without Janus structures.
more » « less- NSF-PAR ID:
- 10460367
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Materials
- Volume:
- 31
- Issue:
- 28
- ISSN:
- 0935-9648
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
more » « less
-
more » « less
Abstract 2D Janus transition metal dichalcogenides (TMDs) have attracted attention due to their emergent properties arising from broken mirror symmetry and self‐driven polarization fields. While it has been proposed that their vdW superlattices hold the key to achieving superior properties in piezoelectricity and photovoltaic, available synthesis has ultimately limited their realization. Here, the first packed vdW nanoscrolls made from Janus TMDs through a simple one‐drop solution technique are reported. The results, including ab initio simulations, show that the Bohr radius difference between the top sulfur and the bottom selenium atoms within Janus (M = Mo, W) results in a permanent compressive surface strain that acts as a nanoscroll formation catalyst after small liquid interaction. Unlike classical 2D layers, the surface strain in Janus TMDs can be engineered from compressive to tensile by placing larger Bohr radius atoms on top (to yield inverted C scrolls. Detailed microscopy studies offer the first insights into their morphology and readily formed Moiré lattices. In contrast, spectroscopy and FETs studies establish their excitonic and device properties and highlight significant differences compared to 2D flat Janus TMDs. These results introduce the first polar Janus TMD nanoscrolls and introduce inherent strain‐driven scrolling dynamics as a catalyst to create superlattices.
-
more » « less
Abstract The impact of tunable morphologies and plasmonic properties of gold nanostars is evaluated for the surface‐enhanced Raman scattering (SERS) detection of uranyl. To do so, gold nanostars are synthesized with varying concentrations of the Good's buffer reagent, 2‐[4‐(2‐hydroxyethyl)‐1‐piperazinyl]propanesulfonic acid (EPPS). EPPS plays three roles including as a reducing agent for nanostar nucleation and growth, as a nanostar‐stabilizing agent for solution phase stability, and as a coordinating ligand for the capture of uranyl. The resulting nanostructures exhibit localized surface plasmon resonance (LSPR) spectra that contain two visible and one near‐infrared plasmonic modes. All three optical features arise from synergistic coupling between the nanostar core and branches. The tunability of these optical resonances is correlated with nanostar morphology through careful transmission electron microscopy (TEM) analysis. As the EPPS concentration used during synthesis increases, both the length and aspect ratio of the branches increase. This causes the two lower energy extinction features to grow in magnitude and become ideal for the SERS detection of uranyl. Finally, uranyl binds to the gold nanostar surface directly and via sulfonate coordination. Changes in the uranyl signal are directly correlated to the plasmonic properties associated with the nanostar branches. Overall, this work highlights the synergistic importance of nanostar morphology and plasmonic properties for the SERS detection of small molecules.
-
With arms radiating from a central core, gold nanostars represent a unique and fascinating class of nanomaterials from which extraordinary plasmonic properties are derived. Despite their relevance to sensing applications, methods for fabricating homogeneous populations of nanostars on large-area planar surfaces in truly periodic arrays is lacking. Herein, the fabrication of nanostar arrays is demonstrated through the formation of hexagonal patterns of near-hemispherical gold seeds and their subsequent exposure to a liquid-state chemical environment that is conducive to colloidal nanostar formation. Three different colloidal nanostar protocols were targeted where HEPES, DMF, and ascorbic acid represent a key reagent in their respective redox chemistries. Only the DMF-driven synthesis proved readily adaptable to the substrate-based platform but nanostar-like structures emerged from the other protocols when synthetic controls such as reaction kinetics, the addition of Ag + ions, and pH adjustments were applied. Because the nanostars were derived from near-hemispherical seeds, they acquired a unique geometry that resembles a conventional nanostar that has been truncated near its midsection. Simulations of plasmonic properties of this geometry reveal that such structures can exhibit maximum near-field intensities that are as much as seven-times greater than the standard nanostar geometry, a finding that is corroborated by surface-enhanced Raman scattering (SERS) measurements showing large enhancement factors. The study adds nanostars to the library of nanostructure geometries that are amenable to large-area periodic arrays and provides a potential pathway for the nanofabrication of SERS substrates with even greater enhancements.more » « less
-
more » « less
Abstract 2D materials exhibit strong excitonic effects due to low dimensionality and enhanced Coulomb interactions, resulting in fascinating many‐particle phenomena like excitons. Though perovskite is a classical type of material hosting abundant correlated electronic phases, freestanding 2D perovskite oxides are not easy to fabricate and yet to be extensively studied. Here the realization of large size (1 × 1 cm2) freestanding perovskite SrTiO3films, which show unexpected excitonic photoluminescence (PL) spectra and carrier dynamics, is reported. Two pronounced broad PL peaks emerge in 2D freestanding SrTiO3films at 2.34–2.4 and 1.8–1.9 eV, of which the 2.34–2.4 eV emission originates from self‐trapped excitons localized within TiO6octahedra, and the 1.8–1.9 eV peak from Ti vacancies. The time‐resolved PL shows a remarkable enhancement of nonradiative Auger recombination through three‐particle process, in which electron–hole excitons transfer their kinetic energy to other free electrons or holes. The results demonstrate unique excitonic properties in 2D perovskite SrTiO3films and unravel their potential for high‐performance optoelectronic devices.
