The discovery of the photoelectric effect by Heinrich Hertz in 1887 set the foundation for over 125 years of hot carrier science and technology. In the early 1900s it played a critical role in the development of quantum mechanics, but even today the unique properties of these energetic, hot carriers offer new and exciting opportunities for fundamental research and applications. Measurement of the kinetic energy and momentum of photoejected hot electrons can provide valuable information on the electronic structure of materials. The heat generated by hot carriers can be harvested to drive a wide range of physical and chemical processes. Their kinetic energy can be used to harvest solar energy or create sensitive photodetectors and spectrometers. Photoejected charges can also be used to electrically dope two-dimensional materials. Plasmon excitations in metallic nanostructures can be engineered to enhance and provide valuable control over the emission of hot carriers. This Review discusses recent advances in the understanding and application of plasmon-induced hot carrier generation and highlights some of the exciting new directions for the field.

Plasmon-induced hot carrier science and technology

日本物理学会誌及びJournal of the Physical Society of Japanの月刊について

Optical generation of hot electrons in metallic structures and its potential as an alternative to conventional electron–hole separation in semiconductor devices are reviewed. The possibilities for realizing high conversion efficiencies with low fabrication costs are discussed along with challenges in terms of the materials, architectures and fabrication methods

Plasmon-induced hot-electron generation at nanoparticle/metal-oxide interfaces for photovoltaic and photocatalytic devices

The importance of the Fano resonance concept is recognized across multiple fields of physics. In this Review, Fano resonance is explored in the context of optics, with particular emphasis on dielectric nanostructures and metasurfaces. Rapid progress in photonics and nanotechnology brings many examples of resonant optical phenomena associated with the physics of Fano resonances, with applications in optical switching and sensing. For successful design of photonic devices, it is important to gain deep insight into different resonant phenomena and understand their connection. Here, we review a broad range of resonant electromagnetic effects by using two effective coupled oscillators, including the Fano resonance, electromagnetically induced transparency, Kerker and Borrmann effects, and parity–time symmetry breaking. We discuss how to introduce the Fano parameter for describing a transition between two seemingly different spectroscopic signatures associated with asymmetric Fano and symmetric Lorentzian shapes. We also review the recent results on Fano resonances in dielectric nanostructures and metasurfaces.

Fano resonances in photonics

Organolead trihalide perovskite is an emerging low-cost, solution-processable material with a tunable bandgap from the violet to near-infrared, which has attracted a great deal of interest for applications in high-performance optoelectronic devices. Here, we present hybrid perovskite single-crystal photodetectors that have a very narrow spectral response with a full-width at half-maximum of <20 nm. The response spectra are continuously tuned from blue to red by changing the halide composition and thus the bandgap of the single crystals synthesized by solution processes. The narrowband photodetection can be explained by the strong surface-charge recombination of the excess carriers close to the crystal surfaces generated by short-wavelength light. The excess carriers generated by below-bandgap excitation locate away from the surfaces and can be much more efficiently collected by the electrodes, assisted by the applied electric field. This provides a new design paradigm for a narrowband photodetector with broad applications where background noise emission needs to be suppressed. Perovskite-based devices typically exhibit broadband spectral responses. Here narrowband (< 20 nm FWHM) response is achieved for a photodetector application.

Highly narrowband perovskite single-crystal photodetectors enabled by surface-charge recombination

In gratings, incident light can couple strongly to plasmons propagating through periodically spaced slits in a metal film, resulting in a strong, resonant absorption whose frequency is determined by the nanostructure periodicity. When a grating is patterned on a silicon substrate, the absorption response can be combined with plasmon-induced hot electron photocurrent generation. This yields a photodetector with a strongly resonant, narrowband photocurrent response in the infrared, limited at low frequencies by the Schottky barrier, not the bandgap of silicon. Here we report a grating-based hot electron device with significantly larger photocurrent responsivity than previously reported antenna-based geometries. The grating geometry also enables more than three times narrower spectral response than observed for nanoantenna-based devices. This approach opens up the possibility of plasmonic sensors with direct electrical readout, such as an on-chip surface plasmon resonance detector driven at a single wavelength.

Narrowband photodetection in the near-infrared with a plasmon-induced hot electron device.

The use of surface plasmons, charge density oscillations of conduction electrons of metallic nanostructures, to boost the efficiency of light-harvesting devices through increased light-matter interactions could drastically alter how sunlight is converted into electricity or fuels. These excitations can decay directly into energetic electron-hole pairs, useful for photocurrent generation or photocatalysis. However, the mechanisms behind plasmonic carrier generation remain poorly understood. Here we use nanowire-based hot-carrier devices on a wide-bandgap semiconductor to show that plasmonic carrier generation is proportional to internal field-intensity enhancement and occurs independently of bulk absorption. We also show that plasmon-induced hot electrons have higher energies than carriers generated by direct excitation and that reducing the barrier height allows for the collection of carriers from plasmons and direct photoexcitation. Our results provide a route to increasing the efficiency of plasmonic hot-carrier devices, which could lead to more efficient devices for converting sunlight into usable energy.

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Distinguishing between plasmon-induced and photoexcited carriers in a device geometry

When plasmonic nanostructures serve as the metallic counterpart of a metal–semiconductor Schottky interface, hot electrons due to plasmon decay are emitted across the Schottky barrier, generating measurable photocurrents in the semiconductor. When the plasmonic nanostructure is atop the semiconductor, only a small percentage of hot electrons are excited with a wavevector permitting transport across the Schottky barrier. Here we show that embedding plasmonic structures into the semiconductor substantially increases hot electron emission. Responsivities increase by 25× over planar diodes for embedding depths as small as 5 nm. The vertical Schottky barriers created by this geometry make the plasmon-induced hot electron process the dominant contributor to photocurrent in plasmonic nanostructure-diode-based devices.

Embedding Plasmonic Nanostructure Diodes Enhances Hot Electron Emission

Here, we report a new nanoantenna for surface-enhanced infrared absorption (SEIRA) detection, consisting of a fan-shaped Au structure positioned at a well-specified distance above a reflective plane with an intervening silica spacer layer. We examine how to optimize both the antenna dimensions and the spacer layer for optimal SEIRA enhancement of the C–H stretching mode. This tunable 3D geometry yields a theoretical SEIRA enhancement factor of 105, corresponding to the experimental detection of 20–200 zeptomoles of octadecanethiol, using a standard commercial FTIR spectrometer. Experimental studies illustrate the sensitivity of the observed SEIRA signal to the gap dimensions. The optimized antenna structure exhibits an order of magnitude greater SEIRA sensitivity than previous record-setting designs.

Fan-Shaped Gold Nanoantennas above Reflective Substrates for Surface-Enhanced Infrared Absorption (SEIRA)

A color-selective, band-engineered photodetector is demonstrated. The device uses two Schottky junctions to accumulate charge in an energy well, which results in photocurrent gain and a plasmonic aluminum grating for photocurrent enhancement and red-green-blue color selectivity. This work provides a more intelligent way to design imaging sensors by integrating amplifiers and color filters directly into pixels.

Bob Zheng

Papers

Narrowband photodetection in the near-infrared with a plasmon-induced hot electron device.

Distinguishing between plasmon-induced and photoexcited carriers in a device geometry

Embedding Plasmonic Nanostructure Diodes Enhances Hot Electron Emission

Fan-Shaped Gold Nanoantennas above Reflective Substrates for Surface-Enhanced Infrared Absorption (SEIRA)

Color‐Selective and CMOS‐Compatible Photodetection Based on Aluminum Plasmonics