Esther Wertz

Single-Molecule Super-Resolution Microscopy Reveals How Light Couples to a Plasmonic Nanoantenna on the Nanometer Scale

The greatly enhanced fields near metal nanoparticles have demonstrated remarkable optical properties and are promising for applications from solar energy to biosensing. However, direct experimental study of these light-matter interactions at the nanoscale has remained difficult due to the limitations of optical microscopy. Here, we use single-molecule fluorescence imaging to probe how a plasmonic nanoantenna modifies the fluorescence emission from a dipole emitter. We show that the apparent fluorophore emission position is strongly shifted upon coupling to an antenna and that the emission of dyes located up to 90 nm away is affected by this coupling. To predict this long-ranged effect, we present a framework based on a distance-dependent partial coupling of the dye emission to the antenna. Our direct interpretation of these light-matter interactions will enable more predictably optimized, designed, and controlled plasmonic devices and will permit reliable plasmon-enhanced single-molecule nanoscopy.

Epitaxial Halide Perovskite Lateral Double Heterostructure

Epitaxial III-V semiconductor heterostructures are key components in modern microelectronics, electro-optics, and optoelectronics. With superior semiconducting properties, halide perovskite materials are rising as promising candidates for coherent heterostructure devices. In this report, spinodal decomposition is proposed and experimentally implemented to produce epitaxial double heterostructures in halide perovskite system. Pristine epitaxial mixed halide perovskites rods and films were synthesized via van der Waals epitaxy by chemical vapor deposition method. At room temperature, photon was applied as a knob to regulate the kinetics of spinodal decomposition and classic coarsening. By this approach, halide perovskite double heterostructures were created carrying epitaxial interfaces and outstanding optical properties. Reduced Fröhlich electron-phonon coupling was discovered in coherent halide double heterostructure, which is hypothetically attributed to the classic phonon confinement effect widely existing in III-V double heterostructures. As a proof-of-concept, our results suggest that halide perovskite-based epitaxial heterostructures may be promising for high-performance and low-cost optoelectronics, electro-optics, and microelectronics. Thus, ultimately, for practical device applications, it may be worthy to pursue these heterostructures via conventional vapor phase epitaxy approaches widely practised in III-V field.

High-Temperature Ionic Epitaxy of Halide Perovskite Thin Film and the Hidden Carrier Dynamics

High-temperature vapor phase epitaxy (VPE) has been proved ubiquitously powerful in enabling high-performance electro-optic devices in III-V semiconductor field. A typical example is the successful growth of p-type GaN by VPE for blue light-emitting diodes. VPE excels as it controls film defects such as point/interface defects and grain boundary, thanks to its high-temperature processing condition and controllable deposition rate. For the first time, single-crystalline high-temperature VPE halide perovskite thin film has been demonstrated-a unique platform on unveiling previously uncovered carrier dynamics in inorganic halide perovskites. Toward wafer-scale epitaxial and grain boundary-free film is grown with alkali halides as substrates. It is shown the metal alkali halides could be used as universal substrates for VPE growth of perovskite due to their similar material chemistry and lattice constant. With VPE, hot photoluminescence and nanosecond photo-Dember effect are revealed in inorganic halide perovskite. These two phenomena suggest that inorganic halide perovskite could be as compelling as its organic-inorganic counterpart regarding optoelectronic properties and help explain the long carrier lifetime in halide perovskite. The findings suggest a new avenue on developing high-quality large-scale single-crystalline halide perovskite films requiring precise control of defects and morphology.

Plasmon-enhanced fluorescence intensities and rates permit super-resolution imaging of enhanced local fields

Single-molecule fluorescence is a powerful tool for imaging structures below the standard diffraction limit of light. The resolution gain comes from fitting the emission of isolated fluorophores, and localization accuracy improves with number of photons detected. Here, we control single-molecule emission by coupling fluorescence to gold nanoparticle local plasmon resonances. These strongly localized electromagnetic modes are generated by the interaction of light with particles smaller than the incident wavelength. We discuss the effects of this plasmonic mode coupling on the fluorescence intensity and lifetime of dye molecules and quantum dots.

Plasmon-enhanced emission from single fluorescent proteins

In this work, we use evaporated gold nanoparticle films (GNPFs) as substrates for plasmon-enhanced imaging of two fluorescent proteins (FPs): mCherry and YFP. Through single-molecule epifluorescence microscopy, we show enhancement of single FP emission in the presence of GNPFs. The gold-coupled FPs demonstrate emission up to four times brighter and seven times longer lived, yielding order-of-magnitude enhancements in total photons detected. Ultimately, this results in increased localization accuracies for single-molecule imaging. Furthermore, we introduce preliminary results for enhancement of mCherry-labeled TcpP membrane proteins inside live Vibrio cholerae cells coupled to GNPFs. Our work indicates that plasmonic substrates are uniquely advantageous for super-resolution imaging and that plasmon-enhanced imaging is a promising technique for improving live cell single-molecule microscopy.

Effect of strain on the Curie temperature and band structure of low-dimensional SbSI

Photoferroelectric materials show great promise for developing alternative photovoltaics and photovoltaic-type non-volatile memories. However, the localized nature of the d orbital and large bandgap of most natural photoferroelectric materials lead to low electron/hole mobility and limit the realization of technologically practical devices. Antimony sulpho-iodide (SbSI) is a photoferroelectric material which is expected to have high electron/hole mobility in the ferroelectric state due to its non-local band dispersion and narrow bandgap. However, SbSI exhibits the paraelectric state close to room temperature. In this report, as a proof of concept, we explore the possibility to stabilize the SbSI ferroelectric phase above room temperature via mechanical strain engineering. We synthesized thin low-dimensional crystals of SbSI by chemical vapor deposition, confirmed its crystal structure with electron diffraction, studied its optical properties via photoluminescence spectroscopy and time-resolved photoluminescence spectroscopy, and probed its phase transition using temperature-dependent steady-state photoluminescence spectroscopy. We found that introducing external mechanical strain to these low-dimensional crystals may lead to an increase in their Curie temperature (by ∼60 K), derived by the strain-modified optical phase transition in SbSI and quantified by Kern formulation and Landau theory. The study suggests that strain engineering could be an effective way to stabilize the ferroelectric phase of SbSI at above room temperature, providing a solution enabling its application for technologically useful photoferroelectric devices.

Merits and Challenges of Ruddlesden–Popper Soft Halide Perovskites in Electro‐Optics and Optoelectronics

Following the rejuvenation of 3D organic-inorganic hybrid perovskites, like CH3 NH3 PbI3 , (quasi)-2D Ruddlesden-Popper soft halide perovskites R2 An -1 Pbn X3 n +1 have recently become another focus in the optoelectronic and photovoltaic device community. Although quasi-2D perovskites were first introduced to stabilize optoelectronic/photovoltaic devices against moisture, more interesting properties and device applications, such as solar cells, light-emitting diodes, white-light emitters, lasers, and polaritonic emission, have followed. While delicate engineering design has pushed the performance of various devices forward remarkably, understanding of the fundamental properties, especially the charge-transfer process, electron-phonon interactions, and the growth mechanism in (quasi)-2D halide perovskites, remains limited and even controversial. Here, after reviewing the current understanding and the nexus between optoelectronic/photovoltaic properties of 2D and 3D halide perovskites, the growth mechanisms, charge-transfer processes, vibrational properties, and electron-phonon interactions of soft halide perovskites, mainly in quasi-2D systems, are discussed. It is suggested that single-crystal-based studies are needed to deepen the understanding of the aforementioned fundamental properties, and will eventually contribute to device performance.

Correction to Epitaxial Halide Perovskite Lateral Double Heterostructure

Lateral Double Heterostructure Yiping Wang,† Zhizhong Chen,† Felix Deschler, Xin Sun,‡ Toh-Ming Lu,‡ Esther A. Wertz,‡ Jia-Mian Hu, and Jian Shi*,† †Department of Materials Science and Engineering and ‡Department of Physics, Applied Physics, and Astronomy, Rensselaer Polytechnic Institute, Troy, New York 12180, United States Cavendish Laboratory, University of Cambridge, Cambridge CB3 0HE, United Kingdom Department of Materials Science and Engineering, The Pennsylvania State University, University Park, Pennsylvania 16802, United States