Stabilizing Ti3C2Tx MXene flakes in air by removing confined water.

MXenes have demonstrated potential for various applications owing to their tunable surface chemistry and metallic conductivity. However, high temperatures can accelerate MXene film oxidation in air. Understanding the mechanisms of MXene oxidation at elevated temperatures, which is still limited, is critical in improving their thermal stability for high-temperature applications. Here, we demonstrate that Ti[Formula: see text]C[Formula: see text]T[Formula: see text] MXene monoflakes have exceptional thermal stability at temperatures up to 600[Formula: see text]C in air, while multiflakes readily oxidize in air at 300[Formula: see text]C. Density functional theory calculations indicate that confined water between Ti[Formula: see text]C[Formula: see text]T[Formula: see text] flakes has higher removal energy than surface water and can thus persist to higher temperatures, leading to oxidation. We demonstrate that the amount of confined water correlates with the degree of oxidation in stacked flakes. Confined water can be fully removed by vacuum annealing Ti[Formula: see text]C[Formula: see text]T[Formula: see text] films at 600[Formula: see text]C, resulting in substantial stability improvement in multiflake films (can withstand 600[Formula: see text]C in air). These findings provide fundamental insights into the kinetics of confined water and its role in Ti[Formula: see text]C[Formula: see text]T[Formula: see text] oxidation. This work enables the use of stable monoflake MXenes in high-temperature applications and provides guidelines for proper vacuum annealing of multiflake films to enhance their stability.

Pulsed Force Kelvin Probe Force Microscopy-A New Type of Kelvin Probe Force Microscopy under Ambient Conditions.

Kelvin probe force microscopy (KPFM) is an increasingly popular scanning probe microscopy technique used for nanoscale imaging of surface potential for various materials, such as metals, semiconductors, biological samples, and photovoltaics, to reveal their surface work function and/or local accumulation of charges. This featured review outlines the operation principles and applications of KPFM, including several typical commercially available variants. We highlight the significance of surface potential measurements, present the details of the method operation, and discuss the causes of the limitation on spatial resolution. Then, we present the pulsed force Kelvin probe force microscopy (PF-KPFM) as an innovative improvement to KPFM, which provides an enhanced spatial resolution of <10 nm under ambient conditions. PF-KPFM is promising for the characterization of heterogeneous materials with spatial variations of electrical properties. It will be especially instrumental for investigating emerging perovskite photovoltaics, heterogeneous catalysts, 2D materials, and ferroelectric materials, among others.

Atomic-force-microscopy-based time-domain two-dimensional infrared nanospectroscopy.

For decades, infrared (IR) spectroscopy has advanced on two distinct frontiers: enhancing spatial resolution and broadening spectroscopic information. Although atomic force microscopy (AFM)-based IR microscopy overcomes Abbe's diffraction limit and reaches sub-10 nm spatial resolutions, time-domain two-dimensional IR spectroscopy (2DIR) provides insights into molecular structures, mode coupling and energy transfers. Here we bridge the boundary between these two techniques and develop AFM-2DIR nanospectroscopy. Our method offers the spatial precision of AFM in combination with the rich spectroscopic information provided by 2DIR. This approach mechanically detects the sample's photothermal responses to a tip-enhanced femtosecond IR pulse sequence and extracts spatially resolved spectroscopic information via FFTs. In a proof-of-principle experiment, we elucidate the anharmonicity of a carbonyl vibrational mode. Further, leveraging the near-field photons' high momenta from the tip enhancement for phase matching, we photothermally probe hyperbolic phonon polaritons in isotope-enriched h10BN. Our measurements unveil an energy transfer between phonon polaritons and phonons, as well as among different polariton modes, possibly aided by scattering at interfaces. The AFM-2DIR nanospectroscopy enables the in situ investigations of vibrational anharmonicity, coupling and energy transfers in heterogeneous materials and nanostructures, especially suitable for unravelling the relaxation process in two-dimensional materials at IR frequencies.

What Do Different Modes of AFM-IR Mean for Measuring Soft Matter Surfaces?

In the past decade, rapidly emerging atomic force microscopy-based photothermal infrared microscopy (AFM-IR) techniques have routinely delivered surface chemical imaging with tens of nanometers spatial resolution. The commercial availability of AFM-IR instruments has accelerated their popularity among soft matter and surface science communities. Various AFM-IR modes exist with different characteristics. In this Perspective, we discuss the challenges and opportunities associated with many AFM-IR modes, clarifying the possible confusion arising from terminologies and describing the possible benefits of using multiple AFM-IR modes for a better understanding of the nanoscale composition organization of the interface.

Pulsed Force Kelvin Probe Force Microscopy through Integration of Lock-In Detection.

Kelvin probe force microscopy measures surface potential and delivers insights into nanoscale electronic properties, including work function, doping levels, and localized charges. Recently developed pulsed force Kelvin probe force microscopy (PF-KPFM) provides sub-10 nm spatial resolution under ambient conditions, but its original implementation is hampered by instrument complexity and limited operational speed. Here, we introduce a solution for overcoming these two limitations: a lock-in amplifier-based PF-KPFM. Our method involves phase-synchronized switching of a field effect transistor to mediate the Coulombic force between the probe and the sample. We validate its efficacy on two-dimensional material MXene and aged perovskite photovoltaic films. Lock-in-based PF-KPFM successfully identifies the contact potential difference (CPD) of stacked flakes and finds that the CPDs of monoflake MXene are different from those of their multiflake counterparts, which are otherwise similar in value. In perovskite films, we uncover electrical degradation that remains elusive with surface topography.

Inducing trained immunity in pro-metastatic macrophages to control tumor metastasis.

Metastasis is the leading cause of cancer-related deaths and myeloid cells are critical in the metastatic microenvironment. Here, we explore the implications of reprogramming pre-metastatic niche myeloid cells by inducing trained immunity with whole beta-glucan particle (WGP). WGP-trained macrophages had increased responsiveness not only to lipopolysaccharide but also to tumor-derived factors. WGP in vivo treatment led to a trained immunity phenotype in lung interstitial macrophages, resulting in inhibition of tumor metastasis and survival prolongation in multiple mouse models of metastasis. WGP-induced trained immunity is mediated by the metabolite sphingosine-1-phosphate. Adoptive transfer of WGP-trained bone marrow-derived macrophages reduced tumor lung metastasis. Blockade of sphingosine-1-phosphate synthesis and mitochondrial fission abrogated WGP-induced trained immunity and its inhibition of lung metastases. WGP also induced trained immunity in human monocytes, resulting in antitumor activity. Our study identifies the metabolic sphingolipid-mitochondrial fission pathway for WGP-induced trained immunity and control over metastasis.

Lock-in amplifier based peak force infrared microscopy.

Nanoscale infrared (nano-IR) microscopy enables label-free chemical imaging with a spatial resolution below Abbe's diffraction limit through the integration of atomic force microscopy and infrared radiation. Peak force infrared (PFIR) microscopy is one of the emerging nano-IR methods that provides non-destructive multimodal chemical and mechanical characterization capabilities using a straightforward photothermal signal generation mechanism. PFIR microscopy has been demonstrated to work for a wide range of heterogeneous samples, and it even allows operation in the fluid phase. However, the current PFIR microscope requires customized hardware configuration and software programming for real-time signal acquisition and processing, which creates a high barrier to PFIR implementation. In this communication, we describe a type of lock-in amplifier-based PFIR microscopy that can be assembled with generic, commercially available equipment without special hardware or software programming. We demonstrate this method on soft matters of structured polymer blends and blocks, as well as biological cells of E. coli. The lock-in amplifier-based PFIR reduces the entry barrier for PFIR microscopy and makes it a competitive nano-IR method for new users.

Fourier-Transform Atomic Force Microscope-Based Photothermal Infrared Spectroscopy with Broadband Source.

The mechanical detection of photothermal expansion from infrared (IR) absorption with an atomic force microscope (AFM) bypasses Abbe's diffraction limit, forming the chemical imaging technique of AFM-IR. Here, we develop a Fourier transform AFM-IR technique with peak force infrared microscopy and broadband femtosecond IR pulses. A Michelson interferometer creates a pair of IR pulses with controlled time delays to generate photothermal signals transduced by AFM to form an interferogram. A Fourier transform is performed to recover IR absorption spectra. We demonstrate the Fourier transform AFM-IR microscopy on a polymer blend and hexagonal boron nitride. An intriguing observation is the vertical asymmetry of the interferogram, which suggests the presence of multiphoton absorption processes under the tip-enhancement and femtosecond IR lasers. Our method demonstrates the feasibility of time-domain detection of the AFM-IR signal in the mid-IR regime and paves the way toward multiphoton vibrational spectroscopy at the nanoscale below the diffraction limit.

Principle and applications of peak force infrared microscopy.

Peak force infrared (PFIR) microscopy is an emerging atomic force microscopy (AFM)-based infrared microscopy that bypasses Abbe's diffraction limit on spatial resolution. The PFIR microscopy utilizes a nanoscopically sharp AFM tip to mechanically detect the tip-enhanced infrared photothermal response of the sample in the time domain. The time-gated mechanical signals of cantilever deflections transduce the infrared absorption of the sample, delivering infrared imaging and spectroscopy capability at sub 10 nm spatial resolution. Both the infrared absorption response and mechanical properties of the sample are obtained in parallel while preserving the surface integrity of the sample. This review describes the constructions of the PFIR microscope and several variations, including multiple-pulse excitation, total internal reflection geometry, dual-color configuration, liquid-phase operations, and integrations with simultaneous surface potential measurement. Representative applications of PFIR microscopy are also included in this review. In the outlook section, we lay out several future directions of innovations in PFIR microscopy and applications in chemical and material research.

Super-resolution mid-infrared spectro-microscopy of biological applications through tapping mode and peak force tapping mode atomic force microscope.

Small biomolecules at the subcellular level are building blocks for the manifestation of complex biological activities. However, non-intrusive in situ investigation of biological systems has been long daunted by the low spatial resolution and poor sensitivity of conventional light microscopies. Traditional infrared (IR) spectro-microscopy can enable label-free visualization of chemical bonds without extrinsic labeling but is still bound by Abbe's diffraction limit. This review article introduces a way to bypass the optical diffraction limit and improve the sensitivity for mid-IR methods - using tip-enhanced light nearfield in atomic force microscopy (AFM) operated in tapping and peak force tapping modes. Working principles of well-established scattering-type scanning near-field optical microscopy (s-SNOM) and two relatively new techniques, namely, photo-induced force microscopy (PiFM) and peak force infrared (PFIR) microscopy, will be briefly presented. With âˆ¼ 10-20 nm spatial resolution and monolayer sensitivity, their recent applications in revealing nanoscale chemical heterogeneities in a wide range of biological systems, including biomolecules, cells, tissues, and biomaterials, will be reviewed and discussed. We also envision several future improvements of AFM-based tapping and peak force tapping mode nano-IR methods that permit them to better serve as a versatile platform for uncovering biological mechanisms at the fundamental level.

Dual-Color Peak Force Infrared Microscopy.

Peak force infrared (PFIR) microscopy achieves nanoscale infrared imaging at sub-10 nm spatial resolution through photothermal mechanical detection of atomic force microscopy (AFM). However, it suffers from a major limitation that only one infrared frequency can be scanned for an AFM frame at a time. To overcome this limitation, we report here dual-color PFIR microscopy that enables simultaneous imaging at two infrared frequencies. This dual-color PFIR microscopy bypasses the limitations of frame drift and distortion of AFM when comparing two images of different infrared frequencies. We benchmark the performance and spatial resolution of this method using structured polymers exhibiting phase separation. We further demonstrate the application of this technique in imaging biological samples by mapping the cell wall of Escherichia coli (E. coli) bacteria. The presence of a bacterial outer membrane was detected without extrinsic labels. This dual-color PFIR microscopy enables simultaneous nondestructive chemical nanoimaging of multiple chemical components and will be useful for potential applications such as in situ dual-channel monitoring of chemical reactions.

Nano-Chemical and Mechanical Mapping of Fine and Ultrafine Indoor Aerosols with Peak Force Infrared Microscopy.

Indoor aerosols can adversely affect human health as we increasingly spend more time indoors. One of the aerosol research challenges is measuring fine and ultrafine aerosol particles with nanoscale dimensions. Spectroscopic tools, often diffraction-limited, cannot access the intra-particle heterogeneity. In this work, we extend the non-invasive nanoscopy method of peak force infrared (PFIR) microscopy to study indoor aerosols. Laboratory-generated fine bioaerosols were collected after filtration with a surgical face mask to serve as a benchmark sample, followed by a variety of field-collected indoor aerosols with and without the filtration of a facemask. A general heterogeneity is observed in individual aerosol particles, despite their nanoscale dimension. The presence of protein, triglycerides, and salt is detected through chemical and mechanical mapping. The PFIR microscopy is suitable to identify the composition of fine and ultrafine aerosols. Its application is particularly meaningful for understanding the particle structure to reduce aerosol-related transmission of diseases.

Integrated Tapping Mode Kelvin Probe Force Microscopy with Photoinduced Force Microscopy for Correlative Chemical and Surface Potential Mapping.

Kelvin probe force microscopy (KPFM) is a popular technique for mapping the surface potential at the nanoscale through measurement of the Coulombic force between an atomic force microscopy (AFM) tip and sample. The lateral resolution of conventional KPFM variants is limited to between ≈35 and 100 nm in ambient conditions due to the long-range nature of the Coulombic force. In this article, a novel way of generating the Coulombic force in tapping mode KPFM without the need for an external AC driving voltage is presented. A field-effect transistor (FET) is used to directly switch the electrical connectivity of the tip and sample on and off periodically. The resulting Coulomb force induced by Fermi level alignment of the tip and sample results in a detectable change of the cantilever oscillation at the FET-switching frequency. The resulting FET-switched KPFM delivers a spatial resolution of ≈25 nm and inherits the high operational speed of the AFM tapping mode. Moreover, the FET-switched KPFM is integrated with photoinduced force microscopy (PiFM), enabling simultaneous acquisitions of high spatial resolution chemical distributions and surface potential maps. The integrated FET-switched KPFM with PiFM is expected to facilitate characterizations of nanoscale electrical properties of photoactive materials, semiconductors, and ferroelectric materials.

Liquid medium annealing for fabricating durable perovskite solar cells with improved reproducibility.

Solution processing of semiconductors is highly promising for the high-throughput production of cost-effective electronics and optoelectronics. Although hybrid perovskites have potential in various device applications, challenges remain in the development of high-quality materials with simultaneously improved processing reproducibility and scalability. Here, we report a liquid medium annealing (LMA) technology that creates a robust chemical environment and constant heating field to modulate crystal growth over the entire film. Our method produces films with high crystallinity, fewer defects, desired stoichiometry, and overall film homogeneity. The resulting perovskite solar cells (PSCs) yield a stabilized power output of 24.04% (certified 23.7%, 0.08 cm2) and maintain 95% of their initial power conversion efficiency (PCE) after 2000 hours of operation. In addition, the 1-cm2 PSCs exhibit a stabilized power output of 23.15% (certified PCE 22.3%) and keep 90% of their initial PCE after 1120 hours of operation, which illustrates their feasibility for scalable fabrication. LMA is less climate dependent and produces devices in-house with negligible performance variance year round. This method thus opens a new and effective avenue to improving the quality of perovskite films and photovoltaic devices in a scalable and reproducible manner.

Liquid-Phase Peak Force Infrared Microscopy for Chemical Nanoimaging and Spectroscopy.

Peak force infrared (PFIR) microscopy is an emerging atomic force microscopy that bypasses Abbe's diffraction limit in achieving chemical nanoimaging and spectroscopy. The PFIR microscopy mechanically detects the infrared photothermal responses in the dynamic tip-sample contact of peak force tapping mode and has been applied for a variety of samples, ranging from soft matters, photovoltaic heterojunctions, to polaritonic materials under the air conditions. In this article, we develop and demonstrate the PFIR microscopy in the liquid phase for soft matters and biological samples. With the capability of controlling fluid compositions on demand, the liquid-phase peak force infrared (LiPFIR) microscopy enables in situ tracking of the polymer surface reorganization in fluids and detecting the product of click chemical reaction in the aqueous phase. Both broadband spectroscopy and infrared imaging with ∼10 nm spatial resolution are benchmarked in the fluid phase, together with complementary mechanical information. We also demonstrate the LiPFIR microscopy on revealing the chemical composition of a budding site of yeast cell wall particles in water as an application on biological structures. The label-free, nondestructive chemical nanoimaging and spectroscopic capabilities of the LiPFIR microscopy will facilitate the investigations of soft matters and their transformations at the solid/liquid interface.

Vibrational Spectroscopic Detection of a Single Virus by Mid-Infrared Photothermal Microscopy.

We report a confocal interferometric mid-infrared photothermal (MIP) microscope for ultra-sensitive and spatially resolved chemical imaging of individual viruses. The interferometric scattering principle is applied to detect the very weak photothermal signal induced by infrared absorption of chemical bonds. Spectroscopic MIP detection of single vesicular stomatitis viruses (VSVs) and poxviruses is demonstrated. The single virus spectra show high consistency within the same virus type. The dominant spectral peaks are contributed by the amide I and amide II vibrations attributed to the viral proteins. The ratio of these two peaks is significantly different between VSVs and poxviruses, highlighting the potential of using interferometric MIP microscopy for label-free differentiation of viral particles. This all-optical chemical imaging method opens a new way for spectroscopic detection of biological nanoparticles in a label-free manner and may facilitate in predicting and controlling the outbreaks of emerging virus strains.

Total Internal Reflection Peak Force Infrared Microscopy.

Total internal reflection (TIR) infrared spectroscopy is a convenient measurement tool for collecting spectra for chemical identification. However, TIR infrared microscopy lacks high spatial resolution due to the optical diffraction limit and difficulty to preserve a high-quality wave front for focus. In this article, we present the peak force infrared microscopy in the TIR geometry to achieve a 10 nm spatial resolution. Instead of optical detection, photothermal responses of the sample are collected in the peak force tapping mode of atomic force microscopy. We demonstrate the technique on two representative samples: structured polymers for soft matters and a hexagonal boron nitride flake for two-dimensional materials. As an extension of the apparatus, we also demonstrate nanoinfrared imaging with the TIR excitation for photoinduced force microscopy. The combination of TIR geometry with nanoinfrared microscopies simplifies the optical alignment, providing alternative instrument-designing principles for atomic force microscopy-based infrared microscopy.

Macrophage activation on "phagocytic synapse" arrays: Spacing of nanoclustered ligands directs TLR1/2 signaling with an intrinsic limit.

The activation of Toll-like receptor heterodimer 1/2 (TLR1/2) by microbial components plays a critical role in host immune responses against pathogens. TLR1/2 signaling is sensitive to the chemical structure of ligands, but its dependence on the spatial distribution of ligands on microbial surfaces remains unexplored. Here, we reveal the quantitative relationship between TLR1/2-triggered immune responses and the spacing of ligand clusters by designing an artificial "phagocytic synapse" nanoarray platform to mimic the cell-microbe interface. The ligand spacing dictates the proximity of receptor clusters on the cell surface and consequently the pro-inflammatory responses of macrophages. However, cell responses reach their maximum at small ligand spacings when the receptor nanoclusters become adjacent to one another. Our study demonstrates the feasibility of using spatially patterned ligands to modulate innate immunity. It shows that the receptor clusters of TLR1/2 act as a driver in integrating the spatial cues of ligands into cell-level activation events.