Single Molecular Layer Research Articles

Topological phases in double layers of bismuthene and antimonene

Two-dimensional topological insulators show great promise for spintronic applications. Much attention has been placed on single atomic or molecular layers, such as bismuthene. The selections of such materials are, however, limited. To broaden the base of candidate materials with desirable properties for applications, we report herein an exploration of the physics of double layers of bismuthene and antimonene. The electronic structure of a film depends on the number of layers, and it can be modified by epitaxial strain, by changing the effective spin–orbit coupling strength, and by the manner in which the layers are geometrically stacked. First-principles calculations for the double layers reveal a number of phases, including topological insulators, topological semimetals, Dirac semimetals, trivial semimetals, and trivial insulators. Their phase boundaries and the stability of the phases are investigated. The results illustrate a rich pattern of phases that can be realized by tuning lattice strain and effective spin–orbit coupling.

Investigation on mechanism of phosphate removal on carbonized sludge adsorbent

For the removal of phosphate (PO43−) from water, an adsorbent was prepared via carbonization of sewage sludge from a wastewater treatment plant: carbonized sludge adsorbent (CSA). The mechanism of phosphate removal was determined after studying the structure and chemical properties of the CSA and its influence on phosphate removal. The results demonstrate that phosphate adsorption by the CSA can be fitted with the pseudo second-order kinetics and Langmuir isotherm models, indicating that the adsorption is single molecular layer adsorption dominated by chemical reaction. The active sites binding phosphate on the surface are composed of mineral particles containing Si/Ca/Al/Fe. The mineral containing Ca, calcite, is the main factor responsible for phosphate removal. The phosphate removal mechanism is a complex process including crystallization via the interaction between Ca2+ and PO43−; formation of precipitates of Ca2+, Al3+, and PO43−; and adsorption of PO43− on some recalcitrant oxides composed of Si/Al/Fe.

Photoexcited State Confinement in Two-Dimensional Crystalline Anthracene Monolayer at Room Temperature.

Organic thin film electronics place a high demand on bottom-up technology to form a two-dimensionally (2D) functional unit consisting of a single molecular crystalline layer bound to a layered structure. As the strong interaction between a substrate and molecules makes it difficult to evaluate the electronic properties of organic films, the nature of electronic excited states has not been elucidated. Here, we study a 2D crystalline anthracene monolayer electronically decoupled by alkanethiolates on a gold substrate using scanning tunneling microscopy and time-resolved two-photon photoemission spectroscopy and unravel the geometric/electronic structures and excited electron dynamics. Our data reveal that dispersive 2D excited electrons on the surface can be highly coupled with an annihilation of nondispersive excitons that facilitate electron emission with vibronic interaction. Our results provide a fundamental framework for understanding photoexcited anthracene monolayer and show how the coupling between dispersive and nondispersive excited states may assist charge separation in crystalline molecular layers.

HFB7 – A novel orphan hydrophobin of the Harzianum and Virens clades of Trichoderma, is involved in response to biotic and abiotic stresses

Hydrophobins are small secreted cysteine-rich proteins exclusively found in fungi. They are able to self-assemble in single molecular layers at hydrophobic-hydrophilic interfaces and can therefore be directly involved in establishment of fungi in their habitat. The genomes of filamentous mycotrophic fungi Trichoderma encode a rich diversity of hydrophobins, which are divided in several groups based on their structure and evolution. Here we describe a new member of class II hydrophobins, HFB7, that has a taxonomically restricted occurrence in Harzianum and Virens clades of Trichoderma. Evolutionary analysis reveals that HFB7 proteins form a separate clade distinct from other Trichoderma class II hydrophobins and that genes encoding them evolve under positive selection pressure. Homology modelling of HFB7 structure in comparison to T. reesei HFB2 reveals that the two large hydrophobic patches on the surface of the protein are remarkably conserved between the two hydrophobins despite significant difference in their primary structures. Expression of hfb7 gene in T. virens increases at interactions with other fungi and a plant and in response to a diversity of abiotic stress conditions, and is also upregulated during formation of aerial mycelium in a standing liquid culture. This upregulation significantly exceeds that of expression of hfb7 under a strong constitutive promoter, and T. virens strains overexpressing hfb7 thus display only changes in traits characterized by low hfb7 expression, i.e. faster growth in submerged liquid culture. The hfb7 gene is not expressed in conidia. Our data allow to conclude that this protein is involved in defence of Trichoderma against a diversity of stress factors related to the oxidative stress. Moreover, HFB7 likely helps in the establishment of the fungus in wetlands or other conditions related to high humidity.

Novel molecular design of culture substrates with amino acids

PurposeBiocompatible and bioactive substrates are important in tissue engineering. The nature of these substrates can directly influence cellular response, ultimately affecting the rate and quality of new tissue formation. A novel atomic layer deposition/molecular layer deposition (ALD/MLD) technique was used to build cell culture substrates to do a preliminary assessment of this techniques’ potential within ocular surface tissue engineering.MethodsOrganic‐inorganic hybrid substrates were prepared with ALD/MLD, which enables deposition of single molecular layers of compounds in a very controlled manner. The substrates are based on amino acids, including lysine, arginine, glycine and aspartic acid, as organic building blocks and titanium as inorganic building blocks. Human corneal epithelial cells were cultured on the substrates for 7 days. The cells were then stained with Hoechst and imaged at 5× magnification with a fluorescence microscope. The number of cell nuclei per field of view was counted to compare cell density. In parallel, cells were also stained with trypan blue to assess the number of dead cells.ResultsConfluent cultures were obtained on all substrates and most of the cells were alive. Substrates with glycine and titanium oxide yielded the highest cell density (1,031 cells ± 65), whereas substrates with aspartic acid and titanium oxide (689 cells ± 48) gave rise to the least number of cells.ConclusionsHuman corneal epithelial cells can be successfully grown on organic‐inorganic hybrid substrates while retaining high viability. The novel ALD/MLD technique can be used to build biocompatible substrates using molecular design and further studies should be conducted to evaluate if this technique can be used to direct cell and tissue development.

Adsorption Behavior of p-hydroxy Biphenyl onto Sediment of the Yellow River in Lanzhou

In order to study the adsorption behavior of organic pollutants in sediment of the Yellow River in Lanzhou, p-hydroxy biphenyl (PHB) was selected as the typical organic pollutants to understand the adsorption kinetics and thermodynamics of PHB onto sediment of the Yellow River in Lanzhou based on the batch experiments. Meanwhile, the effects of systemic temperature, such as the particle size, the initial concentration of PHB, pH value, and the ionic strength, were also investigated for the adsorption of PHB onto sediment of the Yellow River. The results indicated that the adsorption kinetics of PHB onto sediment of the Yellow River could be better described by Pseudo-second-order model, and the boundary layer and intraparticle diffusion were both involved in the adsorption kinetic process. The adsorption thermodynamics of PHB onto sediment of the Yellow River were fitted well with the Langmuir model(R2>0.974), which was a single molecular layer adsorption process. The average adsorption free energy E ranged from 0.913 to 1.00 kJ·mol-1 when the systemic temperatures increased from 25℃ to 45℃, suggesting a physical adsorption. Thermodynamic parameter analysis indicated that Gibbs free energy (ΔGθ) and Entropy (ΔHθ) were less than zero, but Enthalpy (ΔSθ) was more than zero in the adsorption process, which tended to prove the spontaneous nature of the adsorption process, the endothermic nature of the adsorption process and the increased randomness at the sediment surface. Furthermore, the smaller the particle size, the greater the adsorption capacity of the PHB. The adsorption capacity was increased with the increase of the initial concentration of PHB. When the pH value in a range of 4.23 to 7.00, the adsorption capacity of PHB showed a slow decreasing trend, while the decreasing was sharp when pH value was greater than 7.00, and the adsorption capacity was almost zero when pH value was about 10.3. With the increase of ionic strength, the adsorption amount of PHB was also increased, but when the ionic strength increased to a certain value, due to the competitive adsorption, the adsorption of PHB onto sediments would be inhibited, resulting in decreased amount of adsorption.

Modelling of particle-laden flow inside nanomaterials.

In this paper, we demonstrate the usage of the Nernst-Planck equation in conjunction with mean-field theory to investigate particle-laden flow inside nanomaterials. Most theoretical studies in molecular encapsulation at the nanoscale do not take into account any macroscopic flow fields that are crucial in squeezing molecules into nanostructures. Here, a multi-scale idea is used to address this issue. The macroscopic transport of gas is described by the Nernst-Planck equation, whereas molecular interactions between gases and between the gas and the host material are described using a combination of molecular dynamics simulation and mean-field theory. In particular, we investigate flow-driven hydrogen storage inside doubly layered graphene sheets and graphene-oxide frameworks (GOFs). At room temperature and with slow velocity fields, we find that a single molecular layer is formed almost instantaneously on the inner surface of the graphene sheets, while molecular ligands between GOFs induce multi-layers. For higher velocities, multi-layers are also formed between graphene. For even larger velocities, the cavity of graphene is filled entirely with hydrogen, whereas for GOFs there exist two voids inside each periodic unit. The flow-driven hydrogen storage inside GOFs with various ligand densities is also investigated.

Quantitative resonant soft x-ray reflectivity of ultrathin anisotropic organic layers: Simulation and experiment of PTCDA on Au.

Resonant soft X-ray reflectivity at the carbon K edge, with linearly polarized light, was used to derive quantitative information of film morphology, molecular arrangement, and electronic orbital anisotropies of an ultrathin 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA) film on Au(111). The experimental spectra were simulated by computing the propagation of the electromagnetic field in a trilayer system (vacuum/PTCDA/Au), where the organic film was treated as an anisotropic medium. Optical constants were derived from the calculated (through density functional theory) absorption cross sections of the single molecule along the three principal molecular axes. These were used to construct the dielectric tensor of the film, assuming the molecules to be lying flat with respect to the substrate and with a herringbone arrangement parallel to the substrate plane. Resonant soft X-ray reflectivity proved to be extremely sensitive to film thickness, down to the single molecular layer. The best agreement between simulation and experiment was found for a film of 1.6 nm, with flat laying configuration of the molecules. The high sensitivity to experimental geometries in terms of beam incidence and light polarization was also clarified through simulations. The optical anisotropies of the organic film were experimentally determined and through the comparison with calculations, it was possible to relate them to the orbital symmetry of the empty electronic states.

Role of Sub-Nanometer Dielectric Roughness on Microstructure and Charge Carrier Transport in α,ω-Dihexylsexithiophene Field-Effect Transistors

The effect of dielectric roughness on the microstructure evolution of thermally evaporated α,ω-dihexylsexithiophene (α,ω-DH6T) thin films from a single molecular layer to tens of monolayers (ML) is studied. Thereby, the surface roughness of dielectrics is controlled within a sub-nanometer range. It is found that the grain size of an α,ω-DH6T ML is affected by dielectric roughness, especially for 1.5 ML, whereby the transistor performance is barely influenced. This can be attributed to a domain interconnection in the second layer over a long-range formed on the rough surface. With deposition of more layers, both microstructure and charge carrier transport exhibit a roughness-independent behavior. The structural characterization of α,ω-DH6T 10 ML by grazing-incidence wide-angle X-ray scattering reveals that the interlayer distance is slightly decreased from 3.30 to 3.15 nm due to a higher roughness, while an unchanged π-stacking distance is in excellent agreement with the roughness-independent hole mobility. This study excludes the influence of molecular-solvent interaction and preaggregation taking place during solution deposition, and provides further evidence that the microstructure of the interfacial layer of organic semiconductors has only minor impact on the bulk charge carrier transport in thicker films.

STM study of PTCDA on Sn/Si(111)-2√3×2√3.

The electronic structures of perylene tetracarboxylic dianhydride on Sn/Si(111)-2√3×2√3 have been studied by scanning tunneling microscopy and spectroscopy. Individual molecules have been investigated at 0.15 ML, while at 0.3 ML molecules formed short rods. At 0.6 ML, the molecular rods interacted with each other, coupling with the substrate and forming a new 4√3×2√3 super structure. At 0.9 ML, the surface was further reconstructed and consisted of strips with two and three rods of molecules. We found that these surface structures are strongly modified by the molecule/substrate and the intermolecular interactions. As a result, the HOMO-LUMO gaps of these molecules change with respect to the phases and the thickness. For a single molecular layer of the 4√3×2√3 phase, the HOMO-LUMO levels were split with a gap of approximately 2.1 eV, which is caused by charge transfer from the substrate to the molecules.

Modulation of Domain Size in Polycrystalline n-Type Dicyanoperylene Mono- and Bilayer Transistors.

A single molecular layer (monolayer) of organic semiconductors is proven to be sufficient to create a conducting channel for charge carriers in field-effect transistors, which is an ideal platform to investigate the correlation between molecular self-assembly and device performance. Herein, ultrathin films including mono- and bilayers of an n-type dicyanoperylene (PDI8-CN2) are solution-processed by dip-coating. The domain size of the polycrystalline layers is modulated via the surface roughness of the dielectric within an extremely narrow window from 0.15 to 0.39 nm. When the surface roughness is varied from smooth to rough, the domain size and molecular order in the monolayer are significantly decreased, leading to the reduction in electron mobility by 3 orders of magnitude. On the contrary, a lower roughness dependence is observed in the case of the bilayers, with only a slight difference in domain size and charge carrier transport. On the smooth surface, the bilayers exhibit a transistor performance identical to that of the bulk film, confirming that the first few layers near the dielectric dominate the charge carrier transport. Additionally, these results provide insights into the intrinsic role of the interfacial microstructure of small molecular organic semiconductors.

Charge density wave transition in single-layer titanium diselenide.

A single molecular layer of titanium diselenide (TiSe2) is a promising material for advanced electronics beyond graphene—a strong focus of current research. Such molecular layers are at the quantum limit of device miniaturization and can show enhanced electronic effects not realizable in thick films. We show that single-layer TiSe2 exhibits a charge density wave (CDW) transition at critical temperature TC=232±5 K, which is higher than the bulk TC=200±5 K. Angle-resolved photoemission spectroscopy measurements reveal a small absolute bandgap at room temperature, which grows wider with decreasing temperature T below TC in conjunction with the emergence of (2 × 2) ordering. The results are rationalized in terms of first-principles calculations, symmetry breaking and phonon entropy effects. The observed Bardeen-Cooper-Schrieffer (BCS) behaviour of the gap implies a mean-field CDW order in the single layer and an anisotropic CDW order in the bulk.

An Electrically Driven and Readable Molecular Monolayer Switch Based on a Solid Electrolyte.

The potential application of molecular switches as active elements in information storage has been demonstrated through numerous works. Importantly, such switching capabilities have also been reported for self-assembled monolayers (SAMs). SAMs of electroactive molecules have recently been exploited as electrochemical switches. Typically, the state of these switches could be read out through their optical and/or magnetic response. These output reading processes are difficult to integrate into devices, and furthermore, there is a need to use liquid environments for switching the redox-active molecular systems. In this work, both of these challenges were overcome by using an ionic gel as the electrolyte medium, which led to an unprecedented solid-state device based on a single molecular layer. Moreover, electrochemical impedance has been successfully exploited as the output of the system.

An Electrically Driven and Readable Molecular Monolayer Switch Based on a Solid Electrolyte

AbstractThe potential application of molecular switches as active elements in information storage has been demonstrated through numerous works. Importantly, such switching capabilities have also been reported for self‐assembled monolayers (SAMs). SAMs of electroactive molecules have recently been exploited as electrochemical switches. Typically, the state of these switches could be read out through their optical and/or magnetic response. These output reading processes are difficult to integrate into devices, and furthermore, there is a need to use liquid environments for switching the redox‐active molecular systems. In this work, both of these challenges were overcome by using an ionic gel as the electrolyte medium, which led to an unprecedented solid‐state device based on a single molecular layer. Moreover, electrochemical impedance has been successfully exploited as the output of the system.

Structural Investigations of Self-Assembled Monolayers for Organic Electronics: Results from X-ray Reflectivity

Self-assembled monolayers (SAMs) have been established as crucial interlayers and electronically active layers in organic electronic devices, such as organic light emitting diodes (OLEDs), organic photovoltaics (OPVs), organic thin film transistors (OTFTs), and nonvolatile memories (NVMs). The use of self-assembling functionalized organic molecules is beneficial due to mainly three advantages compared with common thin film deposition approaches. (1) Molecular self-assembly occurs with surface selectivity, determined by the interaction between the functional anchor group of the organic molecules and the target surface. (2) The film thickness of the resulting layers is perfectly controllable on the angstrom scale, due to the self-terminating film formation to only a single molecular layer. And finally, (3) the wide variability in the chemical structure of such molecules enables different SAM functionalities for devices, ranging from electrical insulation to charge storage to charge transport. The SAM approach can be further expanded by employing several functionalized molecules to create mixed SAMs with consequently mixed properties. The function of SAMs in devices depends not only on the chemical structure of the molecules but also on their final arrangement and orientation on the surface. A reliable and nondestructive in-depth characterization of SAMs on nonconductive oxide surfaces is still challenging because of the very small thickness and the impracticality of methods such as scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). In this Account, we illustrate how X-ray reflectivity (XRR) provides analytical access to major questions of SAM composition, morphology, and even formation by means of investigations of pure and mixed SAMs based on phosphonic acids (PAs) of various chain structures on flat alumina (AlOx) surfaces. XRR is an analytical method that provides access to spatially averaged structural depth profiles over a relatively large area of several square micrometers. The key outcome of XRR, the surface-normal electron density profile of the SAMs, leads to precise information on the SAM thickness with subangstrom resolution and allows for the determination of molecular tilt angles and packing densities. We have systematically increased the chemical complexity of PA molecules and the resulting SAMs, utilizing XRR to provide insight into the SAM structures. In SAMs composed of functionalized molecules or complex chain structures, the distribution of electron rich and electron poor signatures is detected and thus the molecular order within the SAM is determined. In mixed SAMs of two different molecular species, electron density profiles reveal the morphology and how the surface-normal structure changes if one component of the mixed SAM is altered. Furthermore, XRR was applied to investigate in situ the self-assembly of functionalized PA molecules from solution by tracking the monolayer growth over time. Even though the results provided by XRR on in-plane molecular arrangement are limited, it presents excellent information on the molecular scale along the surface normal and in addition allows for drawing conclusions on the intermolecular interactions within the SAM.

Large-Scale Diffusion of Entangled Polymers along Nanochannels.

Changes in large-scale polymer diffusivity along interfaces, arising from transient surface contacts at the nanometer scale, are not well understood. Using proton pulsed-gradient NMR, we here study the equilibrium micrometer-scale self-diffusion of poly(butadiene) chains along ∼100 μm long, 20 and 60 nm wide channels in alumina, which is a system without confinement-related changes in segmental relaxation time. Unlike previous reports on nonequilibrium start-up diffusion normal to an interface or into particulate nanocomposites, we find a reduction of the diffusivity that appears to depend only upon the pore diameter but not on the molecular weight in a range between 2 and 24 kg/mol. We rationalize this by a simple volume-average model for the monomeric friction coefficient, which suggests a 10-fold surface-enhanced friction on the scale of a single molecular layer. Further support is provided by applying our model to the analysis of published data on large-scale diffusion in thin films.

The remarkable activity and stability of a dye-sensitized single molecular layer MoS2 ensemble for photocatalytic hydrogen production.

Single layer MoS2 synthesized by exfoliation with Li is demonstrated to take up the dye molecule, Eosin Y, with strong binding affinity via sulfur vacancies. This dye-sensitized single layer MoS2 ensemble exhibits remarkable activity and stability for photocatalytic hydrogen production from water.

Transmission mode of a single layer graphene and its performance in the detection of the vibration spectrum of gas molecular

Since its successful preparation in 2004, graphene has attracted a great deal of attention, and the sensing application is an important research field. But nearly all the researches about graphene sensors focus on low frequency band, of which the mechanism is mainly dependent on the detection of charge carrier concentration and conductivity variation induced by the absorption of molecules. However, due to the fact that most of the molecules absorbed on the surface of graphene will induce the change of conductivity, this method is incapable of distinguishing different molecules. Transmission mode of a single molecular layer is studied based on Kubo formula and combined with a numerical method. The relation between transmission properties and effective mode index is analyzed, and the broadband localization capability of the waveguide mode is demonstrated. Meanwhile, the variation of the transmission intensity which is due to the interaction between the first order waveguide mode and the gas is adopted to retrieve the vibration spectrum of molecules. Taking the sensing of SO2, CO and C7H8 as examples, the effectiveness of this method is verified based on eigenmode analysis. Results show that the transmission spectrum is consistent with the variation spectrum of gas molecules; besides, in the transmission direction, the larger the interaction range, the greater the attenuation of mode transmission intensity will be. This study has provided a theoretical foundation for the realization of the detection and identification of gas moleculan fingerprints.

Observation of piezoelectricity in free-standing monolayer MoS₂.

Piezoelectricity allows precise and robust conversion between electricity and mechanical force, and arises from the broken inversion symmetry in the atomic structure. Reducing the dimensionality of bulk materials has been suggested to enhance piezoelectricity. However, when the thickness of a material approaches a single molecular layer, the large surface energy can cause piezoelectric structures to be thermodynamically unstable. Transition-metal dichalcogenides can retain their atomic structures down to the single-layer limit without lattice reconstruction, even under ambient conditions. Recent calculations have predicted the existence of piezoelectricity in these two-dimensional crystals due to their broken inversion symmetry. Here, we report experimental evidence of piezoelectricity in a free-standing single layer of molybdenum disulphide (MoS₂) and a measured piezoelectric coefficient of e₁₁ = 2.9 × 10(-10) C m(-1). The measurement of the intrinsic piezoelectricity in such free-standing crystals is free from substrate effects such as doping and parasitic charges. We observed a finite and zero piezoelectric response in MoS₂ in odd and even number of layers, respectively, in sharp contrast to bulk piezoelectric materials. This oscillation is due to the breaking and recovery of the inversion symmetry of the two-dimensional crystal. Through the angular dependence of electromechanical coupling, we determined the two-dimensional crystal orientation. The piezoelectricity discovered in this single molecular membrane promises new applications in low-power logic switches for computing and ultrasensitive biological sensors scaled down to a single atomic unit cell.

Self-assembled alkanethiol monolayers on gold surfaces: resolving the complex structure at the interface by STM.

The surface properties of metals and metal oxides can be modified by adding a single layer of organic molecules. A most popular route for depositing such a molecular layer is via the formation of self-assembled monolayers (SAMs). The molecules that form SAMs have a functionality which binds to the surface and the adsorption is self-regulated to terminate at exactly one single molecular layer. The very first example, which has become the most widely studied system, of SAMs on metal surfaces consists of chemisorbed alkylthiolate on gold. Despite the simplicity in the preparation of alkanethiol SAMs and the seemingly straightforward structure of such SAMs, the detailed bonding between the sulfur head group and gold is still subject to debate. Experimental and theoretical effort in the last six years has led to a much improved understanding of this classical system of SAMs. In this review, we will highlight the most recent progress in the study of the interfacial structure of alkanethiol SAMs on gold. We focus on the important phenomenon of phase transition that occurs from n-propanethiol to n-butanethiol, and propose a unified structural model to explain how the (3 × 4) phase for short chain alkanethiol monolayers (methyl-, ethyl- and propylthiolate monolayers) changes into the (3 × 2√3)-rect./c(4 × 2) phase for long chain molecular monolayers.