Nicholas Rivera

Shrinking light to allow forbidden transitions on the atomic scale

Making the forbidden allowed Spontaneous emission, in which an excited electron lowers its energy by emitting a photon, is a fundamental process in light-matter interactions. In principle, the electron can relax from the excited state to any unoccupied lower energy level. In practice, however, most of these transitions are too slow and so are effectively forbidden. Rivera et al. show theoretically that the plasmonic excitations associated with two-dimensional materials can be used to enhance and control the light-matter interaction. Transitions that were once considered forbidden can thus be accessed, opening up the entire spectrum of an optical emitter. Science, this issue p. 263 The emission spectrum of an optical emitter can be enhanced by coupling to two-dimensional materials. The diversity of light-matter interactions accessible to a system is limited by the small size of an atom relative to the wavelength of the light it emits, as well as by the small value of the fine-structure constant. We developed a general theory of light-matter interactions with two-dimensional systems supporting plasmons. These plasmons effectively make the fine-structure constant larger and bridge the size gap between atom and light. This theory reveals that conventionally forbidden light-matter interactions—such as extremely high-order multipolar transitions, two-plasmon spontaneous emission, and singlet-triplet phosphorescence processes—can occur on very short time scales comparable to those of conventionally fast transitions. Our findings may lead to new platforms for spectroscopy, sensing, and broadband light generation, a potential testing ground for quantum electrodynamics (QED) in the ultrastrong coupling regime, and the ability to take advantage of the full electronic spectrum of an emitter.

All-angle negative refraction of highly squeezed plasmon and phonon polaritons in graphene–boron nitride heterostructures

Significance Realizing negative refraction of highly squeezed polaritons is an important step toward the active manipulation of light at the extreme nanoscale. To realize negative refraction, an effective means to tailor the coupling of different polaritons is absolutely necessary yet undeveloped. Here, we predict a viable way to flip the sign of group velocities of hybrid plasmon–phonon–polaritons in graphene–boron nitride (BN) heterostructures. The polaritonic strong coupling enables the all-angle negative refraction phenomena between highly squeezed graphene’s plasmons, BN’s phonon polaritons, and their hybrid polaritons. Due to the combined advantages of tunability, low loss, and ultrahigh confinement provided by these polaritons, graphene–BN heterostructures thus provide fundamental tools to explore the manipulation of light at the extreme nanoscale. A fundamental building block for nanophotonics is the ability to achieve negative refraction of polaritons, because this could enable the demonstration of many unique nanoscale applications such as deep-subwavelength imaging, superlens, and novel guiding. However, to achieve negative refraction of highly squeezed polaritons, such as plasmon polaritons in graphene and phonon polaritons in boron nitride (BN) with their wavelengths squeezed by a factor over 100, requires the ability to flip the sign of their group velocity at will, which is challenging. Here we reveal that the strong coupling between plasmon and phonon polaritons in graphene–BN heterostructures can be used to flip the sign of the group velocity of the resulting hybrid (plasmon–phonon–polariton) modes. We predict all-angle negative refraction between plasmon and phonon polaritons and, even more surprisingly, between hybrid graphene plasmons and between hybrid phonon polaritons. Graphene–BN heterostructures thus provide a versatile platform for the design of nanometasurfaces and nanoimaging elements.

Large Photothermal Effect in Sub‐40 nm h‐BN Nanostructures Patterned Via High‐Resolution Ion Beam

The controlled nanoscale patterning of 2D materials is a promising approach for engineering the optoelectronic, thermal, and mechanical properties of these materials to achieve novel functionalities and devices. Herein, high-resolution patterning of hexagonal boron nitride (h-BN) is demonstrated via both helium and neon ion beams and an optimal dosage range for both ions that serve as a baseline for insulating 2D materials is identified. Through this nanofabrication approach, a grating with a 35 nm pitch, individual structure sizes down to 20 nm, and additional nanostructures created by patterning crystal step edges are demonstrated. Raman spectroscopy is used to study the defects induced by the ion beam patterning and is correlated to scanning probe microscopy. Photothermal and scanning near-field optical microscopy measure the resulting near-field absorption and scattering of the nanostructures. These measurements reveal a large photothermal expansion of nanostructured h-BN that is dependent on the height to width aspect ratio of the nanostructures. This effect is attributed to the large anisotropy of the thermal expansion coefficients of h-BN and the nanostructuring implemented. The photothermal expansion should be present in other van der Waals materials with large anisotropy and can lead to applications such as nanomechanical switches driven by light.

Making two-photon processes dominate one-photon processes using mid-IR phonon polaritons

Significance The recent discovery of nanoscale-confined phonon polaritons in polar dielectric materials has generated vigorous interest because it provides a path to low-loss nanoscale photonics at technologically important mid-IR and terahertz frequencies. In this work, we show that these polar dielectrics can be used to develop a bright and efficient spontaneous emitter of photon pairs. The two-photon emission can completely dominate the total emission for realistic electronic systems, even when competing single-photon emission channels exist. We believe this work acts as a starting point for the development of sources of entangled nano-confined photons at frequency ranges where photon sources are generally considered lacking. Additionally, we believe that these results add a dimension to the great promise of phonon polaritonics. Phonon polaritons are guided hybrid modes of photons and optical phonons that can propagate on the surface of a polar dielectric. In this work, we show that the precise combination of confinement and bandwidth offered by phonon polaritons allows for the ability to create highly efficient sources of polariton pairs in the mid-IR/terahertz frequency ranges. Specifically, these polar dielectrics can cause emitters to preferentially decay by the emission of pairs of phonon polaritons, instead of the previously dominant single-photon emission. We show that such two-photon emission processes can occur on nanosecond time scales and can be nearly 2 orders of magnitude faster than competing single-photon transitions, as opposed to being as much as 8–10 orders of magnitude slower in free space. These results are robust to the choice of polar dielectric, allowing potentially versatile implementation in a host of materials such as hexagonal boron nitride, silicon carbide, and others. Our results suggest a design strategy for quantum light sources in the mid-IR/terahertz: ones that prefer to emit a relatively broad spectrum of photon pairs, potentially allowing for new sources of both single and multiple photons.

Shaping Polaritons to Reshape Selection Rules

In this work we show that by imbuing extremely highly confined polaritons with orbital angular momentum it is possible to induce new electronic selection rules in a controllable fashion.

Shaping Long-lived Electron Wavepackets to Create Customizable Optical Spectra

We introduce new shape-invariant electron wavepackets constructed via superpositions of states in the ionization continuum, enabling customizable optical emission spectra in the eV-keV range. Their shape-invariance is prolonged indefinitely in exchange for larger spatial spreads.

Strong light-matter coupling in quantum chemistry and quantum photonics

Abstract In this article, we review strong light-matter coupling at the interface of materials science, quantum chemistry, and quantum photonics. The control of light and heat at thermodynamic limits enables exciting new opportunities for the rapidly converging fields of polaritonic chemistry and quantum optics at the atomic scale from a theoretical and computational perspective. Our review follows remarkable experimental demonstrations that now routinely achieve the strong coupling limit of light and matter. In polaritonic chemistry, many molecules couple collectively to a single-photon mode, whereas, in the field of nanoplasmonics, strong coupling can be achieved at the single-molecule limit. Theoretical approaches to address these experiments, however, are more recent and come from a spectrum of fields merging new developments in quantum chemistry and quantum electrodynamics alike. We review these latest developments and highlight the common features between these two different limits, maintaining a focus on the theoretical tools used to analyze these two classes of systems. Finally, we present a new perspective on the need for and steps toward merging, formally and computationally, two of the most prominent and Nobel Prize-winning theories in physics and chemistry: quantum electrodynamics and electronic structure (density functional) theory. We present a case for how a fully quantum description of light and matter that treats electrons, photons, and phonons on the same quantized footing will unravel new quantum effects in cavity-controlled chemical dynamics, optomechanics, nanophotonics, and the many other fields that use electrons, photons, and phonons.

Metasurface-based multi-harmonic free-electron light source

Metasurfaces are subwavelength spatial variations in geometry and material where the structures are of negligible thickness compared to the wavelength of light and are optimized for far-field applications, such as controlling the wavefronts of electromagnetic waves. Here, we investigate the potential of the metasurface near-field profile, generated by an incident few-cycle pulse laser, to facilitate the generation of high-frequency light from free electrons. In particular, the metasurface near-field contains higher-order spatial harmonics that can be leveraged to generate multiple higher-harmonic X-ray frequency peaks. We show that the X-ray spectral profile can be arbitrarily shaped by controlling the metasurface geometry, the electron energy, and the incidence angle of the laser input. Using ab initio simulations, we predict bright and monoenergetic X-rays, achieving energies of 30 keV (with harmonics spaced by 3 keV) from 5-MeV electrons using 3.4-eV plasmon polaritons on a metasurface with a period of 85 nm. As an example, we present the design of a four-color X-ray source, a potential candidate for tabletop multicolor hard X-ray spectroscopy. Our developments could help pave the way for compact multi-harmonic sources of high-energy photons, which have potential applications in industry, medicine, and the fundamental sciences.Metasurfaces: X-rays from electrons hit by laser‘Metasurfaces’, whose composition and surface geometry vary at scales smaller than the wavelength of light, could become the new tunable sources of high-energy photons such as X-rays and gamma rays. Gilles Rosolen and colleagues at the Massachusetts Institute of Technology, USA, with co-workers in Belgium and Singapore, used simulation studies to explore the possibilities. Their work demonstrates how a pulsed laser could stimulate free electrons traveling close to a metasurface to generate photons with much higher energies than the incident laser light. The emitted frequency spectrum profile could be controlled by changing the metasurface geometry, the energy of the free electrons, and the angle of the applied laser light. The researchers say that the procedure could be developed to build novel tabletop sources of high-energy photons with many potential applications in industry, medicine and fundamental science.

Turning Forbidden Transitions into Dominant Transitions: Towards Efficient Sources of Entangled Light

We demonstrate that using phonon-polaritons in thin (quasi-2D) polar dielectrics, it is possible to turn forbidden transitions into dominant transitions, allowing for emitters of entangled light with quantum efficiencies exceeding 90%.