A guide to nanoscale IR spectroscopy: resonance enhanced transduction in contact and tapping mode AFM-IR.

Infrared (IR) spectroscopy is a broadly applicable, composition sensitive analytical technique. By leveraging the high spatial resolution of atomic force microscopy (AFM), the photothermal effect, and wavelength-tunable lasers, AFM-IR enables IR spectroscopy and imaging with nanoscale (< 10 nm) resolution. The transduction of a sample's photothermal expansion by an AFM probe tip ensures the proportionality between the AFM-IR signal and the sample absorption coefficient, producing images and spectra that are comparable to far-field IR databases and easily interpreted. This convergence of characteristics has spurred robust research efforts to extend AFM-IR capabilities and, in parallel, has enabled AFM-IR to impact numerous fields. In this tutorial review, we present the latest technical breakthroughs in AFM-IR spectroscopy and imaging and discuss its working principles, distinctive characteristics, and best practices for different AFM-IR measurement paradigms. Central to this review, appealing to both expert practitioners and novices alike, is the meticulous understanding of AFM-IR signal transduction, which is essential to take full advantage of AFM-IR capabilities. Here, we critically compile key information and discuss instructive experiments detailing AFM-IR signal transduction and provide guidelines linking experimental parameters to the measurement sensitivity, lateral resolution, and probed depth. Additionally, we provide in-depth tutorials on the most employed AFM-IR variants (resonance-enhanced and tapping mode AFM-IR), discussing technical details and representative applications. Finally, we briefly review recently developed AFM-IR modalities (peak force tapping IR and surface sensitivity mode) and provide insights on the next exciting opportunities and prospects for this fast-growing and evolving field.

High Throughput Nanoimaging of Thermal Conductivity and Interfacial Thermal Conductance.

Thermal properties of materials are often determined by measuring thermalization processes; however, such measurements at the nanoscale are challenging because they require high sensitivity concurrently with high temporal and spatial resolutions. Here, we develop an optomechanical cantilever probe and customize an atomic force microscope with low detection noise ≈1 fm/Hz1/2 over a wide (>100 MHz) bandwidth that measures thermalization dynamics with ≈10 ns temporal resolution, ≈35 nm spatial resolution, and high sensitivity. This setup enables fast nanoimaging of thermal conductivity (η) and interfacial thermal conductance (G) with measurement throughputs ≈6000× faster than conventional macroscale-resolution time-domain thermoreflectance acquiring the full sample thermalization. As a proof-of-principle demonstration, 100 × 100 pixel maps of η and G of a polymer particle are obtained in 200 s with a small relative uncertainty (<10%). This work paves the way to study fast thermal dynamics in materials and devices at the nanoscale.

Visible to Mid-IR Spectromicroscopy with Top-Down Illumination and Nanoscale (≈10 nm) Resolution.

Photothermal induced resonance (PTIR), an atomic force microscopy (AFM) analogue of IR spectroscopy also known as AFM-IR, is capable of nanoscale lateral resolution and finds broad applications in biology and materials science. Here, the spectral range of a top-illumination PTIR setup operating in contact-mode is expanded for the first time to the visible and near-IR spectral ranges. The result is a tool that yields absorption spectra and maps of electronic and vibrational features with spatial resolution down to ≈10 nm. In addition to the improved resolution, the setup enables light-polarization-dependent PTIR experiments in the visible and near-IR ranges for the first time. While previous PTIR implementations in the visible used total internal reflection illumination requiring challenging sample preparations on an optically transparent prism, the top illumination used here greatly simplifies sample preparation and will foster a broad application of this method.

Understanding Cantilever Transduction Efficiency and Spatial Resolution in Nanoscale Infrared Microscopy.

Photothermal induced resonance (PTIR), also known as AFM-IR, enables nanoscale infrared (IR) imaging and spectroscopy by using the tip of an atomic force microscope to transduce the local photothermal expansion and contraction of a sample. The signal transduction efficiency and spatial resolution of PTIR depend on a multitude of sample, cantilever, and illumination source parameters in ways that are not yet well understood. Here, we elucidate and separate the effects of laser pulse length, pulse shape, sample thermalization time (τ), interfacial thermal conductance, and cantilever detection frequency by devising analytical and numerical models that link a sample's photothermal excitations to the cantilever dynamics over a broad bandwidth (10 MHz). The models indicate that shorter laser pulses excite probe oscillations over broader bandwidths and should be preferred for measuring samples with shorter thermalization times. Furthermore, we show that the spatial resolution critically depends on the interfacial thermal conductance between dissimilar materials and improves monotonically, but not linearly, with increasing cantilever detection frequencies. The resolution can be enhanced for samples that do not fully thermalize between pulses (i.e., laser repetition rates ≳ 1/3τ) as the probed depth becomes smaller than the film thickness. We believe that the insights presented here will accelerate the adoption and impact of PTIR analyses across a wide range of applications by informing experimental designs and measurement strategies as well as by guiding future technical advances.

Micro to Nano: Multiscale IR Analyses Reveal Zinc Soap Heterogeneity in a 19th-Century Painting by Corot.

Formation and aggregation of metal carboxylates (metal soaps) can degrade the appearance and integrity of oil paints, challenging efforts to conserve painted works of art. Endeavors to understand the root cause of metal soap formation have been hampered by the limited spatial resolution of Fourier transform infrared microscopy (µ-FTIR). We overcome this limitation using optical photothermal infrared spectroscopy (O-PTIR) and photothermal-induced resonance (PTIR), two novel methods that provide IR spectra with ≈500 and ≈10 nm spatial resolutions, respectively. The distribution of chemical phases in thin sections from the top layer of a 19th-century painting is investigated at multiple scales (µ-FTIR ≈ 102 µm3, O-PTIR ≈ 10-1 µm3, PTIR ≈ 10-5 µm3). The paint samples analyzed here are found to be mixtures of pigments (cobalt green, lead white), cured oil, and a rich array of intermixed, small (often ≪ 0.1 µm3) zinc soap domains. We identify Zn stearate and Zn oleate crystalline soaps with characteristic narrow IR peaks (≈1530-1558 cm-1) and a heterogeneous, disordered, water-permeable, tetrahedral zinc soap phase, with a characteristic broad peak centered at ≈1596 cm-1. We show that the high signal-to-noise ratio and spatial resolution afforded by O-PTIR are ideal for identifying phase-separated (or locally concentrated) species with low average concentration, while PTIR provides an unprecedented nanoscale view of distributions and associations of species in paint. This newly accessible nanocompositional information will advance our knowledge of chemical processes in oil paint and will stimulate new art conservation practices.

Infrared and Raman chemical imaging and spectroscopy at the nanoscale.

The advent of nanotechnology, and the need to understand the chemical composition at the nanoscale, has stimulated the convergence of IR and Raman spectroscopy with scanning probe methods, resulting in new nanospectroscopy paradigms. Here we review two such methods, namely photothermal induced resonance (PTIR), also known as AFM-IR and tip-enhanced Raman spectroscopy (TERS). AFM-IR and TERS fundamentals will be reviewed in detail together with their recent crucial advances. The most recent applications, now spanning across materials science, nanotechnology, biology, medicine, geology, optics, catalysis, art conservation and other fields are also discussed. Even though AFM-IR and TERS have developed independently and have initially targeted different applications, rapid innovation in the last 5 years has pushed the performance of these, in principle spectroscopically complimentary, techniques well beyond initial expectations, thus opening new opportunities for their convergence. Therefore, subtle differences and complementarity will be highlighted together with emerging trends and opportunities.

Nanoscale Mapping and Spectroscopy of Nonradiative Hyperbolic Modes in Hexagonal Boron Nitride Nanostructures.

The inherent crystal anisotropy of hexagonal boron nitride (hBN) provides the ability to support hyperbolic phonon polaritons, that is, polaritons that can propagate with very large wave vectors within the material volume, thereby enabling optical confinement to exceedingly small dimensions. Indeed, previous research has shown that nanometer-scale truncated nanocone hBN cavities, with deep subdiffractional dimensions, support three-dimensionally confined optical modes in the mid-infrared. Because of optical selection rules, only a few of the many theoretically predicted modes have been observed experimentally via far-field reflection and scattering-type scanning near-field optical microscopy (s-SNOM). The photothermal induced resonance (PTIR) technique probes optical and vibrational resonances overcoming weak far-field emission by leveraging an atomic force microscope (AFM) probe to transduce local sample expansion caused by light absorption. Here we show that PTIR enables the direct observation of previously unobserved, dark hyperbolic modes of hBN nanostructures. Leveraging these optical modes and their wide range of angular and radial momenta could provide a new degree of control over the electromagnetic near-field concentration, polarization in nanophotonic applications.

Revealing the Distribution of Metal Carboxylates in Oil Paint from the Micro- to Nanoscale.

Oil paints comprise pigments, drying oils, and additives that together confer desirable properties, but can react to form metal carboxylates (soaps) that may damage artworks over time. To obtain information on soap formation and aggregation, we introduce a new tapping-mode measurement paradigm for the photothermal induced resonance (PTIR) technique that enables nanoscale IR spectroscopy and imaging on highly heterogenous and rough paint thin sections. PTIR is used in combination with µ-computed tomography and IR microscopy to determine the distribution of metal carboxylates in a 23-year old oil paint of known formulation. Results show that heterogeneous agglomerates of Al-stearate and a Zn-carboxylate complex with Zn-stearate nano-aggregates in proximity are distributed randomly in the paint. The gradients of zinc carboxylates are unrelated to the Al-stearate distribution. These measurements open a new chemically sensitive nanoscale observation window on the distribution of metal soaps that can bring insights for understanding soap formation in oil paint.

Nanostructured Lipid-based Films for Substrate Mediated Applications in Biotechnology.

Amphiphilic in nature, lipids spontaneously self-assemble into a range of nanostructures in the presence of water. Among lipid self-assembled structures, liposomes and supported lipid bilayers have long held scientific interest for their main applications in drug delivery and plasma membrane models, respectively. In contrast, lipid-based multi-layered membranes on solid supports only recently begun drawing scientists' attention. New studies on lipid films show that the stacking of multiple bilayers on a solid support yields interestingly complex features to these systems. Namely, multiple layers exhibit cooperative structural and dynamic behavior. In addition, the materials enable compartmentalization, templating, and enhanced release of several molecules of interest. Importantly, supported lipid phases exhibit long-range periodic nano-scale order and orientation that is tunable in response to a changing environment. Herein, we summarize current and pertinent understanding of lipid-based film research focusing on how unique structural characteristics enable the emergence of new applications in biotechnology including label-free biosensors, macroscale drug delivery, and substrate-mediated gene delivery. Our very recent contributions to lipid-based films, focusing on the structural characterization at the meso, nano, and molecular-scale, using Small-Angle X-ray Scattering, Atomic Force Microscopy, Photothermal Induced Resonance, and Solid-State NMR will be also highlighted.

Nanoscale partitioning of paclitaxel in hybrid lipid-polymer membranes.

Paclitaxel is a powerful drug against restenosis and many forms of cancer. However, its clinical application hinges on the ability to achieve suitable stabilized drug concentrations in an aqueous suspension while hindering drug crystallization. To engineer such formulations, it is imperative to understand paclitaxel's partitioning and crystallization within the carrier matrix. Lipid-polymer hybrid films have been recently shown to accommodate large paclitaxel loads and suppress crystallization. Additionally, such hybrid materials promote synergistic drug release compared to the pure constituents. Here, we leverage the composition sensitive photo-thermal induced resonance (PTIR) technique to study paclitaxel partitioning within hybrid films at the nanoscale. PTIR data reveal that paclitaxel nano-crystals segregate from lipid-only films but are well dispersed in polymer-only films. Remarkably, lipid-polymer hybrid films show enhanced partitioning of paclitaxel at the lipid-polymer phase boundaries, but still stifle crystallization, thus paving the way towards compositional and microstructural engineering of small-drug delivery systems.

Nanophotonic Atomic Force Microscope Transducers Enable Chemical Composition and Thermal Conductivity Measurements at the Nanoscale.

The atomic force microscope (AFM) offers a rich observation window on the nanoscale, yet many dynamic phenomena are too fast and too weak for direct AFM detection. Integrated cavity-optomechanics is revolutionizing micromechanical sensing; however, it has not yet impacted AFM. Here, we make a groundbreaking advance by fabricating picogram-scale probes integrated with photonic resonators to realize functional AFM detection that achieve high temporal resolution (<10 ns) and picometer vertical displacement uncertainty simultaneously. The ability to capture fast events with high precision is leveraged to measure the thermal conductivity (η), for the first time, concurrently with chemical composition at the nanoscale in photothermal induced resonance experiments. The intrinsic η of metal-organic-framework individual microcrystals, not measurable by macroscale techniques, is obtained with a small measurement uncertainty (8%). The improved sensitivity (50×) increases the measurement throughput 2500-fold and enables chemical composition measurement of molecular monolayer-thin samples. Our paradigm-shifting photonic readout for small probes breaks the common trade-off between AFM measurement precision and ability to capture transient events, thus transforming the ability to observe nanoscale dynamics in materials.

Quantitative Chemical Analysis at the Nanoscale Using the Photothermal Induced Resonance Technique.

Photothermal induced resonance (PTIR), also known as AFM-IR, is a scanning probe technique that provides sample composition information with a lateral resolution down to 20 nm. Interest in PTIR stems from its ability to identify unknown samples at the nanoscale thanks, in first approximation, to the direct comparability of PTIR spectra with far-field infrared databases. The development of rapidly tuning quantum cascade lasers has increased the PTIR throughput considerably, making nanoscale hyperspectral imaging within a reasonable time frame possible. Consequently, a better understanding of PTIR signal generation and of the fine details of PTIR analysis has become of paramount importance for extending complex IR analysis methods developed in the far-field, e.g., for classification and hyperspectral imaging, to nanoscale PTIR spectra. Here we calculate PTIR spectra via thin-film optics, to identify subtle changes (band shifts, deviation from linear approximation, etc.) for common sample parameters in the case of PTIR with total internal reflection illumination. Results show signal intensity linearity and small band shifts as long as the sample is prepared correctly, with band shifts typically smaller than macroscale attenuated total reflection (ATR) spectroscopy. Finally, a generally applicable algorithm to retrieve the pure imaginary component of the refractive index (i.e., the chemically specific information) is provided to overcome the PTIR spectra nonlinearity.

Chloride Incorporation Process in CH3NH3PbI(3-x)Cl(x) Perovskites via Nanoscale Bandgap Maps.

CH3NH3PbI(3-x)Cl(x) perovskites enable fabrication of highly efficient solar cells. Chloride ions benefit the morphology, carrier diffusion length, and stability of perovskite films; however, whether those benefits stem from the presence of Cl(-) in the precursor solution or from their incorporation in annealed films is debated. In this work, the photothermal-induced resonance, an in situ technique with nanoscale resolution, is leveraged to measure the bandgap of CH3NH3PbI(3-x)Cl(x) films obtained by a multicycle coating process that produces high efficiency (∼16%) solar cells. Because chloride ions modify the perovskite lattice, thereby widening the bandgap, measuring the bandgap locally yields the local chloride content. After a mild annealing (60 min, 60 °C) the films consist of Cl-rich (x < 0.3) and Cl-poor phases that upon further annealing (110 °C) evolve into a homogeneous Cl-poorer (x < 0.06) phase, suggesting that methylammonium-chrloride is progressively expelled from the film. Despite the small chloride content, CH3NH3PbI(3-x)Cl(x) films show better thermal stability up to 140 °C with respect CH3NH3PbI3 films fabricated with the same methodology.

Absorption spectroscopy and imaging from the visible through mid-infrared with 20 nm resolution.

Absorption spectroscopy and mapping from visible through mid-IR wavelengths has been achieved with spatial resolution exceeding the limit imposed by diffraction via the photothermal induced resonance technique. Correlated vibrational (chemical), and electronic properties are obtained simultaneously with topography with a wavelength-independent resolution of ≈20 nm using a single laboratory-scale instrument. This marks the highest resolution reported for PTIR, as determined by comparing height and PTIR images, and its first extension to near-IR and visible wavelengths.

Metal-dielectric-metal resonators with deep subwavelength dielectric layers increase the near-field SEIRA enhancement.

Plasmonic nanostructures presenting either structural asymmetry or metal-dielectric-metal (M-D-M) architecture are commonly used structures to increase the quality factor and the near-field confinement in plasmonic materials. This characteristic can be leveraged for example to increase the sensitivity of IR spectroscopy, via the surface enhanced IR absorption (SEIRA) effect. In this work, we combine structural asymmetry with the M-D-M architecture to realize Ag-Ag(2)O-Ag asymmetric ring resonators where two Ag layers sandwich a native silver oxide (Ag(2)O) layer. Their IR response is compared with the one of fully metallic (Ag) resonators of the same size and shape. The photothermal induced resonance technique (PTIR) is used to obtain near-field SEIRA absorption maps and spectra with nanoscale resolution. Although the native Ag(2)O layer is only 1 nm to 2 nm thick, it increases the quality factor of the resonators' dark-mode by ≈27% and the SEIRA enhancement by ≈44% with respect to entirely Ag structures.

Nanoscale imaging of plasmonic hot spots and dark modes with the photothermal-induced resonance technique.

The collective oscillation of conduction electrons, responsible for the localized surface plasmon resonances, enables engineering nanomaterials by tuning their optical response from the visible to terahertz as a function of nanostructure size, shape, and environment. While theoretical calculations helped tremendously in understanding plasmonic nanomaterials and optimizing their light matter interaction, only a few experimental techniques are available to study these materials with high spatial resolution. In this work, the photothermal-induced resonance (PTIR) technique is applied for the first time to image the dark plasmonic resonance of gold asymmetric split ring resonators (A-SRRs) in the mid-infrared (IR) spectral region with nanoscale resolution. Additionally, the chemically specific PTIR signal is used to map the local absorption enhancement of poly(methyl methacrylate) coated on A-SRRs, revealing hot spots with local enhancement factors up to ≈30 at 100 nm lateral resolution. We argue that PTIR nanoscale characterization will facilitate the engineering and application of plasmonic nanomaterials for mid-IR applications.

Assessing chemical heterogeneity at the nanoscale in mixed-ligand metal-organic frameworks with the PTIR technique.

Recently, the use of mixtures of organic-building-block linkers has given chemists an additional degree of freedom for engineering metal-organic frameworks (MOFs) with specific properties; however, the poor characterization of the chemical complexity of such MixMOF structures by conventional techniques hinders the verification of rational design. Herein, we describe the application of a technique known as photothermal induced resonance to individual MixMOF microcrystals to elucidate their chemical composition with nanoscale resolution. Results show that MixMOFs isoreticular to In-MIL-68, obtained either directly from solution or by postsynthetic linker exchange, are homogeneous down to approximately 100 nm. Additionally, we report a novel in situ process that enables the engineering of anisotropic domains in MOF crystals with submicron linker-concentration gradients.

Isotopic effects on in-plane hyperbolic phonon polaritons in MoO3.

Hyperbolic phonon polaritons (HPhPs), hybrids of light and lattice vibrations in polar dielectric crystals, empower nanophotonic applications by enabling the confinement and manipulation of light at the nanoscale. Molybdenum trioxide (α-MoO3) is a naturally hyperbolic material, meaning that its dielectric function deterministically controls the directional propagation of in-plane HPhPs within its reststrahlen bands. Strategies such as substrate engineering, nano- and heterostructuring, and isotopic enrichment are being developed to alter the intrinsic die ectric functions of natural hyperbolic materials and to control the confinement and propagation of HPhPs. Since isotopic disorder can limit phonon-based processes such as HPhPs, here we synthesize isotopically enriched 92MoO3 (92Mo: 99.93 %) and 100MoO3 (100Mo: 99.01 %) crystals to tune the properties and dispersion of HPhPs with respect to natural α-MoO3, which is composed of seven stable Mo isotopes. Real-space, near-field maps measured with the photothermal induced resonance (PTIR) technique enable comparisons of inplane HPhPs in α-MoO3 and isotopically enriched analogues within a reststrahlen band (≈820 cm-1 to ≈ 972 cm-1). Results show that isotopic enrichment (e.g., 92MoO3 and 100MoO3) alters the dielectric function, shifting the HPhP dispersion (HPhP angular wavenumber × thickness vs IR frequency) by ≈-7% and ≈ +9 %, respectively, and changes the HPhP group velocities by ≈ ±12 %, while the lifetimes (≈ 3 ps) in 92MoO3 were found to be slightly improved (≈ 20 %). The latter improvement is attributed to a decrease in isotopic disorder. Altogether, isotopic enrichment was found to offer fine control over the properties that determine the anisotropic in-plane propagation of HPhPs in α-MoO3, which is essential to its implementation in nanophotonic applications.

Nanoscale infrared spectroscopy: improving the spectral range of the photothermal induced resonance technique.

Photothermal induced resonance (PTIR) is a new technique which combines the chemical specificity of infrared (IR) spectroscopy with the lateral resolution of atomic force microscopy (AFM). PTIR requires a pulsed tunable laser for sample excitation and an AFM tip to measure the sample expansion induced by light absorption. The limited tunability of commonly available laser sources constrains the application of the PTIR technique to a portion of the IR spectrum. In this work, a broadly tunable pulsed laser relying on a difference frequency generation scheme in a GaSe crystal to emit light tunable from 1.55 µm to 16 µm (from 6450 cm(-1) to 625 cm(-1)) was interfaced with a commercial PTIR instrument. The result is a materials characterization platform capable of chemical imaging, in registry with atomic force images, with a spatial resolution that notably surpasses the light diffraction limit throughout the entire mid-IR spectral range. PTIR nanoscale spectra and images allow the identification of compositionally and optically similar yet distinct materials; organic, inorganic, and composite samples can be studied with this nanoscale analog of infrared spectroscopy, suggesting broad applicability. Additionally, we compare the results obtained with the two tunable lasers, which have different pulse lengths, to experimentally assess the recently developed theory of PTIR signal generation.