Scanning Probe Microscopy Experiments Research Articles

Advancing scanning probe microscopy simulations: A decade of development in probe-particle models

The Probe-Particle Model combine theories designed for the simulation of scanning probe microscopy experiments, employing non-reactive, flexible tip apices to achieve sub-molecular resolution. In the article we present the latest version of the Probe-Particle Model implemented in the open-source ppafm package, highlighting substantial advancements in accuracy, computational performance, and user-friendliness. To demonstrate this we provide a comprehensive review of approaches for simulating non-contact Atomic Force Microscopy. They vary in complexity from simple Lennard-Jones potential to the latest full density-based model. We compared those approaches with ab initio calculated references, showcasing their respective merits. All parts of the ppafm package have undergone acceleration by 1-2 orders of magnitude using OpenMP and OpenCL technologies. The updated package includes an interactive graphical user interface and seamless integration into the Python ecosystem via pip, facilitating advanced scripting and interoperability with other software. This adaptability positions ppafm as an ideal tool for high-throughput applications, including the training of machine learning models for the automatic recovery of atomic structures from nc-AFM measurements. We envision significant potential for this application in future single-molecule analysis, synthesis, and advancements in surface science in general. Additionally, we discuss simulations of other sub-molecular scanning-probe imaging techniques, such as bond-resolved scanning tunneling microscopy and kelvin probe force microscopy, all built on the robust foundation of the Probe-Particle Model. Altogether this demonstrates the broad impact of the model across diverse domains of on-surface science and molecular chemistry.

On-Surface Synthesis of Macrocycles, Non-Planar Carbon Ribbons and Heteroatom-Doped Nanographenes

On-surface synthesis via covalent coupling of adsorbed molecules on metal surfaces has attracted significant attention recently due to its potential to fabricate low-dimensional carbon materials with atomic precision. The bottom-up, atomically precise synthesis of carbon nanostructures enables the tailoring of their electronic properties at a molecular level. To understand and control the surface-chemistry-driven synthesis, many efforts have been made to design innovative precursors, explore novel reaction schemes, and utilize templating effects from the substrate.My presentation focuses on high-resolution scanning probe microscopy experiments combined with density functional theory to demonstrate recent highlights on the assembly of surface-supported low-dimensional carbon structures on metal surfaces. First, the assembly and electronic structure of planar π-extended cycloparaphenylene macrocycles, representing the first nanographene with an all-armchair edge topology, will be presented [1]. The second part will discuss the bottom-up synthesis of covalently-linked non-planar carbon ribbons and their electronic properties depending on their adsorption geometry. Finally, I will conclude with the on-surface cyclomerization of oxygen heterocycles to understand the on-surface synthesis of furan and pyran derivatives from ketone-functionalized precursors on metal surfaces.[1] Xiang, et al. Nature Chem., 2022 14, 871–876.

Complete Selective Switching of Ferroelastic Domain Stripes in Multiferroic Thin Films by Tip Scanning

AbstractBiFeO3 is a rare single‐phase multiferroic which shows coupled ferroelectricity, ferroelasticity and antiferromagnetism at room temperature. Many fantastic properties of BiFeO3 are regulated by its domain structure. While (001) rhombohedral BiFeO3 thin films can possibly develop up‐to eight degenerate states of two‐variant 71° ferroelastic domain stripes, complete selective control of all possible switching paths between these states has not yet been achieved. Here, combining phase field simulations and scanning probe microscopy experiments, we demonstrated such a complete selective control. The tip bias and the built‐in field were shown to affect the volume fraction of the 71°, 109° and 180° switched domains in rhombohedral BiFeO3 thin films under single‐point loading. Meanwhile, tip scanning further broke the symmetry of the nucleated domains, leading to different switched domain patterns. We then grew BiFeO3 thin films with a specific two‐variant 71° ferroelastic domain state and showed that such a state could be deterministically switched into the other seven two‐variant domain states by collaborative controlling tip scanning and tip bias in scanning probe microscopy experiments. These results should deepen our current understanding on the domain switching kinetics in BiFeO3 thin films and indicate they are promising platforms for developing configurable electronic and spintronic devices.

Regulation of flux-closure domain structures via oxygen vacancies and charged scanning probe microscopy

Manipulation of topological structures has become one of the most interesting topics in ferroelectrics through multiple excitations due to their prospective applications in electro-mechanical-optic devices. Scanning probe microscopy (SPM) has been developed as a powerful tool to manipulate the polar state in ferroic materials, in which the electric field induced by charged SPM enables dynamic coupling between the switching of the polar states and electromigration of oxygen vacancies, resulting in unknown influences of oxygen vacancy on the polar state in ferroelectric topological structures. Here, we regulate the polar state by considering oxygen vacancies and a non-uniform electric field under the charged SPM experiment for flux-closure domain structures in PbTiO3 thin films. The charged SPM probe can excite the growth of newly flux-closure domains to improve the density of topological states. In contrast, oxygen vacancies are found to suddenly prohibit the evolution of the flux-closure domain structure, when their concentration jumps to a threshold value. Our results might give guidelines to increase and stabilize the memory unit through co-modulating the electric field and ions injection in the information field.

Probe conditioning via convolution neural network for scanning probe microscopy automation

We present an automation system for conditioning a scanning probe microscopy (SPM) probe into different states on a Si(111)–(7 × 7) surface at room temperature. Topography images representing multiple surface states and probe condition states divided into 11 categories and trained by a convolution neural network with an accuracy of 87% were used to estimate the effectiveness of the probe with an accuracy of 98%. We demonstrate the responsiveness of the method by experimentally reforming a probe into different conditions defined by preset categories. This system will promote advancements in autonomous SPM experiments at atomic scale and room temperature.

Degradation phenomena of quantum dot light-emitting diodes induced by high electric field

Quantum dots possess exceptional optoelectronic properties, such as narrow bandwidth, controllable wavelength, and compatibility with solution-based processing. However, for efficient and stable operation in electroluminescence mode, several issues require resolution. Particularly, as device dimensions decrease, a higher electric field may be applied through next-generation quantum dot light-emitting diode (QLED) devices, which could further degrade the device. In this study, we conduct a systematic analysis of the degradation phenomena of a QLED device induced by a high electric field, using scanning probe microscopy (SPM) and transmission electron microscopy (TEM). We apply a local high electric field to the surface of a QLED device using an atomic force microscopy (AFM) tip, and we investigate changes in morphology and work function in the Kelvin probe force microscopy mode. After the SPM experiments, we perform TEM measurements on the same degraded sample area affected by the electric field of the AFM tip. The results indicate that a QLED device could be mechanically degraded by a high electric field, and work function changes significantly in degraded areas. In addition, the TEM measurements reveal that In ions migrate from the indium tin oxide (ITO) bottom electrode to the top of the QLED device. The ITO bottom electrode also deforms significantly, which could induce work function variation. The systematic approach adopted in this study can provide a suitable methodology for investigating the degradation phenomena of various optoelectronic devices.

Facile Control of Ferroelastic Domain Patterns in Multiferroic Thin Films by a Scanning Tip Bias.

BiFeO3, known as the "holy grail of all multiferroics", provides an appealing platform for exploration of multifield coupling physics and design of functional devices. Many fantastic properties of BiFeO3 are regulated by its ferroelastic domain structure. However, a facile programable control on the ferroelastic domain structure in BiFeO3 remains challenging and our understanding on the existing control strategies is also far from complete. This work reports a facile control of ferroelastic domain patterns in BiFeO3 thin films under area scanning poling by exploiting the tip bias as the control parameter. Combining scanning probe microscopy experiments and simulations, we found that BiFeO3 thin films with pristine 71° rhombohedral-phase stripe domains exhibit at least four switching pathways solely by controlling the scanning tip bias. As a result, one can readily write mesoscopic topological defects into the films without the necessity to change the tip motion. The correlation between conductance of the scanned region and the switching pathway is further investigated. Our results extend the current understanding on the domain switching kinetics and the coupled electronic transport properties in BiFeO3 thin films. The facile voltage control of ferroelastic domains should facilitate the development of configurable electronic and spintronic devices.

The Role of Metal Adatoms in a Surface‐Assisted Cyclodehydrogenation Reaction on a Gold Surface

AbstractDehydrogenation reactions are key steps in many metal‐catalyzed chemical processes and in the on‐surface synthesis of atomically precise nanomaterials. The principal role of the metal substrate in these reactions is undisputed, but the role of metal adatoms remains, to a large extent, unanswered, particularly on gold substrates. Here, we discuss their importance by studying the surface‐assisted cyclodehydrogenation on Au(111) as an ideal model case. We choose a polymer theoretically predicted to give one of two cyclization products depending on the presence or absence of gold adatoms. Scanning probe microscopy experiments observe only the product associated with adatoms. We challenge the prevalent understanding of surface‐assisted cyclodehydrogenation, unveiling the catalytic role of adatoms and their effect on regioselectivity. The study adds new perspectives to the understanding of metal catalysis and the design of on‐surface synthesis protocols for novel carbon nanomaterials.

The Role of Metal Adatoms in a Surface-Assisted Cyclodehydrogenation Reaction on a Gold Surface.

Dehydrogenation reactions are key steps in many metal-catalyzed chemical processes and in the on-surface synthesis of atomically precise nanomaterials. The principal role of the metal substrate in these reactions is undisputed, but the role of metal adatoms remains, to a large extent, unanswered, particularly on gold substrates. Here, we discuss their importance by studying the surface-assisted cyclodehydrogenation on Au(111) as an ideal model case. We choose a polymer theoretically predicted to give one of two cyclization products depending on the presence or absence of gold adatoms. Scanning probe microscopy experiments observe only the product associated with adatoms. We challenge the prevalent understanding of surface-assisted cyclodehydrogenation, unveiling the catalytic role of adatoms and their effect on regioselectivity. The study adds new perspectives to the understanding of metal catalysis and the design of on-surface synthesis protocols for novel carbon nanomaterials.

Automated tip functionalization via machine learning in scanning probe microscopy

Auto-CO-AFM is an open-source software package for scanning probe microscopes that enables the automatic functionalization of scanning probe tips with carbon monoxide molecules. This enables machine operators to specify the quality of the tip needed utilizing a pre-trained library with off-the-shelf software. From a single image, the software package can determine which molecules on a surface are carbon monoxide, perform the necessary tip functionalization procedures, interface with microscope software to control the tip position, and determines the centeredness of the tip after a successful functionalization. This is of particular interest for atomic force microscopy imaging of molecules on surfaces, where the tip functionalization is a necessary and time consuming step needed for sub-molecular resolution imaging. This package is freely available under the MIT License. Program summaryProgram Title: Auto-CO-AFMCPC Library link to program files:https://doi.org/10.17632/khfvjhx4vb.1Developer's repository link:https://github.com/SINGROUP/Auto-CO-AFMLicensing provisions: MITProgramming language: PythonSupplementary material: Supplementary Information as PDFNature of problem: Scanning probe microscopy experiments are limited by the lack of automated tools in tip preparation, particularly when functionalizing an adatom or molecule on the end of a tip. These tip functionalizations are commonly manually-driven processes that are time-consuming for the operator.Solution method: We have developed an automated solution for tip functionalization for carbon monoxide molecules, which combines machine learning descriptors with automated software control of the tip preparation process. The Python program interfaces with a major vendor's software to scan, functionalize, and verify the tip quality for the operator. The source code, documentation, and basic program are posted online.Additional comments including restrictions and unusual features: Current version of software in publication requires STMAFM software from CreaTec GmbH in physical connection with a CreaTec DSP.

Double sample holder for efficient high-resolution studies of an insulator and a metal surface.

A double sample holder supporting both a metal sample and an insulator crystal for high-resolution scanning probe microscopy experiments is described. The metal sample serves as a substrate for tip preparation and tip functionalization to efficiently and reliably enable high-resolution studies of the adjacent insulator surface. Imaging of Ag(111)/mica, Au(111)/mica, CaF2(111), and calcite(104) surfaces is demonstrated at 5K, including images on calcite(104) produced with a CO terminated tip, which was prepared on the adjacent metal sample.

Amplitude Dependence of Resonance Frequency and its Consequences for Scanning Probe Microscopy.

With recent advances in scanning probe microscopy (SPM), it is now routine to determine the atomic structure of surfaces and molecules while quantifying the local tip-sample interaction potentials. Such quantitative experiments using noncontact frequency modulation atomic force microscopy is based on the accurate measurement of the resonance frequency shift due to the tip-sample interaction. Here, we experimentally show that the resonance frequency of oscillating probes used for SPM experiments change systematically as a function of oscillation amplitude under typical operating conditions. This change in resonance frequency is not due to tip-sample interactions, but rather due to the cantilever strain or geometric effects and thus the resonance frequency is a function of the oscillation amplitude. Our numerical calculations demonstrate that the amplitude dependence of the resonance frequency is an additional yet overlooked systematic error source that can result in nonnegligible errors in measured interaction potentials and forces. Our experimental results and complementary numerical calculations reveal that the frequency shift due to this amplitude dependence needs to be corrected even for experiments with active oscillation amplitude control to be able to quantify the tip-sample interaction potentials and forces with milli-electron volt and pico-Newton resolutions.

Porphine Homocoupling on Au(111)

The covalent coupling of porphine molecules on Au(111) is studied by scanning probe microscopy experiments and density functional theory. At sufficient temperatures, dehydrogenative C–C coupling of...

Pauli blockade microscopy of quantum dots

We propose a spin-sensitive scanning probe microscopy experiment on double quantum dots in Pauli blockade conditions. Electric spin resonance is induced by an AC voltage applied to the scanning gate which causes lifting of the Pauli blockade of the current. The stationary Hamiltonian eigenstates are used as a basis for description of the spin dynamics with the AC potential of the probe. For the two-electron system we evaluate the transition rates from triplet T+ state to singlet S or triplet T0 states, i.e. to conditions in which the Pauli blockade of the current is lifted. The rates of the spin-flip transitions are consistent with the transition matrix elements and strongly dependent on the tip position. Probing the spin densities and identification of the final transition state are discussed.

Compression-Induced Modification of Boron Nitride Layers: A Conductive Two-Dimensional BN Compound.

The ability to create materials with improved properties upon transformation processes applied to conventional materials is the keystone of materials science. Here, hexagonal boron nitride (h-BN), a large-band-gap insulator, is transformed into a conductive two-dimensional (2D) material- bonitrol-that is stable at ambient conditions. The process, which requires compression of at least two h-BN layers and hydroxyl ions, is characterized via scanning probe microscopy experiments and ab initio calculations. This material and its creation mechanism represent an additional strategy for the transformation of known 2D materials into artificial advanced materials with exceptional properties.

Apparent Softening of Wet Graphene Membranes on a Microfluidic Platform.

Graphene is regarded as the toughest two-dimensional material (highest in-plane elastic properties) and, as a consequence, it has been employed/proposed as an ultrathin membrane in a myriad of microfluidic devices. Yet, an experimental investigation of eventual variations on the apparent elastic properties of a suspended graphene membrane in contact with air or water is still missing. In this work, the mechanical response of suspended monolayer graphene membranes on a microfluidic platform is investigated via scanning probe microscopy experiments. A high elastic modulus is measured for the membrane when the platform is filled with air, as expected. However, a significant apparent softening of graphene is observed when water fills the microfluidic system. Through molecular dynamics simulations and a phenomenological model, we associate such softening to a water-induced uncrumpling process of the suspended graphene membrane. This result may bring substantial modifications on the design and operation of microfluidic devices which exploit pressure application on graphene membranes.

Cryogenic positioning and alignment with micrometer precision in a magnetic resonance force microscope.

Aligning a microcantilever to an area of interest on a sample is a critical step in many scanning probe microscopy experiments, particularly those carried out on devices and rare, precious samples. We report a series of protocols that rapidly and reproducibly align a high-compliance microcantilever to a <10 μm sample feature under high vacuum and at cryogenic temperatures. The first set of protocols, applicable to a cantilever oscillating parallel to the sample surface, involve monitoring the cantilever resonance frequency while laterally scanning the tip to map the sample substrate through electrostatic interactions of the substrate with the cantilever. We demonstrate that when operating a cantilever a few micrometers from the sample surface, large shifts in the cantilever resonance frequency are present near the edges of a voltage-biased sample electrode. Surprisingly, these "edge-finder" frequency shifts are retained when the electrode is coated with a polymer film and a ∼10 nm thick metallic ground plane. The second series of methods, applicable to any scanning probe microscopy experiment, integrate a single-optical fiber to image line scans of the sample surface. The microscope modifications required for these methods are straightforward to implement, provide reliable micrometer-scale positioning, and decrease the experimental setup time from days to hours in a vacuum, cryogenic magnetic resonance force microscope.

An On-Surface Reaction Confined within a Porous Molecular Template.

On-surface reactions based on metal-catalysed Ullmann coupling have been successfully employed to synthesise a wide variety of covalently coupled structures. Substrate chemistry and topology are both known to effect the progression of an on-surface reaction; offering routes to control efficiency and selectivity. Here, we detail ultra-high vacuum scanning probe microscopy experiments showing that templating a catalytically active surface, via a supramolecular template, influences the reaction pathway of an on-surface Ullmann-type coupling reaction by inhibiting one potential intermediate structure and stabilising another.

Contact atomic force microscopy using piezoresistive cantilevers in load force modulation mode

Scanning probe microscopy (SPM) encompasses several techniques for imaging of the physical and chemical material properties at nanoscale. The scanning process is based on the detection of the deflection of the cantilever, which is caused by near field interactions, while the tip runs over the sample's surface. The variety of deflection detection methods including optical, piezoresistive, piezoelectric technologies has been developed and applied depending on the measurement mode and measurement environment. There are many advantages (compactness, vacuum compatibility, etc.) of the piezoresistive detection method, which makes it very attractive for almost all SPM experiments. Due to the technological limitations the stiffness of the piezoresistive beams is usually higher than the stiffness of the cantilever detected using optical methods. This is the basic constraint for the application of the piezoresistive beams in contact mode (CM) atomic force microscopy (AFM) investigations performed at low load forces (usually less than 20 nN). Drift of the deflection signal, which is related to thermal fluctuations of the measurement setup, causes that the microscope controller compensates the fluctuations instead of compensating the strength of tip-surface interactions. Therefore, it is quite difficult to keep near field interaction precisely at the setpoint level during the whole scanning process. This can lead to either damage of the cantilever's tip and material surface or loosing the contact with the investigated sample and making the measurement unreliable.For these reasons, load force modulation (LoFM) scanning mode, in which the interaction at the tip is precisely controlled at every point of the sample surface, is proposed to enable precise AFM surface investigations using the piezoresistive cantilevers. In this article we describe the developed measurement algorithm as well as proposed and introduced hardware and software solutions. The results of the experiments confirm strong reduction of the AFM entire setup drift. The results demonstrating contactless tip lateral movements are presented. It is common knowledge that such a scanning reduces tip wear.

Atomic force microscope imaging and force measurements at electrified and actively corroding interfaces: Challenges and novel cell design

We report the design of an improved electrochemical cell for atomic force microscope measurements in corrosive electrochemical environments. Our design improvements are guided by experimental requirements for studying corrosive reactions such as selective dissolution, dealloying, pitting corrosion, and∕or surface and interface forces at electrified interfaces. Our aim is to examine some of the limitations of typical electrochemical scanning probe microscopy (SPM) experiments and in particular to outline precautions and cell-design elements, which must necessarily be taken into account in order to obtain reliable experimental results. In particular, we discuss electrochemical requirements for typical electrochemical SPM experiments and introduce novel design features to avoid common issues such as crevice formations; we discuss the choice of electrodes and contaminations from ions of reference electrodes. We optimize the cell geometry and introduce standard samples for electrochemical AFM experiments. We have tested the novel design by performing force-distance spectroscopy as a function of the applied electrochemical potential between a bare gold electrode surface and a SAM-coated AFM tip. Topography imaging was tested by studying the well-known dealloying process of a Cu(3)Au(111) surface up to the critical potential. Our design improvements should be equally applicable to in situ electrochemical scanning tunneling microscope cells.