STM Study of the Self-Assembly of Biphenyl-3,3',5,5'-Tetracarboxylic Acid and Its Mixing Behavior with Coronene at the Liquid-Solid Interface.

We report a scanning tunneling microscopy (STM) study of the molecular self-assembly of biphenyl-3,3',5,5'-tetracarboxylic acid (BPTC) at the octanoic acid/graphite interface. STM revealed that the BPTC molecules generated stable bilayers and monolayers under high and low sample concentrations, respectively. Besides hydrogen bonds, the bilayers were stabilized by molecular π-stacking, whereas the monolayers were maintained by solvent co-adsorption. A thermodynamically stable Kagomé structure was obtained upon mixing BPTC with coronene (COR), while kinetic trapping of COR in the co-crystal structure was found by the subsequent deposition of COR onto a preformed BPTC bilayer on the surface. Force field calculation was conducted to compare the binding energies of different phases, which helped to provide plausible explanations for the structural stability formed via kinetic and thermodynamic pathways.

A Paradigm Shift from 2D to 3D: Surface Supramolecular Assemblies and Their Electronic Properties Explored by Scanning Tunneling Microscopy and Spectroscopy.

Exploring supramolecular architectures at surfaces plays an increasingly important role in contemporary science, especially for molecular electronics. A paradigm of research interest in this context is shifting from 2D to 3D that is expanding from monolayer, bilayers, to multilayers. Taking advantage of its high-resolution insight into monolayers and a few layers, scanning tunneling microscopy/spectroscopy (STM/STS) turns out a powerful tool for analyzing such thin films on a solid surface. This review summarizes the representative efforts of STM/STS studies of layered supramolecular assemblies and their unique electronic properties, especially at the liquid-solid interface. The superiority of the 3D molecular networks at surfaces is elucidated and an outlook on the challenges that still lie ahead is provided. This review not only highlights the profound progress in 3D supramolecular assemblies but also provides researchers with unusual concepts to design surface supramolecular structures with increasing complexity and desired functionality.

Surface supramolecular assemblies tailored by chemical/physical and synergistic stimuli: a scanning tunneling microscopy study.

Supramolecular self-assemblies formed by various non-covalent interactions can produce diverse functional networks on solid surfaces. These networks have recently attracted much interest from both fundamental and application points of view. Unlike covalent organic frameworks (COFs), the properties of the assemblies differ from each other depending on the constituent motifs. These various motifs may find diverse applications such as in crystal engineering, surface modification, and molecular electronics. Significantly, these interactions between/among the molecular tectonics are relatively weak and reversible, which makes them responsive to external stimuli. Moreover, for a liquid-solid-interface environment, the dynamic processes are amenable to in situ observation using scanning tunneling microscopy (STM). In the literature, most review articles focus on supramolecular self-assembly interactions. This review summarizes the recent literature in which stimulation sources, including chemical, physical, and their combined stimuli, cooperatively tailor supramolecular assemblies on surfaces. The appropriate design and synthesis of functional molecules that can be integrated on different surfaces permits the use of nanostructured materials and devices for bottom-up nanotechnology. Finally, we discuss synergic effect on materials science.

Flow-induced-crystallization: tailoring host-guest supramolecular co-assemblies at the liquid-solid interface.

Here, we report that using the method of simply contacting a sample solution droplet with a piece of tissue paper can create a solvent flow (capillary force). During this process, the dynamics and solvent removal can promote the formation and stabilization of a meta-stable linear quasi-crystal composed of p-terphenyl-3,5,3',5'-tetracarboxylic acid (TPTC) molecules, which would otherwise pack into thermodynamically favored random tiling. The tailored quasi-crystal (linear) template allows atop it higher-efficiency accommodation of fullerene molecules (C60) from 40.1% to 97.5%, compared with that obtained in the random-tiling (porous) case. Overall, the result of this study presents an unusual yet remarkably simple strategy for tailoring complex host-guest supramolecular systems at the liquid-solid interface.

An Assessment of MXenes through Scanning Probe Microscopy.

Recently, exploring the unique properties of 2D materials has constituted a new wave of research, which lead these materials to enormous applications ranging from optoelectronics to healthcare systems. Due to the profusion of surface terminated functionalities, MXenes have become an emerging class of 2D materials that can be easily integrated with other materials. The versatility of MXenes allows to tune their finest material properties for further device applications. This review initiates with the classification of preparation methods of MXenes, where the authors elaborate on the significance of top-down approaches including the exfoliation of solid layers. Next, the focus is diverted toward the materials analysis of MXenes including their terminations analysis as well as their intriguing electrical and mechanical behaviors through scanning probe microscopy. Finally, critical challenges and perspectives for MXenes analysis and applications are explored and discussed. Therefore, this comprehensive review can encourage researchers, and offer a precise direction to employ MXenes in various applications.

Odd-Even Effect on Supramolecular Co-Assemblies: Control over the Two-Dimensional Self-Assemblies of a Fluorenone Derivative with Asymmetrically Substituted Alkyl Chains.

The precise control of two-dimensional supramolecular co-assemblies presents a research topic related to advance nanotechnology. Here, we report a scanning tunneling microscopy (STM) study of the mixture behavior of three fluorenone derivatives at the liquid-solid interface. The target molecule is F-C12C13 whose structure bears asymmetrical alkyls, whereas the regulating molecules, either F-C12C12 or F-C13C13, are structurally symmetric. By STM imaging of systematic mixtures with various volumes among the sample solutions, we found that the mixing ratio mainly determined the binary outcomes. Compared with F-C12C12, F-C13C13 shows a stronger ability to dominate the patterning, explained by the larger binding and adsorption energies calculated by the force field simulations. Moreover, the odd-even effect exists in the system. Overall, we acquired knowledge about the regulating ability of bi-component supramolecular assembling, especially for structurally asymmetric molecular systems.

Monolayer and Bilayer Formation of Molecular 2D Networks Assembled at the Liquid/Solid Interfaces by Solution-Based Drop-Cast Method.

In recent years, extending self-assembled structures from two-dimensions (2D) to three-dimensions (3D) has been a paradigm in surface supramolecular chemistry and contemporary nanotechnology. Using organic molecules of p-terphenyl-3,5,3',5'-tetracarboxylic acid (TPTC), and scanning tunneling microscopy (STM), we present a simple route, that is the control of the solute solubility in a sample solution, to achieve the vertical growth of supramolecular self-assemblies, which would otherwise form monolayers at the organic solvent/graphite interface. Presumably, the bilayer formations were based on π-conjugated overlapped molecular dimers that worked as nuclei to induce the yielding of the second layer. We also tested other molecules, including trimesic acid (TMA) and 1,3,5-tris(4-carboxyphenyl)-benzene (BTB), as well as the further application of our methodology, demonstrating the facile preparation of layered assemblies.

Supramolecular Chemistry: Host-Guest Molecular Complexes.

In recent times, researchers have emphasized practical approaches for capturing coordinated and selective guest entrap. The physisorbed nanoporous supramolecular complexes have been widely used to restrain various guest species on compact supporting surfaces. The host-guest (HG) interactions in two-dimensional (2D) permeable porous linkages are growing expeditiously due to their future applications in biocatalysis, separation technology, or nanoscale patterning. The different crystal-like nanoporous network has been acquired to enclose and trap guest molecules of various dimensions and contours. The host centers have been lumped together via noncovalent interactions (such as hydrogen bonds, van der Waals (vdW) interactions, or coordinate bonds). In this review article, we enlighten and elucidate recent progress in HG chemistry, explored via scanning tunneling microscopy (STM). We summarize the synthesis, design, and characterization of typical HG structural design examined on various substrates, under ambient surroundings at the liquid-solid (LS) interface, or during ultrahigh vacuum (UHV). We emphasize isoreticular complexes, vibrant HG coordination, or hosts functional cavities responsive to the applied stimulus. Finally, we critically discuss the significant challenges in advancing this developing electrochemical field.

Substrate Impact on MR Characteristics of Carbon Nano Films Explored via AFM and Raman Analysis.

Recent advances in the fabrication and classification of amorphous carbon (a-Carbon) thin films play an active part in the field of surface materials science. In this paper, a pulsed laser deposition (PLD) technique through controlling experimental parameters, including deposition time/temperature and laser energy/frequency, has been employed to examine the substrate effect of amorphous carbon thin film fabrication over SiO2 and glass substrates. In this paper, we have examined the structural and magnetoresistance (MR) properties of these thin films. The intensity ratio of the G-band and D-band (ID/IG) were 1.1 and 2.4, where the C(sp2) atomic ratio for the thin films samples that were prepared on glass and SiO2 substrates, were observed as 65% and 85%, respectively. The MR properties were examined under a magnetic field ranging from -9 T to 9 T within a 2-K to 40-K temperature range. A positive MR value of 15% was examined at a low temperature of 2 K for the thin films grown on SiO2 substrate at a growth temperature of 400 °C using a 300 mJ/pulse laser frequency. The structural changes may tune the magnetoresistance properties of these a-Carbon materials. These results were demonstrated to be highly promising for carbon-based spintronics and magnetic sensors.

Recent progress in hybrid perovskite solar cells through scanning tunneling microscopy and spectroscopy.

Currently, sustainable renewable energy sources are urgently required to fulfill the cumulative energy needs of the world's 7.8 billion population, since the conventional coal and fossil fuels will be exhausted soon. Photovoltaic devices are a direct and efficient means to produce a huge amount of energy to meet these energy targets. In particular, hybrid-perovskite-based photovoltaic devices merit special attention not only due to their exceptional efficiency for generating appreciable energy but also their tunable band gaps and the ease of device fabrication. However, the commercialization of such devices suffers from the instability of the compositional materials. The cause of instability is the perovskite's structure and its morphology at the sub-molecular level; thereby revealing and eliminating these instabilities are a striking challenge. To address this issue, scanning tunneling microscopy/spectroscopy (STM/STS) presents a comprehensive method to allow the visualization of the morphology and electronic structure of materials at atomic-level resolution. Here, we review the recent developments of perovskite-based solar cells (PSCs), the STM/STS analysis of photoactive halide/hybrid and oxide materials, and the real-time STM/STS investigation of electronic structures with defects and traps that are believed to mainly affect device performances. The detailed STM/STS analysis can facilitate a better understanding of the properties of materials at the nanoscale. This informative study may hold great promise to advance the development of stable PSCs under atmospheric conditions.

Electric-field-induced supramolecular phase transitions at the liquid/solid interface: cat-assembly from solvent additives.

We demonstrate by using scanning tunneling microscopy that a series of trace organic solvent additives can efficiently promote the electrically triggered phase transition of trimesic acid (TMA), which would otherwise occur rather sporadically. DFT simulations taking into account the electric field effect elucidate such tailored phase transformations, based on the Gibbs activation and free energies of the deprotonation reactions of TMA.

Nanoscale tailoring of supramolecular crystals via an oriented external electric field.

The oriented external electric field of a scanning tunneling microscope (STM) has recently been adapted for controlling the chemical reaction and supramolecular phase transition at surfaces with molecular precision. However, to date, advance controls using such electric-fields for crystal engineering have not been achieved yet. Here, we present how the directional electric-field of an STM can be utilized to harness supramolecular crystallization on a solid surface. We show that a glass-like random-tiling assembly composed of p-terphenyl-3,5,3',5'-tetracarboxylic acid can transform into close-packed periodic assemblies under positive substrate bias conditions at the liquid/solid interface. Importantly, the nucleation and subsequent crystal growth for such field-induced products can be artificially tailored at the early stage in a real-time fashion. Through this method, we were able to produce a two-dimensional supramolecular single crystal. The as-prepared crystals with apparent brightness are ascribed to a spectroscopic feature linked to the electron density of states, which is thus strongly STM bias dependent.

One-step preparation of single-layered graphene quantum dots for the detection of Fe3.

Single-layer graphene quantum dots are highly desirable while their facile and controllable preparations remain challenging. Herein, single-layered graphene quantum dots (sl-GQDs) were developed via a facile one-step hydrothermal synthesis, with citric acid and ß-cyclodextrin (CD) as starting materials. The sl-GQDs decorated with CD molecules emit green fluorescence with a quantum yield of 5.34%, and exhibit a good response exclusively to ferric ions for their structural oxygenous groups. The linear range of the proposed sensor for ferric ions was found in a wide concentration range of 0-85 µM. The detection limit is about 0.26 µM. The sl-GQDs based sensing platform also demonstrates its feasibility in real water sample analysis with recoveries of 93.8%-101.5%.

Newtonian flow inside carbon nanotube with permeable boundary taking into account van der Waals forces.

Here, water flow inside large radii semi-infinite carbon nanotubes is investigated. Permeable wall taking into account the molecular interactions between water and a nanotube, and the slip boundary condition will be considered. Furthermore, interactions among molecules are approximated by the continuum approximation. Incompressible and Newtonian fluid is assumed, and the Navier-Stokes equations, after certain assumptions, transformations and derivations, can be reduced into two first integral equations. In conjunction with the asymptotic expansion technique, we are able to derive the radial and axial velocities analytically, capturing the effect of the water leakage, where both mild and exceptionally large leakages will be considered. The radial velocity obeys the prescribed boundary condition at the (im)permeable wall. Through the mean of the radial forces, the sufficiently large leakages will enhance the radial velocity at the center of the tube. On the other hand, unlike the classical laminar flow, the axial velocity attains its maximum at the wall due to the coupling effect with the radial forces as water is being pushed into the proximity of the inner wall. In addition, the axial velocity and the flux with the consideration of the suck-in forces, induced by the tubes' entry turn out to be one order higher than that without the suck-in forces. All the aforementioned considerations might partially resolve the mysteriously high water penetration through nanotubes. Axial velocity also drops with the tube's length when the water leakage is permitted and the suck-in forces will ease the decline rate of the axial velocity. The present mathematical framework can be directly employed into the water flow inside other porous nano-materials, where large water leakage is permitted and therefore are of huge practical impact on ultra-filtration and environmental protection.

A continuum study of layer analysis for single species ion transport inside double-layered graphene sheets with various separations.

We investigate the formation of thin ionic layers driven by electro-osmotic forces, that are commonly found in micro- and nano-channels. Recently, multi-layers have been reported in the literature. However, the relation between classical Debye layers and multi-layers, which is a practically and fundamentally important question, was previously unexplained. Here, we fill this gap by using a continuum approach to investigate the flow of lithium ions inside double-layered graphene sheets. Fluid flow, charge conductivity and thermal stability will be investigated. We show that the separation and strength of forces between the sheets, the external electric field and thermal effects determine the topology of the ionic layers between the graphene sheets.

Influence of Zn+2 Doping on Ni-Based Nanoferrites; (Ni1-x ZnxFe2O4).

Nickel zinc nanoferrites (Ni1-xZnxFe2O4) were synthesized via a chemical co-precipitation method having stoichiometric proportion (x) altering from 0.00 to 1.00 in steps of 0.25. The synthesized nanoparticles were sintered at 800 °C for 12 h. X-ray diffraction patterns illustrate that the nanocrystalline cubic spinel ferrites have been obtained after sintering. The Scherrer formula is used to evaluate the particle size using the extreme intense peak (311). The experimental results demonstrate that precipitated particles' size was in the range of 20-60 nm. Scanning electron microscopy (SEM) is used to investigate the elemental configuration and morphological characterizations of all the prepared samples. FTIR spectroscopy data for respective sites were examined in the range of 300-1000 cm-1. The higher frequency band ν1 were assigned due to tetrahedral complexes while lower frequency band ν2 were allocated due to octahedral complexes. Our experimental results demonstrate that the lattice constant a0 increases while lattice strain decreases with increasing zinc substitution in nickel zinc nanoferrites.

Hydrophobic surface modified HfO2 antireflective coatings.

A multifunctional antireflective (AR) thin film is always a prerequisite for growing high-tech applications. Herein we proposed a surface modification technique to transform the hydrophilic behaviour of HfO2 AR nanofilms into hydrophobic without influencing the nanostructure, morphology, refractive index (η) or AR efficacy of HfO2 nanofilms. Our experimental results demonstrate that the fabricated HfO2 AR nanofilms retain its AR efficiency after surface modification to <1% in the visible wavelength range (450-700 nm) on FTO and sapphire. HfO2 AR nanofilms show hydrophilic behaviour before surface modification with a water contact angle (WCA) of 29° on FTO and 22° on sapphire. However, after surface treatment, they display hydrophobic nature θ w > Î¸ > 90° with a contact angle of (127°-130°). The experimental result demonstrates that the η of the thin layers fabricated at deposition angle 0°, 80°, and 88° before and after modification remains almost the same. HfO2 AR nanofilms exhibit long term AR permanency as AR efficiency measured within a year practically displays the equivalent reflectance curves similar to as deposit AR thin films, i.e. <1% in the wavelength range of 450-700 nm. We proposed a cost-effective procedure to make hydrophilic AR films to show non-wetting behaviour for its long-term exposure in a moist, damp environment without affecting the refractive index of AR thin film.

Influence of Refractive Index on Antireflectance Efficiency of Thin Films.

In today's world, scientific development is tremendously strengthened by imitating natural processes. This development remarkably validates progressive and efficient operation of multifunctional thin films in variable ecological circumstances. We use TFCalc thinfilm software, a reliable and trustworthy simulation tool, to design antireflective (AR) coatings for solar cells that can operate in varying environmental conditions and can be functional according to user-defined conditions. Silicon nearly reflects 36% light in the 550 nm wavelength region, causing a significant loss in solar cell efficiency. We used silicon as the substrate on which we designed and fabricated a trilayer inorganic oxide AR thin films, and this reduced it reflectance to <4% in the 300~800 nm wavelength range. Because of their distinguishing physical physiognomies, we used a combination of different inorganic oxides, comprising high-, low-, and medium-refractive indices, to model AR coatings in the desired wavelength range. Experimental implementation of the designed AR thin films in the present study unlocks new techniques for production of competent, wideband-tunable AR coatings that are applicable in high-performance photovoltaic applications.

Synergic Effect: Temperature-Assisted Electric-Field-Induced Supramolecular Phase Transitions at the Liquid/Solid Interface.

Using trimesic acid (TMA) as a model system by means of scanning tunneling microscope (STM) equipped with a temperature controller, here, we report a temperature-assisted method to cooperatively control electric-field-induced supramolecular phase transitions at the liquid/solid interface. Octanoic acid is used as a solvent due to its good solubility for TMA and its less complicated pattern formed under negative STM bias (e.g., only chicken-wire polymorphs existing). At positive substrate bias, STM revealed that TMA assembly based on temperature modulations underwent phase transitions from a porous (22 °C) to a flower (45 °C) and further to a zigzag (68 °C) structure. The transitions are ascribed to the partial deprotonation of the carboxyl groups of TMA. Both the temperature and electrical polarity of the substrate are crucial, i.e., the transitions only take place at positive substrate bias and elevated temperatures. Molecular mechanics simulations were carried out to calculate the temperature and electric field dependence of the adsorption enthalpy and free energy of the chicken-wire assembly of TMA on the two layers of graphene surface. The calculated decrease in adsorption enthalpy with the increase of temperature and electric field values that causes the TMA chicken-wire assembly to be less stable is proposed to promote the occurrence of the phase transition observed by STM. This study paves the way toward program-controlled supramolecular phase switching via the synergic effect of electrical and thermal stimuli.

Superstructure manipulation and electronic measurement of monolayers comprising discotic liquid crystals with intrinsic dipole moment using STM/STS.

In this work, we studied the discotic liquid crystals (DLCs) of dibenzo[a,c]phenazine at the liquid-solid interface using scanning tunnelling microscopy/spectroscopy, by which we show how to tailor the DLC assemblies and in turn their electron-transfer efficiency. This study presents an alternative method for phase control and electronic measurements for DLCs, especially at the microscopic level.