Kevin D. Heylman

Photothermal Microscopy of Nonluminescent Single Particles Enabled by Optical Microresonators.

A powerful new paradigm for single-particle microscopy on nonluminescent targets is reported using ultrahigh-quality factor optical microresonators as the critical detecting element. The approach is photothermal in nature as the microresonators are used to detect heat dissipated from individual photoexcited nano-objects. The method potentially satisfies an outstanding need for single-particle microscopy on nonluminescent objects of increasingly smaller absorption cross section. Simultaneously, our approach couples the sensitivity of label-free detection using optical microresonators with a means of deriving chemical information on the target species, a significant benefit. As a demonstration, individual nonphotoluminescent multiwalled carbon nanotubes are spatially mapped, and the per-atom absorption cross section is determined. Finite-element simulations are employed to model the relevant thermal processes and elucidate the sensing mechanism. Finally, a direct pathway to the extension of this new technique to molecules is laid out, leading to a potent new method of performing measurements on individual molecules.

Chip-Scale Fabrication of High-Q All-Glass Toroidal Microresonators for Single-Particle Label-Free Imaging.

Whispering-gallery-mode microresonators enable materials for single-molecule label-free detection and imaging because of their high sensitivity to their micro-environment. However, fabrication and materials challenges prevent scalability and limit functionality. All-glass on-chip microresonators significantly reduce these difficulties. Construction of all-glass toroidal microresonators with high quality factor and low mode volume is reported and these are used as platforms for label-free single-particle imaging.

Photothermal mapping and free-space laser tuning of toroidal optical microcavities

We report a tuning method for ultrahigh-quality factor toroidal optical microcavities capable of rapid modulation and resonance position control over multiple decades. A free-space laser is focused onto the resonators silicon support pillar, rapidly heating the mode-containing silica. Microcavity photothermal response is spatially mapped. Resonance shift varies inversely with pillar diameter, reaching 1.5 × 105 fm/mW at 2 μm diameter, allowing switching with 1 μW control power. Larger pillar resonators can be modulated at high speeds (>4 kHz). Heat flow simulations accurately model observed shifts. This versatile approach fulfills an outstanding need for fast, flexible control over toroid resonances.

Optical Microresonators for Sensing and Transduction: A Materials Perspective

Optical microresonators confine light to a particular microscale trajectory, are exquisitely sensitive to their microenvironment, and offer convenient readout of their optical properties. Taken together, this is an immensely attractive combination that makes optical microresonators highly effective as sensors and transducers. Meanwhile, advances in material science, fabrication techniques, and photonic sensing strategies endow optical microresonators with new functionalities, unique transduction mechanisms, and in some cases, unparalleled sensitivities. In this progress report, the operating principles of these sensors are reviewed, and different methods of signal transduction are evaluated. Examples are shown of how choice of materials must be suited to the analyte, and how innovations in fabrication and sensing are coupled together in a mutually reinforcing cycle. A tremendously broad range of capabilities of microresonator sensors is described, from electric and magnetic field sensing to mechanical sensing, from single-molecule detection to imaging and spectroscopy, from operation at high vacuum to in live cells. Emerging sensing capabilities are highlighted and put into context in the field. Future directions are imagined, where the diverse capabilities laid out are combined and advances in scalability and integration are implemented, leading to the creation of a sensor unparalleled in sensitivity and information content.

Exploring Electronic Structure and Order in Polymers via Single-Particle Microresonator Spectroscopy

PEDOT PSS, a transparent electrically conductive polymer, finds widespread use in electronic devices. While empirical efforts have increased conductivity, a detailed understanding of the coupled electronic and morphological landscapes in PEDOT:PSS has lagged due to substantial structural heterogeneity on multiple length-scales. We use an optical microresonator-based absorption spectrometer to perform single-particle measurements, providing a bottom-up examination of electronic structure and morphology ranging from single PEDOT:PSS polymers to nascent films. Using single-particle spectroscopy with complementary theoretical calculations and ultrafast spectroscopy, we demonstrate that PEDOT:PSS displays bulk-like optical response even in single polymers. We find highly ordered PEDOT assemblies with long-range ordering mediated by the insulating PSS matrix and reveal a preferential surface orientation of PEDOT nanocrystallites absent in bulk films with implications for interfacial electronic communication. Our single-particle perspective provides a unique window into the microscopic structure and electronic properties of PEDOT:PSS.

Sculpting Fano Resonances To Control Photonic–Plasmonic Hybridization

Hybrid photonic-plasmonic systems have tremendous potential as versatile platforms for the study and control of nanoscale light-matter interactions since their respective components have either high-quality factors or low mode volumes. Individual metallic nanoparticles deposited on optical microresonators provide an excellent example where ultrahigh-quality optical whispering-gallery modes can be combined with nanoscopic plasmonic mode volumes to maximize the systems photonic performance. Such optimization, however, is difficult in practice because of the inability to easily measure and tune critical system parameters. In this Letter, we present a general and practical method to determine the coupling strength and tailor the degree of hybridization in composite optical microresonator-plasmonic nanoparticle systems based on experimentally measured absorption spectra. Specifically, we use thermal annealing to control the detuning between a metal nanoparticles localized surface plasmon resonance and the whispering-gallery modes of an optical microresonator cavity. We demonstrate the ability to sculpt Fano resonance lineshapes in the absorption spectrum and infer system parameters critical to elucidating the underlying photonic-plasmonic hybridization. We show that including decoherence processes is necessary to capture the evolution of the lineshapes. As a result, thermal annealing allows us to directly tune the degree of hybridization and various hybrid mode quantities such as the quality factor and mode volume and ultimately maximize the Purcell factor to be 104.

Revealing Conformational Variants of Solution‐Phase Intrinsically Disordered Tau Protein at the Single‐Molecule Level

Intrinsically disordered proteins, such as tau protein, adopt a variety of conformations in solution, complicating solution-phase structural studies. We employed an anti-Brownian electrokinetic (ABEL) trap to prolong measurements of single tau proteins in solution. Once trapped, we recorded the fluorescence anisotropy to investigate the diversity of conformations sampled by the single molecules. A distribution of anisotropy values obtained from trapped tau protein is conspicuously bimodal while those obtained by trapping a globular protein or individual fluorophores are not. Time-resolved fluorescence anisotropy measurements were used to provide an explanation of the bimodal distribution as originating from a shift in the compaction of the two different families of conformations.

Cleaning procedure for improved photothermal background of toroidal optical microresonators

High Q-factors and small mode volumes have made toroidal optical microresonators exquisite sensors to small shifts in the effective refractive index of the WGM modes. Eliminating contaminants and improving quality factors is key for many different sensing techniques, and is particularly important for photothermal imaging as contaminants add photothermal background obscuring objects of interest. Several different cleaning procedures including wet- and dry-chemical procedures are tested for their effect on Q-factors and photothermal background. RCA cleaning was shown to be successful in contrast to previously described acid cleaning procedures, most likely due to the different surface reactivity of the acid reagents used. UV-ozone cleaning was shown to be vastly superior to O2 plasma cleaning procedures, significantly reducing the photothermal background of the resonator.

Optical Microresonators: Chip‐Scale Fabrication of High‐Q All‐Glass Toroidal Microresonators for Single‐Particle Label‐Free Imaging (Adv. Mater. 15/2016)

On page 2945, R. H. Goldsmith and co-workers describe an all-glass, high-Q, low-mode-volume optical microresonator for label-free sensing and imaging, which overcomes scalability barriers and also brings other advantages, including optical transparency. By using the microresonators as transducers to detect heat dissipated by individual nano-objects upon photoexcitation, label-free single-particle imaging is demonstrated.

Photothermal imaging of individual carbon nanofibers with optical microresonators

A new method is described for measuring the absorption of light by single non-emissive nanoparticles. Individual carbon nanofibers are imaged using a photonic transducer to quantify the heat dissipated after the electronic energy is thermalized. Leveraging the high sensitivity of ultrahigh-quality-factor optical microresonators as photothermal transducers provides high sensitivity. Polarization-resolved measurements indicate that the orientation of the absorption dipole of a nanofiber matches the long axis of the fiber. The per-atom absorption cross-section is determined to be (2.9 x 10-18 cm2 /carbon atom), in close agreement with the value for bulk graphite.