Resolving resonance effects in the theory of single particle photothermal imaging
Harrison J. Goldwyn, Stephan Link, David J. Masiello
备注：
Submitted to the Journal of Chemical Physics. This version contains updates to the Introduction, reframing the work in the context of past literature. Discussions around the mathematical derivations have been updated throughout. Minor updates to the theory (including the phase of the transmitted/reflected probe beam, SI Section S1) have propagated through all figures
Photothermal spectroscopy and microscopy provides a route to measure the spectral and spatial properties of individual nanoscopic absorbers, independent from scattering, extinction, and emission. The approach relies upon use of two light sources, one that resonantly excites and heats the target and its surrounding environment and a second off-resonant probe that scatters from the resulting volume of thermally modified refractive index. Over the past twenty years, considerable effort has been extended to apply photothermal methods to detect, spatially resolve, and perform absorption spectroscopy on single non-emissive molecules and other absorbers like plasmonic nanoparticles at room temperature conditions. Companion theoretical models have been developed to interpret these experimental advances, yet it is not clear how they are related to each other nor how the effects of lock-in detection modify the theory. For larger target systems that host their own intrinsic scattering resonances as well as for background media that do not instantaneously thermalize with the absorbing target, additional dependencies arise that are yet to be explored theoretically. The aim of this Perspective is to overview the theory of photothermal spectroscopy and microscopy and present a unifying theoretical approach that recovers past models in certain limits while explicitly including the effects of target scattering resonances, thermal and optical retardation, and lock-in detection. Focus is made on plasmonic particles to interpret the photothermal signal, yet all results are applicable equally to individual molecules or nanoparticle absorbers. Consequently, we expect this review to provide a useful foundation for the understanding of photothermal measurements independent of target identity.
Mid-infrared photothermal microscopy is a new chemical imaging technology in which a visible beam senses the photothermal effect induced by a pulsed infrared laser. This technology provides infrared spectroscopic information at sub-micron spatial resolution and enables infrared spectroscopy and imaging of living cells and organisms. Yet, current mid-infrared photothermal imaging sensitivity suffers from a weak dependance of scattering on temperature and the image quality is vulnerable to the speckles caused by scattering. Here, we present a novel version of mid-infrared photothermal microscopy…
Infrared (IR) imaging has become a viable tool for visualizing various chemical bonds in a specimen. The performance, however, is limited in terms of spatial resolution and imaging speed. Here, instead of measuring the loss of the IR beam, we utilize a pulsed visible light for a high-throughput, widefield sensing of the transient photothermal effect induced by absorption of single mid-IR pulses. To extract such transient signals, we built a virtual lock-in camera synchronized to the visible probe and IR light pulses with precisely-controlled delays, allowing sub-microsecond temporal resolution…
Amyloid proteins are associated with a broad spectrum of neurodegenerative diseases. However, it remains a grand challenge to extract molecular structure information from intracellular amyloid proteins in their native cellular environment. To address this challenge, we developed a computational chemical microscope integrating 3D mid-infrared photothermal imaging with fluorescence imaging, termed Fluorescence-guided Bond-Selective Intensity Diffraction Tomography (FBS-IDT). Based on a low-cost and simple optical design, FBS-IDT enables chemical-specific volumetric imaging and 3D site-specific m…
While the thermal and electromagnetic properties of plasmonic nanostructures are well understood, nanoscale thermometry still presents an experimental and theoretical challenge. Plasmonic structures can confine electromagnetic energy at the nanoscale, resulting in local, inhomogeneous, controllable heating. But reading out the temperature with nanoscale precision using optical techniques poses a difficult challenge. Here we report on the optical thermometry of individual gold nanorod trimers that exhibit multiple wavelength-dependent plasmon modes resulting in measurably different local temper…
The literature on the theory of the photothermal imaging of single nano objects is reviewed. Several models have been devised to describe the signals magnitude, phase and shape in dependence on the experimental and sample parameters (particle position and optical properties, laser beams and their offset, modulation frequency, (thermo-)refractive coefficients, thermal constants). The benefits and limitations of these models are summarized allowing the proper choice of a framework for future investigations using photothermal microscopy of single absorbers.
Leibniz Institute of Photonic Technology（莱布尼茨光子技术研究所）；Friedrich-Schiller-University Jena（耶拿弗里德里希·席勒大学）；InfectoGnostics Research Campus Jena（耶拿感染诊断研究园区）
Label-free Imaging of Single-Biomolecule Structure and Interaction by Stimulated Raman Photothermal Encoded Scattering
Boston University（波士顿大学）；Stowers Institute for Medical Research（斯图沃医学研究所）；University of Washington（华盛顿大学）；Northeastern University（东北大学）；Georgia Institute of Technology（佐治亚理工学院）；Emory University（埃默里大学）；University of Virginia School of Medicine（弗吉尼亚大学医学院）；Howard Hughes Medical Institute（霍华德·休斯医学研究所）
Mid-infrared photothermal (MIP) microscopy has been a promising label-free chemical imaging technique for functional characterization of specimens owing to its enhanced spatial resolution and high specificity. Recently developed wide-field MIP imaging modalities have drastically improved speed and enabled high-throughput imaging of micron-scale subjects. However, the weakly scattered signal from sub-wavelength particles becomes indistinguishable from the shot-noise as a consequence of the strong background light, leading to limited sensitivity. Here, we demonstrate background-suppressed chemic…
Several fields of applications require a reliable characterization of the photothermal response and heat dissipation of nanoscopic systems, which remains a challenging task both for modeling and experimental measurements. Here, we present a new implementation of anti-Stokes thermometry that enables the in situ photothermal characterization of individual nanoparticles (NPs) from a single hyperspectral photoluminescence confocal image. The method is label-free, applicable to any NP with detectable anti-Stokes emission, and does not require any prior information about the NP itself or the surroun…
Millimeter-scale wide-field mid-infrared photothermal imaging enabled by a broadly tunable picosecond optical parametric oscillator
Leibniz Institute of Photonic Technology（莱布尼茨光子技术研究所）；Otto Schott Institute of Materials Research, Friedrich-Schiller-University Jena（弗里德里希·席勒大学耶拿分校奥托·肖特材料研究所）；Friedrich-Schiller-University Jena（弗里德里希·席勒大学耶拿分校）
A unified framework for sensitivity comparison across stimulated Raman, stimulated Raman photothermal, and mid-infrared photothermal microscopy
Institute for Photon Science and Technology, The University of Tokyo（东京大学光子科学研究所）；Department of Advanced Materials Science, The University of Tokyo（东京大学先进材料科学系）；RIKEN Center for Advanced Photonics, RIKEN（理化学研究所先进光子学中心）
The photothermal heterodyne imaging technique enabled studies of individual weakly absorbing nano-objects in various environments. It uses a photo-induced change in the refractive index of the environment. Taking advantage of the dramatic index of refraction change occurring around a thermotropic liquid crystalline phase transition, we demonstrate a 40-fold signal-to-noise ratio enhancement for gold nanoparticles imaged in 4-Cyano-4'-pentylbiphenyl (5CB) liquid crystals over those in a water environment. We studied the photothermal signal as a function of probe laser polarization, heating powe…
Over the last decade, single-molecule optical microscopy has become the gold-standard approach to decipher complex molecular processes in cellular environments. [1-3] Single-molecule fluorescence microscopy has several advantages such as ease of application, high sensitivity, low invasiveness and versatility due the large number of available fluorescent probes. It bears however some drawbacks related to the poor photostability of organic dye molecules [4] and auto-fluorescent proteins [5-7] and and to the relatively large size of semiconductor nanoparticles in the context of live cell applicat…
Single-molecule microscopy has become an indispensable tool for biochemical analysis. The capability of characterizing distinct properties of individual molecules without averaging has provided us with a different perspective for the existing scientific issues and phenomena. Recently, the super-resolution fluorescence microscopy techniques have overcome the optical diffraction limit by the localization of molecule positions. However, the labelling process can potentially modify the intermolecular dynamics. Based on the highly-sensitive nanomechanical photothermal microscopy reported previously…
Free-electron laser-based extended wide-field mid-infrared photothermal imaging for biomedical and microplastic analysis
Leibniz Institute of Photonic Technology（莱布尼兹光子技术研究所）；Research Center Borstel, Leibniz Lung Center（博斯特尔研究中心，莱布尼兹肺科中心）；German Center for Infection Research (DZIF)（德国感染研究联合会）；Jena University Hospital（耶拿大学医院）；Helmholtz-Zentrum Dresden Rossendorf（德累斯顿-罗斯多夫亥姆霍兹中心）；Friedrich-Schiller-University Jena（耶拿弗里德里希·席勒大学）
Featured with a plethora of electric and magnetic Mie resonances, high index dielectric nanostructures offer a versatile platform to concentrate light-matter interactions at the nanoscale. By integrating unique features of far-field scattering control and near-field concentration from radiationless anapole states, here, we demonstrate a giant photothermal nonlinearity in single subwavelength-sized silicon nanodisks. The nanoscale energy concentration and consequent near-field enhancements mediated by the anapole mode yield a reversible nonlinear scattering with a large modulation depth and a b…
Thermonanophotonics, i.e. the study of photothermal effects in optical nanoantennas, has recently attracted growing interest. While thermoplasmonic structures enable a broad range of applications, from imaging and optofluidics devices to medical and photochemical systems, dielectric nanoantennas open new opportunities for thermo-optical modulation and reconfigurable metasurfaces. However, computing both photo-thermal and thermo-optical effects in large arrays of nanoantennas remains a challenge. In this work, we implement a fast numerical method to compute the temperature increase of multi-dim…
Fundamental understanding of biological pathways requires minimally invasive nanoscopic optical resolution imaging. Many approaches to high-resolution imaging rely on localization of single emitters, such as fluorescent molecule or quantum dot. Exact determination of the number of such emitters in an imaging volume is essential for a number of applications; however, in a commonly employed intensity-based microscopy it is not possible to distinguish individual emitters without initial knowledge of system parameters. Here we explore how quantum measurements of the emitted photons using photon nu…
Massachusetts Institute of Technology（麻省理工学院）；University of Waikato（怀卡托大学）
Time-of-flight (ToF) cameras calculate depth maps by reconstructing phase shifts of amplitude-modulated signals. For broad illumination or transparent objects, reflections from multiple scene points can illuminate a given pixel, giving rise to an erroneous depth map. We report here a sparsity regularized solution that separates K-interfering components using multiple modulation frequency measurements. The method maps ToF imaging to the general framework of spectral estimation theory and has applications in improving depth profiles and exploiting multiple scattering.
Imaging through opaque, highly scattering walls is a long sought after capability with potential applications in a variety of fields. The use of wavefront shaping to compensate for scattering has brought a renewed interest as a potential solution to this problem. A key to the practicality of any imaging technique is the capability to focus light without direct access behind the scattering wall. Here, we address this problem using photoacoustic feedback for wavefront optimization. By combining the spatially non-uniform sensitivity of the ultrasound transducer to the generated photoacoustic wave…
Optical coherence tomography (OCT) is a label-free, non-invasive 3D imaging tool widely used in both biological research and clinical diagnosis. Current OCT modalities can only visualize specimen tomography without chemical information. Here, we report a bondselective full-field OCT (BS-FF-OCT), in which a pulsed mid-infrared laser is used to modulate the OCT signal through the photothermal effect, achieving label-free bond-selective 3D sectioned imaging of highly scattering samples. We first demonstrate BS-FF-OCT imaging of 1 μm PMMA beads embedded in agarose gel. Next, we then show 3D hypers…
The wave-particle duality of light introduces two fundamental problems to imaging, namely, the diffraction limit and the photon shot noise. Quantum information theory can tackle them both in one holistic formalism: model the light as a quantum object, consider any quantum measurement, and pick the one that gives the best statistics. While Helstrom pioneered the theory half a century ago and first applied it to incoherent imaging, it was not until recently that the approach offered a genuine surprise on the age-old topic by predicting a new class of superior imaging methods. For the resolution …
Optical lenses are pervasive in various areas of sciences and technologies. It is well-known that the resolving power of a lens and thus optical systems is limited by the diffraction of light. Recently, various plasmonics and metamaterials based superlenses have been emerging to achieve super resolution. Here, we show that the phase compensated negative refraction lenses perform as "Janus Lenses", i.e. either converging lenses or diverging lenses depending on the illumination directions. Extraordinary imaging equations and properties that are different from those of all the existing optical le…
Imaging in a broad light-intensity regime with a high signal-to-noise ratio is a key capability in fields as diverse as Quantum Metrology and Astronomy. Achieving high signal-to-noise ratios in quantum imaging leads to surpassing the classical limit in parameter estimation. In astronomical detection, the search for habitable exoplanets demands imaging in the infrared its atmospheres looking for biosignatures. These optical applications are hampered by detection noise, which critically limits their potential, and thus demands photon-number and spatial resolution detectors. Here we report an ima…
For developing a detailed network model of the brain based on image reconstructions, it is necessary to spatially resolve crossing nerve fibers. The accuracy hereby depends on many factors, including the spatial resolution of the imaging technique. 3D Polarized Light Imaging (3D-PLI) allows the three-dimensional reconstruction of nerve fiber tracts in whole brain sections with micrometer in-plane resolution, but leaves uncertainties in pixels containing crossing fibers. Here we introduce Scattered Light Imaging (SLI) to resolve the substructure of nerve fiber crossings. The measurement is perf…
Near-field scanning optical microscopy has been an indispensable tool for designing, characterizing and understanding the functionalities of diverse nanoscale photonic devices. As the advances in fabrication technology have driven the devices smaller and smaller, the demand has grown steadily for improving its resolving power, which is determined mainly by the size of the probe attached to the scanner. The use of a smaller probe has been a straightforward approach to increase the resolving power, but it cannot be made arbitrarily small in practice due to the steep reduction of the collection e…
IR spectroscopy has been widely used for chemical identification and quantitative analysis of reactions occurring in a specific time and space domains by measuring an average signal of the entire system1. Achieving IR measurements with nanometer-scale spatial resolution is highly desirable to obtain a detailed understanding of the composition, structure and function of interfaces2-5. The challenges in IR nanoscopy yet exist owing to the small molecular cross section and pristine optical diffraction limit. Although atomic force microscopy (AFM) based techniques, such as scattering-type scanning…
