Surface-phonon-polariton-enhanced photoinduced dipole force for nanoscale infrared imaging.

The photoinduced dipole force (PiDF) is an attractive force arising from the Coulombic interaction between the light-induced dipoles on the illuminated tip and the sample. It shows extreme sample-tip distance and refractive index dependence, which is promising for nanoscale infrared (IR) imaging of ultrathin samples. However, the existence of PiDF in the mid-IR region has not been experimentally demonstrated due to the coexistence of photoinduced thermal force (PiTF), typically one to two orders of magnitude higher than PiDF. In this study, we demonstrate that, with the assistance of surface phonon polaritons, the PiDF of c-quartz can be enhanced to surpass its PiTF, enabling a clear observation of PiDF spectra reflecting the properties of the real part of permittivity. Leveraging the detection of the PiDF of phonon polaritonic substrate, we propose a strategy to enhance the sensitivity and contrast of photoinduced force responses in transmission images, facilitating the precise differentiation of the heterogeneous distribution of ultrathin samples.

Characterizing and controlling infrared phonon anomaly of bilayer graphene in optical-electrical force nanoscopy.

We, for the first time, report the nanoscopic imaging study of anomalous infrared (IR) phonon enhancement of bilayer graphene, originated from the charge imbalance between the top and bottom layers, resulting in the enhancement of E1u mode of bilayer graphene near 0.2 eV. We modified the multifrequency atomic force microscope platform to combine photo-induced force microscope with electrostatic/Kelvin probe force microscope constituting a novel hybrid nanoscale optical-electrical force imaging system. This enables to observe a correlation between the IR response, doping level, and topographic information of the graphene layers. Through the nanoscale spectroscopic image measurements, we demonstrate that the charge imbalance at the graphene interface can be controlled by chemical (doping effect via Redox mechanism) and mechanical (triboelectric effect by the doped cantilever) approaches. Moreover, we can also diagnosis the subsurface cracks on the stacked few-layer graphene at nanoscale, by monitoring the strain-induced IR phonon shift. Our approach provides new insights into the development of graphene-based electronic and photonic devices and their potential applications.

Photo-induced force microscopy (PiFM) - principles and implementations.

Photo-induced force microscopy (PiFM) is a scan probe technique that offers images with spectroscopic contrast at a spatial resolution in the nanometer range. PiFM utilizes the non-propagating, enhanced near field at the apex of a sharp tip to locally induce a polarization in the sample, which in turn produces an additional force acting on the cantilevered tip. This photo-induced force, though in the pN range or less, can be extracted from the oscillation properties of the cantilever, thus enabling the generation of photo-induced force maps. Since its inception in 2010, the PiFM technique has grown into a useful nano-spectrocopic tool that has expanded its reach in terms of imaging capabilities and applications. In this review, we present various technical implementations of the PiFM approach. In addition, we discuss the physical origin of the PiFM signal, highlighting the contributions from dipole-dipole forces as well as forces that derive from photo-thermal processes.

Enhancement of Photoresponse on Narrow-Bandgap Mott Insulator α-RuCl3 via Intercalation.

Charge doping to Mott insulators is critical to realize high-temperature superconductivity, quantum spin liquid state, and Majorana fermion, which would contribute to quantum computation. Mott insulators also have a great potential for optoelectronic applications; however, they showed insufficient photoresponse in previous reports. To enhance the photoresponse of Mott insulators, charge doping is a promising strategy since it leads to effective modification of electronic structure near the Fermi level. Intercalation, which is the ion insertion into the van der Waals gap of layered materials, is an effective charge-doping method without defect generation. Herein, we showed significant enhancement of optoelectronic properties of a layered Mott insulator, α-RuCl3, through electron doping by organic cation intercalation. The electron-doping results in substantial electronic structure change, leading to the bandgap shrinkage from 1.2 eV to 0.7 eV. Due to localized excessive electrons in RuCl3, distinct density of states is generated in the valence band, leading to the optical absorption change rather than metallic transition even in substantial doping concentration. The stable near-infrared photodetector using electronic modulated RuCl3 showed 50 times higher photoresponsivity and 3 times faster response time compared to those of pristine RuCl3, which contributes to overcoming the disadvantage of a Mott insulator as a promising optoelectronic device and expanding the material libraries.

Direct Chemical Imaging of Ligand-Functionalized Single Nanoparticles by Photoinduced Force Microscopy.

Chemical characterizations of biochemically functionalized single nanoparticles are necessary to optimize the nanoparticle surface functionality in recently advanced nanobiological applications but have not yet been fully explored because of technical difficulties. Exploiting the photoinduced force exerted on a light-illuminated nanoscale tip, nanoscale mid-infrared hyperspectral images with a 10 nm spatial resolution of a monolayer ligand-functionalized single gold nanoparticle under ambient and environmental conditions are presented. We extend our study to the diagnosis of nanoscale heterogeneous chemical contaminants which come from a particle functionalization process but are undetectable in conventional ensemble-averaged imaging technique. High sensitivity and high spatial resolution are achieved via the strongly localized tip-enhanced force at the junction between the gold-coated tip and the functionalized nanoparticle in photoinduced force microscopy, which far exceeds the capability of the conventional methods. The present study paves a new way to directly detect heterogeneous nanochemicals at the single-component level, which is necessary to evaluate nanomaterial safety in biomedical applications.

Tip-Enhanced Infrared Imaging with Sub-10 nm Resolution and Hypersensitivity.

Here we demonstrate sub-10 nm spatial resolution sampling of a volume of ∼360 molecules with a strong field enhancement at the sample-tip junction by implementing noble metal substrates (Au, Ag, Pt) in photoinduced force microscopy (PiFM). This technique shows the versatility and robustness of PiFM and is promising for application in interfacial studies with hypersensitivity and super spatial resolution.

Nanoscale spectroscopic origins of photoinduced tip-sample force in the midinfrared.

When light illuminates the junction formed between a sharp metal tip and a sample, different mechanisms can contribute to the measured photoinduced force simultaneously. Of particular interest are the instantaneous force between the induced dipoles in the tip and in the sample, and the force related to thermal heating of the junction. A key difference between these 2 force mechanisms is their spectral behavior. The magnitude of the thermal response follows a dissipative (absorptive) Lorentzian line shape, which measures the heat exchange between light and matter, while the induced dipole response exhibits a dispersive spectrum and relates to the real part of the material polarizability. Because the 2 interactions are sometimes comparable in magnitude, the origin of the chemical selectivity in nanoscale spectroscopic imaging through force detection is often unclear. Here, we demonstrate theoretically and experimentally how the light illumination gives rise to the 2 kinds of photoinduced forces at the tip-sample junction in the midinfrared. We comprehensively address the origin of the spectroscopic forces by discussing cases where the 2 spectrally dependent forces are entwined. The analysis presented here provides a clear and quantitative interpretation of nanoscale chemical measurements of heterogeneous materials and sheds light on the nature of light-matter coupling in optomechanical force-based spectronanoscopy.

Photo-Induced Force Microscopy by Using Quartz Tuning-Fork Sensor.

We present the photo-induced force microscopy (PiFM) studies of various nano-materials by implementing a quartz tuning fork (QTF), a self-sensing sensor that does not require complex optics to detect the motion of a force probe and thus helps to compactly configure the nanoscale optical mapping tool. The bimodal atomic force microscopy technique combined with a sideband coupling scheme is exploited for the high-sensitivity imaging of the QTF-PiFM. We measured the photo-induced force images of nano-clusters of Silicon 2,3-naphthalocyanine bis dye and thin graphene film and found that the QTF-PiFM is capable of high-spatial-resolution nano-optical imaging with a good signal-to-noise ratio. Applying the QTF-PiFM to various experimental conditions will open new opportunities for the spectroscopic visualization and substructure characterization of a vast variety of nano-materials from semiconducting devices to polymer thin films to sensitive measurements of single molecules.

Substructure imaging of heterogeneous nanomaterials with enhanced refractive index contrast by using a functionalized tip in photoinduced force microscopy.

The opto-mechanical force response from light-illuminated nanoscale materials has been exploited in many tip-based imaging applications to characterize various heterogeneous nanostructures. Such a force can have two origins: thermal expansion and induced dipoles. The thermal expansion reflects the absorption of the material, which enables one to chemically characterize a material at the absorption resonance. The induced dipole interaction reflects the local refractive indices of the material underneath the tip, which is useful to characterize a material in the spectral region where no absorption resonance occurs, as in the infrared (IR)-inactive region. Unfortunately, the dipole force is relatively small, and the contrast is rarely discernible for most organic materials and biomaterials, which only show a small difference in refractive indices for their components. In this letter, we demonstrate that refractive index contrast can be greatly enhanced with the assistance of a functionalized tip. With the enhanced contrast, we can visualize the substructure of heterogeneous biomaterials, such as a polyacrylonitrile-nanocrystalline cellulose (PAN-NCC) nanofiber. From substructural visualization, we address the issue of the tensile strength of PAN-NCC fibers fabricated by several different mixing methods. Our understanding from the present study will open up a new opportunity to provide enhanced sensitivity for substructure mapping of nanobiomaterials, as well as local field mapping of photonic devices, such as surface polaritons on semiconductors, metals and van der Waals materials.

Tip-Enhanced Thermal Expansion Force for Nanoscale Chemical Imaging and Spectroscopy in Photoinduced Force Microscopy.

We investigate the tip-enhanced thermal expansion force for nanoscale chemical imaging and spectroscopy in the tip-sample junction. It is found, both theoretically and experimentally, that the tip-enhanced absorption of the near-field at the tip followed by sample expansion shows characteristic behaviors with respect to the sample thickness and the incident laser pulse width. The van der Waals interaction plays a major role in exerting a force on the tip from the thermally expanded sample. The force behavior of the photoinduced force microscope (PiFM) is compared with that of the existing photothermal-induced resonance technique (PTIR) to unravel the ambiguous thermal expansion force mechanism. The present study opens up new opportunities for enhancing the performance of optical nanoscopy and spectroscopy such as chemical imaging of nanobiomaterials and the local field mapping of photonic devices, including surface polaritons on van der Waals materials with the assistance of the thermal expansion of a functionalized tip.

Fabrication and near-field visualization of a wafer-scale dense plasmonic nanostructured array.

Developing a sensor that identifies and quantifies trace amounts of analyte molecules is crucially important for widespread applications, especially in the areas of chemical and biological detection. By non-invasively identifying the vibrational signatures of the target molecules, surface-enhanced Raman scattering (SERS) has been widely employed as a tool for molecular detection. Here, we report on the reproducible fabrication of wafer-scale dense SERS arrays and single-nanogap level near-field imaging of these dense arrays under ambient conditions. Plasmonic nanogaps densely populated the spaces among globular Ag nanoparticles with an areal density of 120 particles per µm2 upon application of a nanolithography-free simple process consisting of the Ar plasma treatment of a polyethylene terephthalate substrate and subsequent Ag sputter deposition. The compact nanogaps produced a high SERS enhancement factor of 3.3 × 107 and homogeneous (coefficient of variation of 8.1%) SERS response. The local near fields at these nanogaps were visualized using photo-induced force microscopy that simultaneously enabled near-field excitation and near-field force detection under ambient conditions. A high spatial resolution of 3.1 nm was achieved. Taken together, the generation of a large-area SERS array with dense plasmonic nanogaps and the subsequent single-nanogap level characterization of the local near field have profound implications in the nanoplasmonic imaging and sensing applications.

Evans blue dye-enhanced imaging of the brain microvessels using spectral focusing coherent anti-Stokes Raman scattering microscopy.

We performed dye-enhanced imaging of mouse brain microvessels using spectral focusing coherent anti-Stokes Raman scattering (SF-CARS) microscopy. The resonant signals from C-H stretching in forward CARS usually show high background intensity in tissues, which makes CARS imaging of microvessels difficult. In this study, epi-detection of back-scattered SF-CARS signals showed a negligible background, but the overall intensity of resonant CARS signals was too low to observe the network of brain microvessels. Therefore, Evans blue (EB) dye was used as contrasting agent to enhance the back-scattered SF-CARS signals. Breakdown of brain microvessels by inducing hemorrhage in a mouse was clearly visualized using backward SF-CARS signals, following intravenous injection of EB. The improved visualization of brain microvessels with EB enhanced the sensitivity of SF-CARS, detecting not only the blood vessels themselves but their integrity as well in the brain vasculature.

Nanoscale chemical imaging by photoinduced force microscopy.

Correlating spatial chemical information with the morphology of closely packed nanostructures remains a challenge for the scientific community. For example, supramolecular self-assembly, which provides a powerful and low-cost way to create nanoscale patterns and engineered nanostructures, is not easily interrogated in real space via existing nondestructive techniques based on optics or electrons. A novel scanning probe technique called infrared photoinduced force microscopy (IR PiFM) directly measures the photoinduced polarizability of the sample in the near field by detecting the time-integrated force between the tip and the sample. By imaging at multiple IR wavelengths corresponding to absorption peaks of different chemical species, PiFM has demonstrated the ability to spatially map nm-scale patterns of the individual chemical components of two different types of self-assembled block copolymer films. With chemical-specific nanometer-scale imaging, PiFM provides a powerful new analytical method for deepening our understanding of nanomaterials.

Visualizing surface plasmon polaritons by their gradient force.

A new method is presented for visualizing the electric field distributions associated with propagating surface-plasmon-polariton (SPP) modes directly in the near-field. The method is based on detecting the photo-induced gradient force exerted by the evanescent field onto a sharp and polarizable tip. Using a photo-induced force microscope (PiFM), images of propagating SPPs are obtained on flat gold surfaces.

Linear and Nonlinear Optical Spectroscopy at the Nanoscale with Photoinduced Force Microscopy.

The enormous advances made in nanotechnology have also intensified the need for tools that can characterize newly synthesized nanoaterials with high sensitivity and with high spatial resolution. Many existing tools with nanoscopic resolution or better, including scanning electron microscopy (SEM), atomic force microscopy (AFM), and scanning tunneling microscopy (STM) methods, can generate highly detailed maps of nanoscopic structures. However, while these approaches provide great views of the morphological properties of nanomaterials, it has proven more challenging to derive chemical information from the corresponding images. To address this issue, attempts have been made to dress existing nanoscopy methods with spectroscopic sensitivity. A powerful approach in this direction is the combination of scan probe techniques with optical illumination, which aims to marry the nanoscopic resolution provided by a sharp tip with the chemical selectivity provided by optical spectroscopy. Examples of this approach include existing techniques such as scattering-type scanning near-field optical microscopy and tip-enhanced Raman spectroscopy. A new and emerging technique in this direction is photoinduced force microscopy (PiFM), which enables spectroscopic probing of materials with a spatial resolution well under 10 nm. In PiFM, the sample is optically excited and the response of the material is probed directly in the near-field by reading out the time-integrated force between the tip and the sample. Because the magnitude of the force is dependent on the photoinduced polarization in the sample, PiFM exhibits spectroscopic sensitivity. The photoinduced forces measured in PiFM are spatially confined on the nanometer scale, which translates into a very high spatial resolution even under ambient conditions. The PiFM approach is compatible with a wide range optical excitation frequencies, from the visible to the mid-infrared, enabling nanoscale imaging contrast based on either electronic or vibrational transitions in the sample. These properties make PiFM an attractive method for the visualization and spectroscopic characterization of a vast variety of nano materials, from semiconducting nanoparticles to polymer thin films to sensitive measurements of single molecules. In this Account, we review the principles of the PiFM technique and discuss the basic components of the photoinduced force microscope. We highlight the imaging properties of the PiFM instrument and demonstrate the inherent spectroscopic sensitivity of the technique. Furthermore, we show that the PiFM approach can be used to probe both the linear and nonlinear optical properties of nano materials. In addition, we provide several examples of PiFM imaging applications.