Atomic Force Microscopy Characterization Research Articles

Studying the Photoactivity of Ag-Decorated TiO2 Nanotubes with Combined AFM and Raman Spectroscopy

The drive for the development of systems that can simultaneously investigate chemical and morphological information comes from the requisite to fully understand the structure and chemical reactivity relationships of materials. This is particularly relevant in photocatalysis, a field ruled by surface interactions. An in-depth understanding of these complex interactions could lead to significant improvements in materials design, and consequently, in photocatalytic performances. Here, we present a first approach to a combined atomic force microscopy (AFM) and Raman spectroscopy characterization of anodic TiO2 nanotubes arrays decorated with Ag nanoparticle electrodeposition from either the same anodizing organic electrolyte or from an aqueous one. Photocatalytic substrates were used in up to 15 consecutive photocatalysis tests to prove their possible deterioration with reuse. Sample aging can, in principle, produce changes in both the morphology and the chemical compounds that characterize the photocatalyst surface. Adopting multiple characterization techniques, such as a combination of AFM and Raman spectroscopy in an original setup, can profitably enable the observation of surface contamination. A significant drop in photocatalytic activity was observed after 10 cycles on samples where silver was deposited from the organic electrolyte, while the others remained stable. Such a drop was ascribed to photocatalyst deactivation. While in other cases, a simple recovery treatment allowed the initial photoactivity to be restored, this deactivation was not restored even after chemical and thermal cleaning treatments.

Rapid Synthesis of Uniformly Small Nickel Nanoparticles for the Surface Functionalization of Epitaxial Graphene

AbstractNickel nanoparticles (Ni NPs) combined with carbon nanomaterials are of significant interest due to their wide range of applications, including catalysis, hydrogen storage, and sensor technologies. However, it is challenging to develop an efficient process to produce small and stable Ni NPs ideal for functionalizing graphene or substrates with complex geometries. For this purpose, a rapid, simple, and cost‐effective method is presented for synthesizing uniformly small Ni NPs. The process involves cooling aqueous solutions of Ni(OAc)2 and cetyltrimethylammonium bromide (CTAB) to ≈1 °C, followed by the rapid addition of NaBH4. Crucial parameters, such as temperature and stirring rate, are precisely controlled to ensure uniform particle growth, with the reaction completing in just a few minutes. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) characterizations reveal spherical NPs with an average diameter of ≈11 nm and a narrow size distribution. Additionally, epitaxial graphene (EG) samples are functionalized with the synthesized NPs and their arrangement on the surface and their stability upon thermal annealing are investigated. X‐ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM) measurements demonstrate the degradation of CTAB, along with the recovery of Ni(0) under mild conditions (below 350 °C), with the NPs maintaining structural stability up to approximately 550 °C.

Low-Temperature Sintering of Colloidal Gold Nanoparticles by Salt Addition

AbstractGold nanoparticles synthetized by pulsed laser ablation in liquid with a mean diameter of 4 nm were joined together by adding potassium bromide solution at various concentrations. By increasing the salt concentration, there is a significant increase of the particle size up to a mean diameter of 18 nm. We have studied the nanoparticle merging by using atomic force and electron microscopy characterizations, also demonstrating that it is possible to deposit sintered nanoparticles on silanized substrates in a fast, simple, cost-effective, energy-saving method with relevance in industrial manufacturing.

Enhancing tapping mode atomic force microscopy using AutoResonance control and a hybrid dynamic model

We present a novel method for analyzing tapping mode atomic force microscopy (AFM), enhancing topography reconstruction’s accuracy and speed. Our approach integrates an automatic resonance-tracking control scheme with a hybrid dynamic model that considers interactions between the AFM tip and the sample, and the oscillating sensor dynamics. A key aspect of our method is a simplified model that captures intricate dynamic behavior as a function of the distance from the topography. This model enables the immediate approximation of the distance from the topography, eliminating the necessity to lock onto the nominal distance as done with classical AFMs. To validate the accuracy, we conducted numerical simulations of Van der Waals and capillary interaction forces, as well as experimental measurements of a coin’s topography. The results affirm the effectiveness of our approach in enhancing AFM imaging and characterization capabilities.

High-quality Ge/SiGe heterostructure with atomically sharp interface grown by molecular beam epitaxy

Germanium is a versatile material for realization of spin and topological quantum computing. Here, we report on the epitaxial growth of an undoped Ge/SiGe heterostructure in which a hole quantum well is formed in the sandwiched Ge layer. The heterostructure is grown on Si (001) via molecular beam epitaxy (MBE). Atomic force microscopy characterizations display a flat surface with a root mean square roughness of 0.956 nm, and spherical aberration corrected transmission electron microscopy data show a sharp interface with a characteristic length of 0.49 nm. A mobility of up to 1.2 × 105 cm2 V−1 s−1 was achieved in the SiGe/Ge/SiGe two-dimensional hole gas (2DHG). The low percolation density of 3.70 × 1010 cm−2, light effective mass of 0.079 m0 (where m0 is the free electron mass), and large effective g-factor of 9.5 were obtained. These results show the potential of MBE-grown Ge 2DHG for semiconductor quantum computing.

Modified nanosphere lithography: application to the fabrication of ordered arrays of gold nanopyramids

In this work a modified approach to improve the capabilities of nanosphere lithography was performed to obtain ordered arrays of gold nanopyramids that can be used as Surface-Enhanced Raman Scattering (SERS) substrates. Specifically, shadow sphere lithography in combination with nanosphere lithography was used to fabricate metallic nanostructures of different sizes starting from the same mask of silica microspheres. An extensive study of the obtained samples with scanning electron microscopy, atomic force microscopy and Raman characterizations confirms that indeed this modification of the standard nanosphere lithography is an excellent candidate to produce ordered arrays of Au nanopyramids with good control on their geometric properties. Rhodamine 6G dye was used as a probe molecule to test our SERS substrates. These features can be used in turn to optimize the SERS substrates for several potential applications. Remarkably, it is shown that by this simple technique one can achieve enhancement factors and detection capabilities of dyes that are comparable with those obtained by using more sophisticated techniques as proposed recently in the literature.

Correlation between AFM characterizations and dynamic mechanical testing to assess the ductile-to-brittle transition during ABS photodegradation

The extensive use of Acrylonitrile Butadiene Styrene (ABS) raises challenges due to its vulnerability to oxidative degradation, primarily impacting its mechanical behavior. Photodegradation appears to be the pivotal driver in this degradation process. The main aim of the present study is to provide a comprehensive approach to the underlying mechanisms governing the transition from ductile to brittle behavior in ABS after exposure to UV-induced photodegradation. This study thus focuses on the multiphase nature of ABS, wherein polybutadiene (PB) nodules are dispersed within a matrix of styrene-acrylonitrile. Dynamic mechanical tensile tests have been employed to highlight aged layer mechanical impact by blocking the dissipative response of the matrix and applying a homogenous stress field, while atomic force microscopy (AFM) has been used to characterize the local mechanical properties of ABS finely. The evolution of global mechanical properties has been correlated with changes in microstructural behavior. One of the main contributions of the present work is the correlation between the formation of brittle layers with the brittle state of aged ABS. Mechanical testing using dynamical tensile test revealed a critical aging time marking the transition from a ductile to a brittle state of the 450 µm thick samples. Chemical analysis using infrared spectroscopy revealed evolutions in the material composition, especially in the carbonyl, hydroxyl, and PB unsaturation groups. Distinct thin oxidized layers on each exposed surface were observed using optical microscopy. Finally, AFM analysis on the exposed surface shows the stiffening of PB nodules, indicating the formation of brittle thin layers due to oxidation causing an apparent fragile behavior of ABS.

A hybrid effective medium description for nanoporous gold films and thickness-mediated control of optical absorption.

With the increasing demand for sensing platforms operating across UV, visible, and near-infrared wavelengths, nanoporous gold has emerged as an ideal substrate for rapid, quantitative detection of analytes with excellent specificity and high sensitivity. This study investigates thickness-mediated compositional changes and their impact on scattering characteristics of thin nanoporous gold films fabricated using selective chemical etching. Specifically, we observe thickness-induced morphological and structural changes across different fabricated samples from 25 to 100 nm in thickness. Upon their optical characterization across UV-VIS-NIR spectral regime, we notice that the constitutional differences among samples manifest distinctively & deterministically in their total optical scattering response. In order to gain insights into these observed scattering responses and to fathom the subtle connections between structural properties of NPG films and their optical response, a hybrid theoretical model comprising Maxwell-Garnett & Bruggeman effective medium approximations has been adopted. Our approach not only allows to appropriately account for the inhomogeneous nature of these films, but also corroborates well with the atomic force microscopy characterizations of the fabricated samples. Furthermore, tracing such a theoretical model is important as it helps in systematically ascertaining additional loss terms emerging in the complex dielectric function of films due to their nanoscale porosity & roughness, permitting a good reproduction of measured optical spectra. We believe, our approach will not only facilitate accurate regulation of losses in NPG thin films but will also aid in deriving customized optical performance from them, thereby advancing their potential applications in sensing and beyond.

Atomic force microscopy characterization of white and beige adipocyte differentiation.

Adipose tissue plays an essential role in systemic metabolism with white adipose tissue (WAT) making up most of the tissue and being involved in the regulation of energy homeostasis, and brown and beige adipose tissue (BAT) exhibiting thermogenic activity. There is promise in the conversion of white adipocytes into beige ones as a therapeutic potential to control and enhance systemic metabolism, but it is difficult to maintain this transformation in vivo because we do not fully understand the mechanism of conversion. In this study, we applied atomic force microscopy (AFM) to characterize beige or white adipocytes during the process of differentiation for morphology, roughness, adhesion, and elasticity at different time points. As cells differentiated to white and beige adipocytes, they exhibited morphological changes as they lipid loaded, transitioning from flattened elongated cells to a rounded shape indicating adipogenesis. While there was an initial decrease in elasticity for both beige and white adipocytes, white adipocytes exhibited a higher elasticity than beige adipocytes at all time points. Beige and white adipogenesis exhibited a decrease in adhesion energy compared to preadipocytes, yet at day 12, white adipocytes had a significant increase in adhesion energy compared to beige adipocytes. This work shows significant differences in the mechanical properties of white vs. beige adipocytes during differentiation. Results from this study contribute to a better understanding of the differentiation of adipocytes which are vital to the therapeutic induction, engineered models, and maintenance of beige adipocytes as a potential approach for enhancing systemic metabolism.

Direct deposition of Ti/MgF2 photoabsorber on PTFE membrane with enhanced robustness via plasma pretreatment for photothermal membrane distillation

Deposition of metal-dielectric hybrid composite on the polymer based membrane is important for the electrochemical, photochemical and photothermal reactions on the membrane surface. The hydrophilic reactants such as catalysts and photothermal materials are not easy to be deposited directly on the hydrophobic membrane surface, so in most cases, binder material has been adapted to stably combine them. In this study, commercial PTFE membrane and Ti/MgF2 photothermal layers were combined without any binder. Ar plasma pretreatment was applied to a membrane surface before depositing optimized Ti/MgF2 stacks to fabricate a mechanically robust photothermal membrane. The successful fabrication of Ar plasma pretreated Ti/MgF2 photothermal membrane was demonstrated by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), atomic force microscope (AFM) characterization. Through Ar plasma pretreatment, an increase in Ti/MgF2 photothermal membrane heating temperature of 40.5 % was achieved under 1 sun condition compared with unpretreated membrane. This membrane showed improved performance and reduced energy loss in solar desalination. Utilizing these membranes in a membrane distillation system, water flux increased by up to 26.9 %, performance ratio (PR) increased by 18.9 % and thermal efficiency improved by 21.9 %. After 24-h stress test, the Ar plasma pretreated Ti/MgF2 photothermal membranes demonstrated durability and maintained thermal efficiency.

Hydrophobic Coatings with Charge Permeability via Plasma Deposition of Long-Chain Perfluorocarbons.

Hydrophobization of nanotextured catalyst materials is a promising route to enhance the yield of N2 and CO2 conversion into green fuels. However, these applications require a hydrophobic coating to not only promote air trapping but also allow charge transfer at the electrode-electrolyte interface. In this work, nano thin films with thicknesses as low as 7 nm were deposited from the plasma phase of perfluorohexene, perfluorodecene, and perfluorooctane (PFO) precursors using a mild vacuum and gentle powers. Atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) characterization reveal that the resulting films are conformal and hydrophobic thanks to a good retention of CF2 and CF3 moieties. The PFO films exhibited the highest water contact angle and achieved superhydrophobic states when deposited on top of re-entrant nano features, an indication of successful air trapping. Electrochemical studies further demonstrated that the plasma-deposited PFO films allow charge transfer but could only sustain repeated cyclic voltammetry cycles without losing their hydrophobicity when deposited under optimal conditions. This result indicates that plasma deposition could become a viable route for the hydrophobization of electrocatalysts required to enhance the yield of poorly soluble gas reduction reactions.

Fluorination Modification of Methyl Vinyl Silicone Rubber and Its Compatibilization Effect on Fluorine/Silicone Rubber Composites.

Among numerous rubbers, high-performance rubber composites can be obtained by mixing fluororubber (FKM) with excellent oil resistance and silicone rubber (SiR) with excellent low-temperature resistance. While the difference in polarity between these two kinds of rubbers leads to a reduction in the properties of the composites. To solve the compatibility problem between the two-phase interfaces in FKM/SiR composites, in this research, fluorinated silicone rubbers (MVQ-g-PFDT) of methyl vinyl silicone rubber (MVQ) grafted with 1H,1H,2H,2H-perfluorodecanethiol (PFDT) were prepared via a facile and efficient thiol-ene click reaction, which was then added into FKM/SiR composites. The results showed that the fluorine-containing side chains could effectively inhibit the low-temperature crystallization phenomenon of silicone rubber and further broaden its application ranges in low-temperature environments. The properties of FKM/SiR composites with the addition of MVQ-g-PFDT were significantly improved, with the highest tensile strength of 14.1 MPa and the lowest mass change rate of 6.71% after 48h immersion at 200 °C in IRM903 oil. Additionally, the hydroxyl groups between the fluorine-containing side chains of MVQ-g-PFDT and the surface of silica facilitate the enhancement of the uniform dispersion of fillers. Atomic force microscopy (AFM) characterization results showed a distinct enhancement of the compatibility between the two phases of FKM and SiR. This work would provide further insight into efforts to improve compatibility between rubbers with widely different polarities.

Protein-derived carbon dots as green corrosion inhibitors for carbon steel in sulfuric acid solution

At present, the development of eco-friendly corrosion inhibitors (CIs) is considered an important and attractive method for controlling the corrosion of metals in acidic media. In this study, protein-derived carbon dots (P-CDs) were prepared via hydrothermal reaction using protein as the raw material, and the corrosion inhibition performances of P-CDs for carbon steel (CS) were investigated systematically. The electrochemical test results showed that the corrosion inhibition efficiency of 500 mg/L P-CDs on CS reached 95.1 % in 0.5 M H2SO4, and the corrosion inhibition efficiency was enhanced to 98.1 % after 8 h of immersion time. The composition and characterization of P-CDs was analysed using Fourier Transform Infrared Spectroscopy (FTIR), Ultraviolet Spectroscopy (UV), X-ray Diffraction (XRD) and Transmission Electron Microscopy (TEM). Atomic force microscopy (AFM) and scanning electron microscopy (SEM) characterization showed that the surface of CS with P-CDs was smoother than that without P-CDs, and that P-CDs was able to adsorb on the surface of CS to form a protective layer, thereby inhibiting corrosion. Adsorption studies indicate that P-CDs form a protective layer on the surface of CS through both physisorption and chemisorption. Overall, these findings demonstrate that P-CDs exhibit superior protective effects against the corrosion of CS in 0.5 M H2SO4.

Chiroplasmonic DNA Scaffolded "Fusilli" Structures.

DNA is an ideal template for the design of nanoarchitectures with molecular-like features. Here, we present an optimized assembly strategy for the concatenation of DNA quasi-rings into long scaffolds. Ionic strength, which played a major role during self-assembly, produced the expected high quality only at 15 mM MgCl2. Atomic force microscopy (AFM) characterization showed several micrometer long tubular structures that were used as templates for the positioning of plasmonic nanoparticles (NPs) along a three-dimensional helical path using DNA tethers. As imaged by high-resolution scanning transmission electron microscopy (HR-STEM) and modeled by theoretical calculations, the NPs distributed into a "fusilli" fashion (i.e., a helical pasta shape), displaying chiroptical activity as revealed by a bisignated CD absorption, centered at the plasmon resonance wavelength. The present structures contribute to enrich the ever-developing arena of chiroplasmonic DNA-based nanomaterials and demonstrate that large assemblies are attainable for their future application to develop metamaterials.

De novo design of pH-responsive self-assembling helical protein filaments

Biological evolution has led to precise and dynamic nanostructures that reconfigure in response to pH and other environmental conditions. However, designing micrometre-scale protein nanostructures that are environmentally responsive remains a challenge. Here we describe the de novo design of pH-responsive protein filaments built from subunits containing six or nine buried histidine residues that assemble into micrometre-scale, well-ordered fibres at neutral pH. The cryogenic electron microscopy structure of an optimized design is nearly identical to the computational design model for both the subunit internal geometry and the subunit packing into the fibre. Electron, fluorescent and atomic force microscopy characterization reveal a sharp and reversible transition from assembled to disassembled fibres over 0.3 pH units, and rapid fibre disassembly in less than 1 s following a drop in pH. The midpoint of the transition can be tuned by modulating buried histidine-containing hydrogen bond networks. Computational protein design thus provides a route to creating unbound nanomaterials that rapidly respond to small pH changes.

Deformation mechanisms in the α phase of the Ti-6Al-2Sn-4Zr-2Mo titanium alloy: In situ experiments and simulations

Titanium alloys are widely employed in aerospace applications due to an outstanding combination of properties. The variety of loading conditions and microstructures encountered in industrial components is urging the development of microstructure sensitive modeling capabilities. In particular, reliable predictions require a good knowledge of operating deformation mechanisms. The present study aims at providing a thorough characterization of deformation mechanisms in the near-α Ti-6Al-2Sn-4Zr-2Mo alloy using experiments and simulations. The sequential activation of deformation mechanisms in the α phase was monitored in situ during a tensile test carried out in a scanning electron microscope using a combination of slip traces analysis and electron back-scattered diffraction. Basal slip is activated first, and prismatic slip activity, which proceeds at a higher macroscopic stress level, is needed for a significant creep/relaxation to occur. While little evidence of 〈a〉-type pyramidal slip was found, 〈c + a〉 pyramidal slip involved first-order pyramidal planes and operates at stress levels near or above the 0.2% proof stress. Atomic force microscopy characterization of the features of the different slip modes revealed that 〈a〉 slip is coarser and wavier than 〈c + a〉 slip. Twinning, which is usually neglected in such alloys within this strain regime, was observed to be slip stimulated at a plastic strain as low as 0.5%. Crystal plasticity parameters leading to an accurate simulation of the activation sequence of deformation mechanisms were then determined. For this purpose, critical resolved shear stress values were derived for the different slip and twinning modes using specific approaches and subsequently validated using crystal plasticity simulations based on fast-Fourier transforms.

Polyelectrolyte Platforms with Copper Nanoparticles as a Multifunctional System Aimed at Healing Process Support

(1) Purpose: The aim of the study was to develop a nanocomposite with copper nanoparticles constituting a bacteriostatic surface to maintain human lung cell function. (2) Methods: A polyelectrolyte layer coating that incorporated copper nanoparticles was designed. As a bacteriostatic factor, copper nanoparticles were applied as a colloidal solution of copper nanoparticles (ColloidCuNPs) and a solution of copper nanoparticles (CuNPs). The influence of the polyelectrolytes on selected Gram (+) and Gram (−) strains was examined. The function and morphology of the human adenocarcinoma A549 cell line, comprising human epithelial lung cells cultured in the presence of nanocomposite layer coatings, were evaluated. We applied fluorescence and scanning electron microscopies, as well as flow cytometry, for these studies. Furthermore, the layer coating material was characterized by atomic force microscopy (AFM) and energy dispersive X-ray analysis (EDX). (3) Results: It was observed that the polyelectrolytes polyethyleneimine (PEI) and poly-L-lysine (PLL) did not induce proliferation of the E. coli strain. However, they did induce the proliferation of the S. aureus strain. Due to the effectiveness of the CuNPs against the E. coli strain, CuNPs were selected for further research. The designed coatings of proper NPs shared the sustained function of human lung cells within 10 days of culture. The AFM and EDX characterization confirmed the presence of copper in the layer coating nanomaterial. The presence of CuNPs in polyethyleneimine-based nanocomposite deepened the bacteriostatic effect on E. coli compared with PEI alone. Meanwhile, incorporating CuNPs in PLL allowed A549 cell maintenance but did not exert a bacteriostatic influence on the examined strain. (4) Conclusions: The platform based on polyelectrolytes, incorporated with copper nanoparticles, that ensures the growth and appropriate morphology of the human lung epithelial cells, might be considered an element of a system for medical devices used to maintain the function of human lung cells.

Fabrication of Micro/Nano Dual Needle Structures with Morphological Gradient Based on Two-Photon Polymerization Laser Direct Writing with Proactive Focus Compensation

Micro/nano structures with morphological gradients possess unique physical properties and significant applications in various research domains. This study proposes a straightforward and precise method for fabricating micro/nano structures with morphological gradients utilizing single-voxel synchronous control and a nano-piezoelectric translation stage in a two-photon laser direct writing technique. To address the defocusing issue in large-scale fabrication, a methodology for laser focus dynamic proactive compensation was developed based on fluorescence image analysis, which can achieve high-precision compensation of laser focus within the entire range of the nano-piezoelectric translation stage. Subsequently, the fabrication of micro/nano dual needle structures with morphological gradients were implemented by employing different writing speeds and voxel positions. The minimum height of the tip in the dual needle structure is 80 nm, with a linewidth of 171 nm, and a dual needle total length reaching 200 μm. Based on SEM (scanning electron microscope) and AFM (atomic force microscope) characterization, the dual needle structures fabricated by the method proposed in this study exhibit high symmetry and nanoscale gradient accuracy. Additionally, the fabrication of hexagonal lattice periodic structures assembled from morphological gradient needle structures and the size gradient Archimedean spiral structures validate the capability of the single voxel-based fabrication and proactive focus compensation method for complex gradient structure fabrication.

Label-free electrochemical biosensor for direct detection of Oncostatin M (OSM) inflammatory bowel diseases (IBD) biomarker in human serum

Oncostatin M (OSM) is an interleukin-6 (IL-6) member family cytokine implicated in the pathogenesis of chronic diseases including inflammatory bowel disease (IBD). OSM is a novel diagnostic biomarker over-expressed in the serum of IBD patients. This paper reports on the first electrochemical OSM immunosensor, developed using a multistep fabrication process aimed at covalently immobilizing OSM antibodies on a mixed self-assembled monolayer coated gold working electrode. Cyclic voltammetry, atomic force microscopy (AFM), IR spectroscopy and optical characterizations were used to validate the sensor functionalization protocol. Electrochemical impedance spectroscopy (EIS) measurements were performed to assess the reliability of the immunosensor preparation and to verify the antibody-antigen complexes formation. The label-free immunosensor showed high sensitivity identifying OSM at clinically relevant concentrations (37–1000 pg mL−1) with low detection limit of 2.86 pg mL−1. Both sensitivity and selectivity of the proposed immunosensor were also demonstrated in human serum in the presence of interfering biomarkers, making it an innovative potential platform for the OSM biomarker detection in IBD patients’ serum.

Atomic Force Microscopy Characterization of Reconstituted Protein-DNA Complexes.

Atomic force microscopy is a high-resolution imaging technique useful for observing the structures of biomolecular complexes. This approach provides a straightforward method to characterize the binding behavior of different chromatin architectural proteins and to analyze the increasingly complex structural units assembled on the DNA. The protocol describes the preparation, AFM imaging, and structural analysis of chromatin that is reconstituted in vitro using purified proteins and DNA. Here, we describe the successful application of the method on the chromatin architectural proteins of the archaeon Sulfolobus solfataricus.