Photothermal Heterodyne Imaging Research Articles

Investigating the Role of Plasmonics in Electrospun Fibers by Combined Photothermal Heterodyne Imaging and Raman Measurements

Investigating the Role of Plasmonics in Electrospun Fibers by Combined Photothermal Heterodyne Imaging and Raman Measurements

Single-Particle Analysis of the Photodegradation of Submicron Polystyrene Particles Using Infrared Photothermal Heterodyne Imaging.

Sunlight irradiation is the predominant process for degrading plastics in the environment, but our current understanding of the degradation of smaller, submicron (<1000 nm) particles is limited due to prior analytical constraints. We used infrared photothermal heterodyne imaging (IR-PHI) to simultaneously analyze the chemical and morphological changes of single polystyrene (PS) particles (∼1000 nm) when exposed to ultraviolet (UV) irradiation (λ = 250-400 nm). Within 6 h of irradiation, infrared bands associated with the backbone of PS decreased, accompanied by a reduction in the particle size. Concurrently, the formation of several spectral features due to photooxidation was attributed to ketones, carboxylic acids, aldehydes, esters, and lactones. Spectral outcomes were used to present an updated reaction scheme for the photodegradation of PS. After 36 h, the average particle size was reduced to 478 ± 158 nm. The rates of size decrease and carbonyl band area increase were -24 ± 3.0 nm h-1 and 2.1 ± 0.6 cm-1 h-1, respectively. Using the size-related rate, we estimated that under peak terrestrial sunlight conditions, it would take less than 500 h for a 1000 nm PS particle to degrade to 1 nm.

Photothermal heterodyne imaging of micron-sized objects.

Micron-sized dye-doped polymer beads were imaged using transmitted/reflected light microscopy and photothermal heterodyne imaging (PHI) measurements. The transmitted/reflected light images show distinct ring patterns that are attributed to diffraction effects and/or internal reflections within the beads. In the PHI experiments pump laser induced heating changes the refractive index and size of the bead, which causes changes in the diffraction pattern and internal reflections. This creates an analogous ring pattern in the PHI images. The ring pattern disappears in both the reflected light and PHI experiments when an incoherent light source is used as a probe. When the beads are imaged in an organic medium heat transfer changes the refractive index of the environment, and gives rise to a ring pattern external to the beads in the PHI images. This causes the beads to appear larger than their physical dimensions in PHI experiments. This external signal does not appear when the beads are imaged in air because the refractive index changes in air are very small.

Ultrafast Widefield Mid-Infrared Photothermal Heterodyne Imaging.

Mid-infrared photothermal (MIP) microscopy is a valuable tool for sensitive and fast chemical imaging with high spatial resolution beyond the mid-infrared diffraction limit. The highest sensitivity is usually achieved with heterodyne MIP employing photodetector point-scans and lock-in detection, while the fastest systems use camera-based widefield MIP with pulsed probe light. One challenge is to simultaneously achieve high sensitivity, spatial resolution, and speed in a large field of view. Here, we present widefield mid-infrared photothermal heterodyne (WIPH) imaging, where a digital frequency-domain lock-in (DFdLi) filter is used for simultaneous multiharmonic demodulation of MIP signals recorded by individual camera pixels at frame rates up to 200 kHz. The DFdLi filter enables the use of continuous-wave probe light, which, in turn, eliminates the need for synchronization schemes and allows measuring MIP decay curves. The WIPH approach is characterized by imaging potassium ferricyanide microparticles and applied to detect lipid droplets (alkyne-palmitic acid) in 3T3-L1 fibroblast cells, both in the cell-silent spectral region around 2100 cm–1 using an external-cavity quantum cascade laser. The system achieved up to 4000 WIPH images per second at a signal-to-noise ratio of 5.52 and 1 μm spatial resolution in a 128 × 128 μm field of view. The technique opens up for real-time chemical imaging of fast processes in biology, medicine, and material science.

Deep image restoration for infrared photothermal heterodyne imaging.

Infrared photothermal heterodyne imaging (IR-PHI) is an all-optical table top approach that enables super-resolution mid-infrared microscopy and spectroscopy. The underlying principle behind IR-PHI is the detection of photothermal changes to specimens induced by their absorption of infrared radiation. Because detection of resulting refractive indexand scattering cross section changes is done using a visible (probe) laser, IR-PHI exhibits a spatial resolution of ∼300nm. This is significantly below the mid-infrared diffraction limit and is unlike conventional infrared absorption microscopy where spatial resolution is of order ∼5μm. Despite having achieved mid-infrared super-resolution, IR-PHI's spatial resolution is ultimately limited by the visible probe laser's diffraction limit. This hinders immediate application to studying samples residing in spatially congested environments. To circumvent this, we demonstrate further enhancements to IR-PHI's spatial resolution using a deep learning network that addresses the Abbe diffraction limit as well as background artifacts, introduced by experimental raster scanning. What results is a twofold improvement in feature resolution from 300 to ∼150 nm.

Using Infrared Photothermal Heterodyne Imaging to Characterize Micro- and Nanoplastics in Complex Environmental Matrices.

A key challenge for addressing micro- and nanoplastics (MNPs) in the environment is being able to characterize their chemical properties, morphologies, and quantities in complex matrices. Current techniques, such as Fourier transform infrared spectroscopy, provide these broad characterizations but are unsuitable for studying MNPs in spectrally congested or complex chemical environments. Here, we introduce a new, super-resolution infrared absorption technique to characterize MNPs, called infrared photothermal heterodyne imaging (IR-PHI). IR-PHI has a spatial resolution of ∼300 nm and can determine the chemical identity, morphology, and quantity of MNPs in a single analysis with high sensitivity. Specimens are supported on CaF2 coverslips under ambient conditions from where we (1) quantify MNPs from nylon tea bags after steeping in ultrapure water at 25 and 95 °C, (2) identify MNP chemical or morphological changes after steeping at 95 °C, and (3) chemically identify MNPs in sieved road dust. In all cases, no special sample preparation was required. MNPs released from nylon tea bags at 25 °C were fiber-like and had characteristic IR frequencies corresponding to thermally extruded nylon. At 95 °C, degradation of the nylon chemical structure was observed via the disappearance of amide group IR frequencies, indicating chain scission of the nylon backbone. This degradation was also observed through morphological changes, where MNPs altered shape from fiber-like to quasi-spherical. In road dust, IR-PHI analysis reveals the presence of numerous aggregate and single-particle (<3 μm) MNPs composed of rubber and nylon.

Chemical Interface Damping of Surface Plasmon Resonances.

ConspectusMetal nanoparticles have been utilized for a vast amount of plasmon enhanced spectroscopies and energy conversion devices. Their unique optical properties allow them to be used across the UV-vis-NIR spectrum tuned by their size, shape, and material. In addition to utility in enhanced spectroscopy and energy/charge transfer, the plasmon resonance of metal nanoparticles is sensitive to its surrounding environment in several ways. The local refractive index determines the resonance wavelength, but plasmon damping, as indicated by the homogeneous line width, also depends on the surface properties of the metal nanoparticles. Plasmon oscillations can decay through interband, intraband, radiation, and surface damping. While the first three damping mechanisms can be modeled based on bulk dielectric data using electromagnetic simulations, surface damping does not depend on the material properties of the nanoparticle alone but rather on the interface composition between the nanoparticle and its surrounding environment. In this Account, we will discuss three different metal nanoparticle interfaces, identifying the surface damping contribution from chemical interface damping and how it manifests itself in different interface types. On the way to uncovering the various damping contributions, we use three different single-particle spectroscopic techniques that are essential to measuring homogeneous plasmon line widths: darkfield scattering, photothermal heterodyne imaging, and photoluminescence microscopies. Obtaining the homogeneous plasmon spectrum through single-particle spectroscopy is paramount to measuring changes in plasmon damping, where even minor size and shape heterogeneities can completely obfuscate the broadening caused by surface damping. Using darkfield scattering spectroscopy, we first describe a model for chemical interface damping by expanding upon the surface damping contribution to the plasmon resonance line width to include additional influences due to adsorbed molecules. Based on the understanding of chemical interface damping as a surface damping mechanism, we then carefully compare how two molecular isomers lead to greatly different damping rates upon adsorption to gold nanorods due to differences in the formation of image dipoles within the metal nanoparticles. This plasmon damping dependence on the chemical identity of the interface is strongly correlated with the chemical's electronegativity. A similar damping trend is observed for metal oxide semiconductors, where the metal oxide with greater electron affinity leads to larger interface damping. However, in this case, the mechanism is different for the metal oxide interfaces, as damping occurs through charge transfer into interfacial states. Finally, the damping effect of catalytic metal nanoislands on gold nanorods is compared for the three spectroscopic methods mentioned. Through correlated single-particle scattering, absorption, and photoluminescence spectroscopy, the mechanism for metal-metal interface damping is determined most likely to arise from an enhanced absorption, although charge transfer cannot be ruled out. From this body of research, we conclude that chemical interface damping is a major component of the total damping rate of the plasmon resonance and critically depends on the chemical interface of the metallic nanoparticles. Plasmon damping occurs through distinct mechanisms that are important to differentiate when considering the purpose of the plasmonic nanoparticle: enhanced spectroscopy, energy conversion, or catalysis. It must also be noted that many of the mechanisms are currently indifferentiable, and thus, new single-particle spectroscopic methods are needed to further characterize the mechanisms underlying chemical interface damping.

Quantifying the capabilities of infrared photothermal heterodyne imaging

Determining the signal contrast and detection limit of the infrared imaging technique could help enhance its sensitivity and provide quantitative information for measurements involving multiple chemical specimens.

Infrared photothermal heterodyne imaging: Contrast mechanism and detection limits

Infrared photothermal heterodyne imaging (IR-PHI) is an ultrasensitive technique for achieving super-resolution, infrared imaging throughout the mid-infrared “fingerprint” spectral region (2.5–10μm). An achieved spatial resolution of ∼300nm is up to 30-fold smaller than the infrared diffraction limit. In this study, we establish IR-PHI’s signal contrast mechanism and benchmark the technique’s capabilities using the characteristic infrared vibrational transitions of individual polystyrene (PS) and poly(methyl methacrylate) (PMMA) beads. The analysis of acquired results reveals that IR-PHI contrast originates from a competing, photothermally induced specimen size and refractive index changes to backscattering cross sections. For PS and PMMA, thermo-optic refractive index contributions dominate and are responsible for medium-free IR-PHI signal contrast. Our analysis simultaneously establishes IR-PHI’s current, medium-free peak absorption cross-sectional limit-of-detection to be σabs=3×10−18m2. This improved understanding of IR-PHI signal contrast provides a framework for future developments in super-resolution infrared absorption microscopy and spectroscopy.

Far-field midinfrared superresolution imaging and spectroscopy of single high aspect ratio gold nanowires

Limited approaches exist for imaging and recording spectra of individual nanostructures in the midinfrared region. Here we use infrared photothermal heterodyne imaging (IR-PHI) to interrogate single, high aspect ratio Au nanowires (NWs). Spectra recorded between 2,800 and 4,000 cm-1 for 2.5-3.9-μm-long NWs reveal a series of resonances due to the Fabry-Pérot modes of the NWs. Crucially, IR-PHI images show structure that reflects the spatial distribution of the NW absorption, and allow the resonances to be assigned to the m = 3 and m = 4 Fabry-Pérot modes. This far-field optical measurement has been used to image the mode structure of plasmon resonances in metal nanostructures, and is made possible by the superresolution capabilities of IR-PHI. The linewidths in the NW spectra range from 35 to 75 meV and, in several cases, are significantly below the limiting values predicted by the bulk Au Drude damping parameter. These linewidths imply long dephasing times, and are attributed to reduction in both radiation damping and resistive heating effects in the NWs. Compared to previous imaging studies of NW Fabry-Pérot modes using electron microscopy or near-field optical scanning techniques, IR-PHI experiments are performed under ambient conditions, enabling detailed studies of how the environment affects mid-IR plasmons.

Active Far-Field Control of the Thermal Near-Field via Plasmon Hybridization.

The ability to control and manipulate temperature at nanoscale dimensions has the potential to impact applications including heat-assisted magnetic recording, photothermal therapies, and temperature-driven reactivity. One challenge with controlling temperature at nanometer dimensions is the need to mitigate heat diffusion, such that the temperature only changes in well-defined nanoscopic regions of the sample. Here we demonstrate the ability to use far-field laser excitation to actively shape the thermal near-field in individual gold nanorod heterodimers by resonantly pumping either the in-phase or out-of-phase hybridized dipole plasmon modes. Using single-particle photothermal heterodyne imaging, we demonstrate localization bias in the photothermal intensity due to preferential heating of one of the nanorods within the pair. Theoretical modeling and numerical simulation make explicit how the resulting photothermal images encode wavelength-dependent temperature biases between each nanorod within a heterodimer, demonstrating the ability to actively manage the thermal near-field by simply tuning the color of incident light.

Spectroscopic setup for submicrometer-resolution mapping of low-signal absorption and luminescence using photothermal heterodyne imaging and photon-counting techniques.

A spectroscopic setup that enables the mapping of absorption and photoluminescence with submicrometer spatial resolution and high sensitivity is described. A photothermal heterodyne imaging pump/probe technique is employed for absorption mapping, and low-signal, spatially resolved photoluminescence is recorded using photon counting. High-spatial-resolution mapping is accomplished by using high-numerical-aperture microscope objective focusing laser beams (pump and probe) into a submicrometer spot and raster-scanning sample mounted on the nanopositioning translation stage. Performance of the setup is illustrated by mapping absorption and luminescence of the hafnium oxide film with embedded hafnium nanoparticles and multilayer dielectric grating. In both cases, submicrometer spatial resolution is demonstrated, and possible physical mechanisms leading to image contrast on a submicrometer scale are discussed.

Simultaneous Imaging and Selective Photothermal Therapy through Aptamer-Driven Au Nanosphere Clustering.

Gold (Au) nanoparticles display enhanced near-infrared (NIR) photothermal effects upon the formation of clusters. We studied the photothermal properties of Au nanosphere clusters on the single-particle level using photothermal heterodyne imaging (PTHI) microscopy to understand the enhancement mechanisms. NIR photothermal responses of Au nanoparticle clusters were found to significantly increase from monomers to trimers. The averaged PTHI signal intensity of Au nanosphere dimers and trimers is ∼10 and ∼25 times that of monomers. The NIR photothermal effect of clustered nanospheres strongly correlates with their longitudinal plasmon mode. Clustered Au nanospheres were demonstrated to exhibit dual-capability NIR photothermal imaging and therapy of human prostate cancer cells with high efficiency and selectivity. This strategy can be potentially utilized for simultaneous cancer imaging and therapy with 3D selectivity.

A sensitive, low noise, DC to 12 MHz, large area photodiode preamplifier for photothermal heterodyne imaging.

We report a compact, fast, and low-noise large area photodiode preamplifier designed for photothermal heterodyne imaging (PHI). The preamplifier exhibits a noise level of 7 nV/Hz1/2 and a bandwidth from DC to 12 MHz sufficient for PHI experiments. Simulations of the preamplifier bandwidth and noise agree with the observed experimental characterization and performance in our home-built PHI system. The observed noise is close to the inherent limitations of the SR844 lock-in amplifier used. The results indicate that the preamplifier is also useful for any other single frequency pump-probe detection technique, such as stimulated Raman scattering.

Single Semiconductor Nanostructure Extinction Spectroscopy

While emission-based, single-particle microscopies and spectroscopies have been highly successful in revealing the properties of matter hidden by ensemble averages, their limits have now become apparent. To address recognized future needs and, in particular, the need to go beyond fluorescent specimens, single-particle extinction techniques have been developed. Motivating this has been the desire to acquire information about the electronic structure of nanoscale materials difficult to obtain otherwise using either ensemble or emission-based, single-particle measurements. These techniques are, however, nontrivial since single nanostructures attenuate only 0.0001–1% of the incident light. This Review Article describes the challenges associated with overcoming the low signal-to-noise ratios inherent to low-dimensional semiconductor nanostructure extinction measurements. It simultaneously describes the fundamental operating principles and achievements of photothermal heterodyne imaging (PHI) and spatial modula...

Subdiffraction Infrared Imaging of Mixed Cation Perovskites: Probing Local Cation Heterogeneities

Compositional engineering has led to dramatic improvements in hybrid perovskite-based solar cell stabilities and performance. Mixed cation perovskites have emerged as champion photovoltaic materials with power conversion efficiencies exceeding 22%. However, there has been relatively little work done to explore local cation-related compositional inhomogeneities in mixed cation perovskite films. Such studies are necessary because hybrid perovskite optical properties and, consequently, their photovoltaic performance strongly depend on composition. Here, we perform spatially resolved, subdiffraction infrared photothermal heterodyne imaging measurements to probe cation-specific compositional distributions within FAxMA1–xPbI3 perovskite films. Our measurements reveal that these perovskites possess large compositional spatial heterogeneities with cation distributions varying on average ∼20% from expected ensemble stoichiometries. Correlated emission measurements show intrafilm emission energies differing by over 30 meV due to these compositional differences. These measurements thus reveal cation stoichiometric heterogeneities and their direct impact on local photovoltaic response-determining optical properties of mixed cation perovskites.

Super-Resolution Far-Field Infrared Imaging by Photothermal Heterodyne Imaging.

Infrared (IR) imaging provides chemical-specific information without the need for exogenous labels. Conventional far-field IR imaging techniques are diffraction limited, which means an effective spatial resolution of >5 μm with currently available optics. In this article, we present a novel far-field IR imaging technique based on photothermal heterodyne imaging (IR-PHI). In our version of IR-PHI, an IR pump laser excites the sample, causing a small temperature rise that is detected by a counterpropagating visible probe beam. Images and spectra of several different types of soft matter systems (polystyrene beads, thin polymer films, and single Escherichia coli bacterial cells) are presented to demonstrate the sensitivity and versatility of the technique. Importantly, the spatial resolution in the IR-PHI measurements is determined by the visible probe beam: a spatial resolution of 0.3 μm was achieved with a 0.53 μm probe wavelength and a high numerical aperture focusing objective. This is the highest spatial resolution reported to date for far-field IR imaging. Analysis of the experiments shows that for polymer beads in a dry environment, the magnitude of the IR-PHI signal is determined by the scattering cross section of the nano-object at the probe wavelength. This is in contrast to conventional PHI experiments in a heat-transfer medium, where the signal scales as the absorption cross section. This different scaling can be understood through the optical theorem. Our analysis also shows that both thermal expansion and changes in the refractive index of the material are important and that these two effects, in general, counteract each other.

Photothermal Microscopy of Coupled Nanostructures and the Impact of Nanoscale Heating in Surface Enhanced Raman Spectroscopy.

The optical properties of plasmonic nanoparticles are strongly dependent on interactions with other nanoparticles, which complicates analysis for systems larger than a few particles. In this work we examined heat dissipation in aggregated nanoparticles, and its influence on surface enhanced Raman scattering (SERS), through correlated photothermal heterodyne imaging, electron microscopy and SERS measurements. For dimers the per particle absorption cross-sections show evidence of interparticle coupling, however, the effects are much smaller than those for the field enhancements that are important for SERS. For larger aggregates the total absorption was observed to be simply proportional to aggregate volume. This observation allows us to model light absorption and heating in the aggregates by assuming that the particles act as independent heat sources. The heat dissipation calculations show that very high temperatures can be created at the nanoparticle surface, and that the temperature decreases with increasing thermal conductivity of the surroundings. This is in agreement with the SERS measurements that show faster signal degradation for air compared to water environments.

Role of HfO2/SiO2thin-film interfaces in near-ultraviolet absorption and pulsed laser damage

The role of thin-film interfaces in the near-ultraviolet (near-UV) absorption and pulsed laser-induced damage was studied for ion-beam-sputtered and electron-beam-evaporated coatings comprised from HfO2 and SiO2 thin-film pairs. To separate contributions from the bulk of the film and from interfacial areas, absorption and damage threshold measurements were performed for a one-wave (355-nm wavelength) thick, HfO2 single-layer film and for a film containing seven narrow HfO2 layers separated by SiO2 layers. The seven-layer film was designed to have a total optical thickness of HfO2 layers, equal to one wave at 355 nm and an E-field peak and average intensity similar to a single-layer HfO2 film. Absorption in both types of films was measured using laser calorimetry and photothermal heterodyne imaging. The results showed a small contribution to total absorption from thin-film interfaces as compared to HfO2 film material. The relevance of obtained absorption data to coating near-UV, nanosecond-pulse laser damage was verified by measuring the damage threshold and characterizing damage morphology. The results of this study revealed a higher damage resistance in the seven-layer coating as compared to the single-layer HfO2 film in both sputtered and evaporated coatings. The results are explained through the similarity of interfacial film structure with structure formed during the codeposition of HfO2 and SiO2 materials.

Imaging nano-objects by linear and nonlinear optical absorption microscopies

Absorption based microscopy measurements are emerging as important tools for studying nanomaterials. This review discusses the three most common techniques for performing these experiments: transient absorption microscopy, photothermal heterodyne imaging, and spatial modulation spectroscopy. The focus is on the application of these techniques to imaging and detection, using examples taken from the authors’ laboratory. The advantages and disadvantages of the three methods are discussed, with an emphasis on the unique information that can be obtained from these experiments, in comparison to conventional emission or scattering based microscopy experiments.