Joshua D. Caldwell

In applications such as atmospheric monitoring of greenhouse gases and pollutants, the detection and identification of trace concentrations of harmful gases is commonly achieved using non-dispersive infrared (NDIR) sensors. These devices employ a broadband infrared emitter, thermopile detector, and a spectrally selective bandpass filter tuned to the vibrational resonance of the target analyte. However, the fabrication of these filters is costly and limited to a single frequency. This limitation introduces a fundamental tradeoff, as broadening the optical passband width enhances sensitivity but compromises selectivity, whereas narrowing improves selectivity at the expense of sensitivity. In this work, we validate a filterless NDIR approach using a multi-peak thermal emitter developed through inverse design. This emitter enhances detection sensitivity by targeting multiple absorption bands, demonstrated through the creation of a sensor designed for the C-H vibrational modes of propane. Additionally, a set of single-peak emitters were developed to showcase the capability of designing highly selective sensors operating within close spectral proximity. These emitters, targeting the stretching modes of carbon monoxide and carbon dioxide, exhibit Q-factors above 50 and minimal crosstalk, enabling accurate detection of the target gas without interference from gases with spectrally adjacent absorption bands. This is enabled by the implementation of an aperiodic distributed Bragg reflectors, which allows for higher Q-factors with fewer layers than a periodic Bragg reflector using the same materials and number of layers, thereby reducing fabrication complexity and cost. Experimental results validate that this approach breaks the tradeoff between sensitivity and selectivity. This work highlights the potential of optimized thermal emitters for more efficient and compact gas sensing applications.

The implementation of polaritonic materials into nanoscale devices requires selective tuning of parameters to realize desired spectral or thermal responses. One robust material is α-MoO3, which as an orthorhombic crystal boasts three distinct phonon dispersions, providing three polaritonic dispersions of hyperbolic phonon polaritons (HPhPs) across the mid-infrared (MIR). Here, the tunability of both optical and thermal responses in isotopically enriched α-MoO3 (98MoO3, Mo18O3 and 98Mo18O3) are explored. A uniform ~5 % spectral redshift from 18O enrichment is observed in both Raman- and IR-active TO phonons. Both the in- and out-of-plane thermal conductivities for the isotopic variations are reported. Ab initio calculations both replicate experimental findings and analyze the select-mode three-phonon scattering contributions. The HPhPs from each isotopic variation are probed with s-SNOM and their Q- factors are reported. A Q-factor maxima increase of ~50 % along the [100] in the RB2 and ~100 % along the [001] in the RB3 are reported for HPhPs supported in 98Mo18O3. Observations in both real and Fourier space of higher-order HPhP modes propagating in single slabs of isotopically enriched α-MoO3 without the use of a subdiffractional surface scatterer are presented here. This work illustrates the tunability of α-MoO3 for thermal and nanophotonic applications.

In this work, we develop a rapid reactive vapor transport technique to efficiently utilize limited isotopically pure precursors, particularly gaseous 18O2, and synthesize mm-scale, high-quality crystals within few-minute growth durations. We unlock this capability by using metallic molybdenum precursors with high source temperatures (900 C) and total pressures (1 atm) to maximize precursor efficiency and yield. Subsequently, we grow MoO3 single crystals with high and uniform enrichment levels of 98Mo and 18O isotopes in several different permutations. As probed by Raman spectroscopy, modest and significant phonon energy redshifts occur following 98Mo and 18O enrichment, respectively. By demonstrating control over both molybdenum and oxygen isotopic fractions, we establish a powerful tool to advance nanophotonics and thermal management goals using MoO3. This work is motivated by the possibility to enhance and engineer lattice vibrational mode phenomena including thermal conduction and hyperbolic phonon polariton (HPhP) dispersion, with particular interest in comparing the effects of light and heavy element enrichment.

Hyperbolic phonon polaritons - hybridized modes arising from the ultrastrong coupling of infrared light to strongly anisotropic lattice vibrations in uniaxial or biaxial polar crystals - enable to confine light to the nanoscale with low losses and high directionality. In even lower symmetry materials, such as monoclinic $β$-Ga$_2$O$_3$ (bGO), hyperbolic shear polaritons (HShPs) further enhance the directionality. Yet, HShPs are intrinsically supported only within narrow frequency ranges defined by the phonon frequencies of the host material. Here, we report spectral tuning of HShPs in bGO by isotopic substitution. Employing near-field optical microscopy to image HShPs in $^{18}$O bGO films homo-epitaxially grown on a $^{16}$O bGO substrate, we demonstrate a spectral redshift of $\sim~40~$cm$^{-1}$ for the $^{18}$O bGO, compared to $^{16}$O bGO. The technique allows for direct observation and a model-free estimation of the spectral shift driven by isotopic substitution without the need for knowledge of the dielectric tensor. Complementary far-field measurements and ab initio calculations - in good agreement with the near-field data - confirm the effectiveness of this estimation. This multifaceted study demonstrates a significant isotopic substitution induced spectral tuning of HShPs into a previously inaccessible frequency range, creating new avenues for technological applications of such highly directional polaritons.

Hexagonal boron nitride (hBN) is an important 2D material for van der Waals heterostructures, single photon emitters, and infrared nanophotonics. The optical characterization of mono- and few-layer samples of hBN however remains a challenge as the material is almost invisible optically. Here we introduce phase-resolved sum-frequency microscopy as a technique for imaging monolayers of hBN grown by chemical vapor deposition (CVD) and visualize their crystal orientation. A combination of femtosecond mid-infrared (IR) and visible laser pulses is used for sum-frequency generation (SFG), which is imaged in a wide-field optical microscope. The IR laser resonantly excites a phonon of hBN that leads to an ~800-fold enhancement of the SFG intensity, making it possible to image large 100x100 {\mu}m2 sample areas in less than 1 s. Implementing heterodyne detection in combination with azimuthal rotation of the sample further provides full crystallographic information. Through combined knowledge of topography and crystal orientation, we find that triangular domains of CVD-grown monolayer hBN have nitrogen-terminated zigzag edges. Overall, SFG microscopy can be used as an ultra-sensitive tool to image crystal structure, strain, stacking sequences, and twist angles, and is applicable to the wide range of van der Waals structures, where location and identification of monolayer regions and interfaces with broken inversion symmetry is of paramount importance.

Triggered by the development of exfoliation and the identification of a wide range of extraordinary physical properties in self-standing films consisting of one or few atomic layers, two-dimensional (2D) materials such as graphene, transition metal dichalcogenides (TMDs), and other van der Waals (vdW) crystals currently constitute a wide research field protruding in multiple directions in combination with layer stacking and twisting, nanofabrication, surface-science methods, and integration into nanostructured environments. Photonics encompasses a multidisciplinary collection of those directions, where 2D materials contribute with polaritons of unique characteristics such as strong spatial confinement, large optical-field enhancement, long lifetimes, high sensitivity to external stimuli (e.g., electric and magnetic fields, heating, and strain), a broad spectral range from the far infrared to the ultraviolet, and hybridization with spin and momentum textures of electronic band structures. The explosion of photonics with 2D materials as a vibrant research area is producing breakthroughs, including the discovery and design of new materials and metasurfaces with unprecedented properties as well as applications in integrated photonics, light emission, optical sensing, and exciting prospects for applications in quantum information, and nanoscale thermal transport. This Roadmap summarizes the state of the art in the field, identifies challenges and opportunities, and discusses future goals and how to meet them through a wide collection of topical sections prepared by leading practitioners.

Metal-based thermal metasurfaces exhibit stable spectral characteristics under temperature fluctuations, in contrast to more traditional gray- and near black-bodies, as well as some dielectric metasurfaces, whose emission spectra shift with changing temperatures. However, they often suffer from limited quality (Q) factors due to significant non-radiative ohmic losses. In this study, we address the challenge of achieving high emissivity and Q-factors in metal-based thermal emitters. By leveraging the coupling between a magnetic dipole resonance and two bound-state-in-continuum (BIC) resonances to achieve electromagnetically induced absorption (EIA) in an asymmetric metallic ring structure, we design a metal-based thermal metasurface with a near-unity emissivity (0.96) and a Q factor as high as 320 per simulations. Experimental validation yields an emissivity of 0.82 and a Q factor of 202, representing an approximately five-fold improvement in the experimentally measured Q factor compared to the state-of-the-art metal-based thermal metasurfaces. Our work offers a promising approach for developing efficient, narrow-band, directional thermal emitters with stable emission spectra across a wide temperature range.

The confinement of electromagnetic radiation to subwavelength scales relies on strong light-matter interactions. In the infrared (IR) and terahertz (THz) spectral ranges, phonon polaritons are commonly employed to achieve extremely subdiffractional light confinement, with much lower losses as compared to plasmon polaritons. Among these, hyperbolic phonon polaritons in anisotropic materials offer a highly promising platform for light confinement, which, however, typically plateaus at values of {\lambda}0/100, with {\lambda}0 being the free-space incident wavelength. In this study, we report on ultraconfined phonon polaritons in hafnium-based dichalcogenides with confinement factors exceeding {\lambda}0/250 in the terahertz spectral range. This extreme light compression within deeply sub-wavelength thin films is enabled by the unprecedented magnitude of the light-matter coupling strength in these compounds, and the natural hyperbolicity of HfSe2 in particular. Our findings emphasize the critical role of light-matter coupling for polariton confinement, which for phonon polaritons in polar dielectrics is dictated by the transverse-longitudinal optic phonon energy splitting. Our results demonstrate transition metal dichalcogenides as an enabling platform for THz nanophotonic applications that push the limits of light control.

Low symmetry crystals have recently emerged as a platform for exploring novel light-matter interactions in the form of hyperbolic shear polaritons. These excitations exhibit unique optical properties such as frequency-dispersive optical axes and asymmetric light propagation and energy dissipation, which arise from the presence of non-orthogonal resonances. However, only non-vdW materials have been demonstrated to support hyperbolic shear polaritons, limiting their exotic properties and potential applications. Here we introduce for the first time novel shear phenomena in low symmetry crystal thin films by demonstrating the existence of elliptical and canalized shear phonon polaritons in gypsum, an exfoliable monoclinic sulphate mineral. Our results unveil a topological transition from hyperbolic shear to elliptical shear polaritons, passing through a canalization regime with strong field confinement. Importantly, we observe a significant slowdown of group velocity, reaching values as low as 0.0005c, highlighting the potential of gypsum for "slow light" applications and extreme light-matter interaction control. These findings expand the application scope of low-symmetry crystals with the benefits that an exfoliable material provides, such as stronger field confinement, tunability, and versatility for its incorporation in complex photonic devices that might unlock new optical phenomena at the nanoscale.

Notwithstanding its relevance to many applications in sensing, security, and communications, electrical generation of narrow-band mid-infrared light remains highly challenging. Unlike in the ultraviolet or visible spectral regions few materials possess direct electronic transitions in the mid-infrared and most that do are created through complex band-engineering schemes. An alternative mechanism, independent of dipole active material transitions, relies instead on energy lost to the polar lattice through the Coulomb interaction. Longitudinal phonons radiated in this way can be spectrally tuned through the engineering of polar nanostructures and coupled to localized optical modes in the material, allowing them to radiate mid-infrared photons into the far-field. A recent theoretical work explored this process providing for the first time an indication of its technological relevance when compared to standard thermal emitters. In order to do so it nevertheless used an equilibrium model of the electron gas, making this model difficult to inform the design of an optimal device to experimentally observe the effect. The present paper removes this limitation, describing the electron gas using a rigorous, self-consistent, non-equilibrium Green's function model, accounting for variations in material properties across the device, and electron-electron interactions. Although the instability of the Schrodinger-Poisson iteration limits our studies to the low-bias regime, our results demonstrate emission rates comparable to that of room-temperature thermal emission despite such low biases. These results provide a pathway to design a confirmatory experiment of this new emission channel, that could power a new generation of mid-infrared optoelectronic devices.