Technologies for investigating single-molecule chemical reactions.

Single molecules, the smallest independently stable units in the material world, serve as the fundamental building blocks of matter. Among different branches of single-molecule sciences, single-molecule chemical reactions, by revealing the behavior and properties of individual molecules at the molecular scale, are particularly attractive because they can advance the understanding of chemical reaction mechanisms and help to address key scientific problems in broad fields such as physics, chemistry, biology and materials science. This review provides a timely, comprehensive overview of single-molecule chemical reactions based on various technical platforms such as scanning probe microscopy, single-molecule junction, single-molecule nanostructure, single-molecule fluorescence detection and crossed molecular beam. We present multidimensional analyses of single-molecule chemical reactions, offering new perspectives for research in different areas, such as photocatalysis/electrocatalysis, organic reactions, surface reactions and biological reactions. Finally, we discuss the opportunities and challenges in this thriving field of single-molecule chemical reactions.

AI-Equipped Scanning Probe Microscopy for Autonomous Site-Specific Atomic-Level Characterization at Room Temperature.

An advanced scanning probe microscopy system enhanced with artificial intelligence (AI-SPM) designed for self-driving atomic-scale measurements is presented. This system expertly identifies and manipulates atomic positions with high precision, autonomously performing tasks such as spectroscopic data acquisition and atomic adjustment. An outstanding feature of AI-SPM is its ability to detect and adapt to surface defects, targeting or avoiding them as necessary. It is also designed to overcome typical challenges such as positional drift and tip apex atomic variations due to the thermal effects, ensuring accurate, site-specific surface analysis. The tests under the demanding conditions of room temperature have demonstrated the robustness of the system, successfully navigating thermal drift and tip fluctuations. During these tests on the Si(111)-(7 × 7) surface, AI-SPM autonomously identified defect-free regions and performed a large number of current-voltage spectroscopy measurements at different adatom sites, while autonomously compensating for thermal drift and monitoring probe health. These experiments produce extensive data sets that are critical for reliable materials characterization and demonstrate the potential of AI-SPM to significantly improve data acquisition. The integration of AI into SPM technologies represents a step toward more effective, precise and reliable atomic-level surface analysis, revolutionizing materials characterization methods.

Chirality Detection in Scanning Tunneling Microscopy Data Using Artificial Intelligence.

Enantiospecific effects play an uprising role in chemistry and technical applications. Chiral molecular networks formed by self-assembly processes at surfaces can be imaged by scanning probe microscopy (SPM). Low contrast and high noise in the topography map often interfere with the automatic image analysis using classical methods. The long SPM image acquisition times restrain Artificial Intelligence-based methods requiring large training sets, leaving only tedious manual work, inducing human-dependent errors and biased labeling. By generating realistic looking synthetic images, the acquisition of real datasets is avoided. Two state-of-the-art object detection architectures are trained to localize and classify chiral unit-cells in a regular molecular chiral network formed by self-assembly of linear molecular bricks. The comparison of different architectures and datasets demonstrates that the training on purely synthetic data outperforms models trained using augmented datasets. A Faster R-CNN model trained solely on synthetic data achieved an excellent mean average precision of 99% on real data. Hence this approach and the transfer to real data show high success, also highlighting the high robustness against experimental noise and different zoom levels across the full experimentally reasonable parameter range. The generalizability of this idea is demonstrated by achieving equally high performance on a different structure, too.

Design of an FPGA-Based Controller for Fast Scanning Probe Microscopy.

Atomic-scale imaging using scanning probe microscopy is a pivotal method for investigating the morphology and physico-chemical properties of nanostructured surfaces. Time resolution represents a significant limitation of this technique, as typical image acquisition times are on the order of several seconds or even a few minutes, while dynamic processes-such as surface restructuring or particle sintering, to be observed upon external stimuli such as changes in gas atmosphere or electrochemical potential-often occur within timescales shorter than a second. In this article, we present a fully redesigned field programmable gate array (FPGA)-based instrument that can be integrated into most commercially available standard scanning probe microscopes. This instrument not only significantly accelerates the acquisition of atomic-scale images by orders of magnitude but also enables the tracking of moving features such as adatoms, vacancies, or clusters across the surface ("atom tracking") due to the parallel execution of sophisticated control and acquisition algorithms and the fast exchange of data with an external processor. Each of these measurement modes requires a complex series of operations within the FPGA that are explained in detail.

Advancements in π-Magnetism and Precision Engineering of Carbon-Based Nanostructures.

The emergence of π-magnetism in low-dimensional carbon-based nanostructures, such as nanographenes (NGs), has captured significant attention due to their unique properties and potential applications in spintronics and quantum technologies. Recent advancements in on-surface synthesis under ultra-high vacuum conditions have enabled the atomically precise engineering of these nanostructures, effectively overcoming the challenges posed by their inherent strong chemical reactivity. This review highlights the essential concepts and synthesis methodologies used in studying NGs. It also outlines the remarkable progress made in understanding and controlling their magnetic properties. Advanced characterization techniques, such as scanning tunneling microscopy (STM) and non-contact atomic force microscopy (nc-AFM), have been instrumental in visualizing and manipulating these nanostructures, which highlighting their critical role in the field. The review underscores the versatility of carbon-based π-magnetic materials and their potential for integration into next-generation electronic devices. It also outlines future research directions aimed at optimizing their synthesis and exploring applications in cutting-edge technologies.

Magnetic Excitations in Ferromagnetically Coupled Spin-1 Nanographenes.

In the pursuit of high-spin building blocks for the formation of covalently bonded 1D or 2D materials with controlled magnetic interactions, $\pi$-electron magnetism offers an ideal framework to engineer ferromagnetic interactions between nanographenes. As a first step in this direction, we explore the spin properties of ferromagnetically coupled triangulenes -- triangular nanographenes with spin $S = 1$. By combining in-solution synthesis of rationally designed molecular precursors with on-surface synthesis, we successfully achieve covalently bonded $S = 2$ triangulene dimers and $S = 3$ trimers on Au(111). Starting with the triangulene dimer, we meticulously characterize its low-energy magnetic excitations using inelastic electron tunneling spectroscopy (IETS). IETS reveals conductance steps corresponding to a quintet-to-triplet excitation, and a zero-bias peak resulting from higher-order spin-spin scattering of the five-fold degenerate ferromagnetic ground state. The Heisenberg model captures the key parameters of inter-triangulene ferromagnetic exchange, and its successful extension to the larger $S = 3$ system validates the model's accuracy. We anticipate that incorporating ferromagnetically coupled building blocks into the repertoire of magnetic nanographenes will unlock new possibilities for designing carbon nanomaterials with complex magnetic ground states.

Bottom-up Synthesis and Characterization of Porous 12-Atom-Wide Armchair Graphene Nanoribbons.

Although several porous carbon/graphene nanoribbons (GNRs) have been prepared, a direct comparison of the electronic properties between a nonporous GNR and its periodically perforated counterpart is still missing. Here, we report the synthesis of porous 12-atom-wide armchair-edged GNRs from a bromoarene precursor on a Au(111) surface via hierarchical Ullmann and dehydrogenative coupling. The selective formation of porous 12-GNRs was achieved through thermodynamic and kinetic reaction control combined with tailored precursor design. The structure and electronic properties of the porous 12-GNR were elucidated by scanning tunneling microscopy/spectroscopy and density functional theory calculations, revealing that the pores induce a 2.17 eV band gap increase compared to the nonporous 12-AGNR on the same surface.

Scanning Probe Microscopy of Halide Perovskite Solar Cells.

Scanning probe microscopy (SPM) has enabled significant new insights into the nanoscale and microscale properties of solar cell materials and underlying working principles of photovoltaic and optoelectronic technology. Various SPM modes, including atomic force microscopy, Kelvin probe force microscopy, conductive atomic force microscopy, piezoresponse force microscopy, and scanning near-field optical microscopy, can be used for the investigation of electrical, optical and chemical properties of associated functional materials. A large body of work has improved the understanding of solar cell device processing and synthesis in close synergy with SPM investigations in recent years. This review provides an overview of SPM measurement capabilities and attainable insight with a focus on recently widely investigated halide perovskite materials.

Direct Exfoliation of Nanoribbons from Bulk van der Waals Crystals.

Confinement of monolayers into quasi-1D atomically thin nanoribbons could lead to novel quantum phenomena beyond those achieved in their bulk and monolayer counterparts. However, current experimental availability of nanoribbon species beyond graphene is limited to bottom-up synthesis or lithographic patterning. In this study, a versatile and direct approach is introduced to exfoliate bulk van der Waals crystals as nanoribbons. Akin to the Scotch tape exfoliation method for producing monolayers, this technique provides convenient access to a wide range of nanoribbons derived from their corresponding bulk crystals, including MoS2, WS2, MoSe2, WSe2, MoTe2, WTe2, ReS2, and hBN. The nanoribbons are predominantly monolayer, single-crystalline, parallel-aligned, flat, and exhibit high aspect ratios. The role of confinement, strain, and edge configuration of these nanoribbons is observed in their electrical, magnetic, and optical properties. This versatile exfoliation technique provides a universal route for producing a variety of nanoribbon materials and supports the study of their fundamental properties and potential applications.

Spin-State Switching of Spin-Crossover Complexes on Cu(111) Evidenced by Spin-Flip Spectroscopy.

Spin-crossover compounds can be switched between two stable states with different magnetic moments, conformations, electronic, and optical properties, which opens appealing perspectives for technological applications including miniaturization down to the scale of single molecules. Although control of the spin states is crucial their direct identification is challenging in single-molecule experiments. Here we investigate the spin-crossover complex [Fe(HB(1,2,4-triazol-1-yl)3)2] on a Cu(111) surface with scanning tunneling microscopy and density functional theory calculations. Spin crossover of single molecules in dense islands is achieved via electron injection. Spin-flip excitations are resolved in scanning tunneling spectra in a magnetic field enabling the direct identification of the molecular spin state, and revealing the existence of magnetic anisotropy in the HS molecules.

Transmetalation in Surface-Confined Single-Layer Organometallic Networks with Alkynyl-Metal-Alkynyl Linkages.

Transmetalation represents an appealing strategy toward fabricating and tuning functional metal-organic polymers and frameworks for diverse applications. In particular, building two-dimensional metal-organic and organometallic networks affords versatile nanoarchitectures of potential interest for nanodevices and quantum technology. The controlled replacement of embedded metal centers holds promise for exploring versatile material varieties by serial modification and different functionalization. Herein, we introduce a protocol for the modification of a single-layer carbon-metal-based organometallic network via transmetalation. By integrating external Cu atoms into the alkynyl-Ag organometallic network constructed with 1,3,5-triethynylbenzene precursors, we successfully realized in situ its highly regular alkynyl-Cu counterpart on the Ag(111) surface. While maintaining a similar lattice periodicity and pore morphology to the original alkynyl-Ag sheet, the Cu-based network exhibits increased thermal stability, guaranteeing improved robustness for practical implementation.

Scanning Probe Microscopy Characterization of Biomolecules enabled by Mass-Selective, Soft-landing Electrospray Ion Beam Deposition.

Scanning probe microscopy (SPM), in particular at low temperature (LT) under ultra-high vacuum (UHV) conditions, offers the possibility of real-space imaging with resolution reaching the atomic level. However, its potential for the analysis of complex biological molecules has been hampered by requirements imposed by sample preparation. Transferring molecules onto surfaces in UHV is typically accomplished by thermal sublimation in vacuum. This approach however is limited by the thermal stability of the molecules, i. e. not possible for biological molecules with low vapour pressure. Bypassing this limitation, electrospray ionisation offers an alternative method to transfer molecules from solution to the gas-phase as intact molecular ions. In soft-landing electrospray ion beam deposition (ESIBD), these molecular ions are subsequently mass-selected and gently landed on surfaces which permits large and thermally fragile molecules to be analyzed by LT-UHV SPM. In this concept, we discuss how ESIBD+SPM prepares samples of complex biological molecules at a surface, offering controls of the molecular structural integrity, three-dimensional shape, and purity. These achievements unlock the analytical potential of SPM which is showcased by imaging proteins, peptides, DNA, glycans, and conjugates of these molecules, revealing details of their connectivity, conformation, and interaction that could not be accessed by any other technique.

On-Surface Covalent Synthesis of Carbon Nanomaterials by Harnessing Carbon gem-Polyhalides.

The design of innovative carbon-based nanostructures stands at the forefront of both chemistry and materials science. In this context, π-conjugated compounds are of great interest due to their impact in a variety of fields, including optoelectronics, spintronics, energy storage, sensing and catalysis. Despite extensive research efforts, substantial knowledge gaps persist in the synthesis and characterization of new π-conjugated compounds with potential implications for science and technology. On-surface synthesis has emerged as a powerful discipline to overcome limitations associated with conventional solution chemistry methods, offering advanced tools to characterize the resulting nanomaterials. This review specifically highlights recent achievements in the utilization of molecular precursors incorporating carbon geminal (gem)-polyhalides as functional groups to guide the formation of π-conjugated 0D species, as well as 1D, quasi-1D π-conjugated polymers, and 2D nanoarchitectures. By delving into reaction pathways, novel structural designs, and the electronic, magnetic, and topological features of the resulting products, the review provides fundamental insights for a new generation of π-conjugated materials.

How scanning probe microscopy can be supported by artificial intelligence and quantum computing?

The impact of Artificial Intelligence (AI) is rapidly expanding, revolutionizing both science and society. It is applied to practically all areas of life, science, and technology, including materials science, which continuously requires novel tools for effective materials characterization. One of the widely used techniques is scanning probe microscopy (SPM). SPM has fundamentally changed materials engineering, biology, and chemistry by providing tools for atomic-precision surface mapping. Despite its many advantages, it also has some drawbacks, such as long scanning times or the possibility of damaging soft-surface materials. In this paper, we focus on the potential for supporting SPM-based measurements, with an emphasis on the application of AI-based algorithms, especially Machine Learning-based algorithms, as well as quantum computing (QC). It has been found that AI can be helpful in automating experimental processes in routine operations, algorithmically searching for optimal sample regions, and elucidating structure-property relationships. Thus, it contributes to increasing the efficiency and accuracy of optical nanoscopy scanning probes. Moreover, the combination of AI-based algorithms and QC may have enormous potential to enhance the practical application of SPM. The limitations of the AI-QC-based approach were also discussed. Finally, we outline a research path for improving AI-QC-powered SPM. RESEARCH HIGHLIGHTS: Artificial intelligence and quantum computing as support for scanning probe microscopy. The analysis indicates a research gap in the field of scanning probe microscopy. The research aims to shed light into ai-qc-powered scanning probe microscopy.

Reversible Mechanical Switching of Ferroelastic Stripe Domains in Multiferroic Thin Films.

The application potential of ferroelectric thin films largely relies on the controllability of their domain structure. Among the various proposed strategies, mechanical switching is being considered as a potential alternative to replace electrical switching for control of the domain structure of ferroelectric thin films via, e.g., the flexoelectric effect. So far, studies on mechanical switching are confined to out-of-plane polarization switching in ferroelectric thin films, which are in pristine or prepoled single-domain states. In this work, we report reversible in-plane mechanical switching of the monoclinic phase (MC phase) stripe domains in BiFeO3 thin films can be realized by scanning tip force. Via controlling the fast scan direction of the scanning probe microscopy tip and the magnitude of the tip force, the effective trailing field induced by the local tip force can be rotated to consequently switch the net in-plane polarization of the two-variant stripe domain patterns by either 90° or 180°. Moreover, the monoclinic to rhombohedral (MC-R) phase transition occurs during mechanical switching with the distribution of R-phase domains dependent on the switching paths. These results extend our current understanding of the mechanical switching behavior in ferroelectric thin films and should be instructive for their future applications.

Measuring the Shape, Stiffness, and Interface Tension of Droplets with the Scanning Ion Conductance Microscope.

Imaging and probing liquid-liquid interfaces at the micro- and nanoscale are of high relevance, for example, in materials science, surface chemistry, and microfluidics. However, existing imaging techniques are limited in resolution, average over large sample areas, or interact with the sample. Here, we present a method to quantify the shape, stiffness, and interface tension of liquid droplets with the scanning ion conductance microscope (SICM), providing submicrometer resolution and the ability to perform noncontact mechanical measurements. We show that we can accurately image the three-dimensional shape of micrometer-sized liquid droplets made of, for example, decane, hexane, or different oils. We then introduce numerical models to quantitatively obtain their stiffness and interface tension from SICM data. We verified our method by measuring the interface tension of decane droplets changing under the influence of surfactants at different concentrations. Finally, we use SICM to resolve the dissolution dynamics of decane droplets, showing that droplet shape exhibits different dissolution modes and stiffness continuously increases while the interface tension remains constant. We thereby demonstrate that SICM is a useful method to investigate liquid-liquid interfaces on the microscale with applications in materials or life sciences.

Scanning Probe Microscopies for Characterizations of 2D Materials.

2D materials are intriguing due to their remarkably thin and flat structure. This unique configuration allows the majority of their constituent atoms to be accessible on the surface, facilitating easier electron tunneling while generating weak surface forces. To decipher the subtle signals inherent in these materials, the application of techniques that offer atomic resolution (horizontal) and sub-Angstrom (z-height vertical) sensitivity is crucial. Scanning probe microscopy (SPM) emerges as the quintessential tool in this regard, owing to its atomic-level spatial precision, ability to detect unitary charges, responsiveness to pico-newton-scale forces, and capability to discern pico-ampere currents. Furthermore, the versatility of SPM to operate under varying environmental conditions, such as different temperatures and in the presence of various gases or liquids, opens up the possibility of studying the stability and reactivity of 2D materials in situ. The characteristic flatness, surface accessibility, ultra-thinness, and weak signal strengths of 2D materials align perfectly with the capabilities of SPM technologies, enabling researchers to uncover the nuanced behaviors and properties of these advanced materials at the nanoscale and even the atomic scale.

Ultrastructural 3D Microscopy for Biomedicine: Principles, Applications, and Perspectives.

Modern biomedical research often requires a three-dimensional microscopic analysis of the ultrastructure of biological objects and materials. Conceptual technical and methodological solutions for three-dimensional structure reconstruction are needed to improve the conventional optical, electron, and probe microscopy methods, which to begin with allow one to obtain two-dimensional images and data. This review discusses the principles and potential applications of such techniques as serial section transmission electron microscopy; techniques based on scanning electron microscopy (SEM) (array tomography, focused ion beam SEM, and serial block-face SEM). 3D analysis techniques based on modern super-resolution optical microscopy methods are described (stochastic optical reconstruction microscopy and stimulated emission depletion microscopy), as well as ultrastructural 3D microscopy methods based on scanning probe microscopy and the feasibility of combining them with optical techniques. A comparative analysis of the advantages and shortcomings of the discussed approaches is performed.

Fourier transform-based post-processing drift compensation and calibration method for scanning probe microscopy.

Scanning probe microscopy (SPM) is ubiquitous in nanoscale science allowing the observation of features in real space down to the angstrom resolution. The scanning nature of SPM, wherein a sharp tip rasters the surface during which a physical setpoint is maintained via a control feedback loop, often implies that the image is subject to drift effects, leading to distortion of the resulting image. While there are in-operando methods to compensate for the drift, correcting the residual linear drift in obtained images is often neglected. In this paper, we present a reciprocal space-based technique to compensate the linear drift in atomically-resolved scanning probe microscopy images without distinction of the fast and slow scanning directions; furthermore this method does not require the set of SPM images obtained for the different scanning directions. Instead, the compensation is made possible by the a priori knowledge of the lattice parameters. The method can also be used to characterize and calibrate the SPM instrument.

Automated Structure Discovery for Scanning Tunneling Microscopy.

Scanning tunneling microscopy (STM) with a functionalized tip apex reveals the geometric and electronic structures of a sample within the same experiment. However, the complex nature of the signal makes images difficult to interpret and has so far limited most research to planar samples with a known chemical composition. Here, we present automated structure discovery for STM (ASD-STM), a machine learning tool for predicting the atomic structure directly from an STM image, by building upon successful methods for structure discovery in noncontact atomic force microscopy (nc-AFM). We apply the method on various organic molecules and achieve good accuracy on structure predictions and chemical identification on a qualitative level while highlighting future development requirements for ASD-STM. This method is directly applicable to experimental STM images of organic molecules, making structure discovery available for a wider scanning probe microscopy audience outside of nc-AFM. This work also allows more advanced machine learning methods to be developed for STM structure discovery.