Monolayer Thin Films Research Articles

Regulation of monolayer MgGeN2 thin film with uniaxial and biaxial strain

The regulation of electronic and optical properties with uniaxial and biaxial strain is computationally investigated for the monolayer thin film of a newly discovered quasi-layered MgGeN2 phase. It is found that, under uniaxial compression in both [100] and [010] directions with the perpendicular lattice parameter relaxable, the band gap will first increases and then decreases, while under uniaxial tensile strain the band gap decreases monotonically and the light absorption in the visible region is strongly enhanced. When uniaxial compression was applied with the perpendicular lattice constant fixed, the band gap behaves like the first kind of uniaxial compression and the light absorption is enhanced in visible range by compression. When biaxial strain was applied, the band gap shows a monotonic decrease from the largest compression down to the largest tensile strain, while the light absorption behaves in the opposite way. Therefore, the band structure and light absorption of monolayer MgGeN2 can be efficiently tuned with strain and stress, which can potentially be used for the MgGeN2 film in device design, thus promoting its applications in optoelectronics and photocatalysis.

Interface Engineering-Driven Room-Temperature Ultralow Gas Sensors with Elucidating Sensing Performance of Heterostructure Transition Metal Dichalcogenide Thin Films.

In this report, we investigate the room-temperature gas sensing performance of heterostructure transition metal dichalcogenide (MoSe2/MoS2, WS2/MoS2, and WSe2/MoS2) thin films grown over a silicon substrate using a pulse laser deposition technique. The sensing response of the aforementioned sensors to a low concentration range of NO2, NH3, H2, CO, and H2S gases in air has been assessed at room temperature. The obtained results reveal that the heterojunctions of metal dichalcogenide show a drastic change in gas sensing performance compared to the monolayer thin films at room temperature. Nevertheless, the WSe2/MoS2-based sensor was found to have an excellent selectivity toward NO2 gas with a particularly high sensitivity of 10 ppb. The sensing behavior is explained on the basis of a change in electrical resistance as well as carrier localization prospects. Favorably, by developing a heterojunction of diselenide and disulfide nanomaterials, one may find a simple way of improving the sensing capabilities of gas sensors at room temperature.

Polyhexamethylene guanidine hydrochloride‐functionalized wound dressings: Physical, mechanical and biological evaluations

AbstractThe objective of the present study is fabrication of wound dressing membranes with effective antibacterial activity, good biocompatibility with fibroblast cells, appropriate mechanical properties in both dry and wet states to potentially provide physical protection to wounds at different stages of healing, and the ability to maintain an optimum moist environment over the wounded area. To achieve this, a new silane functional polyhexamethylene guanidine hydrochloride was synthesized and utilized as a crosslinker for a polymeric matrix consisting of poly(vinyl alcohol) and gelatin. Thin monolayer films of the resulting polymeric networks were characterized and subjected to different physical and biological assays. The tensile test results indicated that the prepared dressing membranes exhibit good tensile strength in both dry (44 MPa) and hydrated (700 KPa) states. The fluid handling capacity of the dressings was found to be in the range of 2.23 to 2.29 g 10−1 m−2 day−1, which is appropriate for treating wounds with “light” to “moderate” exudate levels. The MTT assay showed excellent biocompatibility, evidenced by high fibroblast cells viability cultured directly over dressings (over 70%) or cultured in media containing the leachates extracted from the dressings (over 90%). Moreover, the dressings exhibited potent antibacterial activity against Staphylococcus aureus (87% killing) and Escherichia coli (99% killing) bacterial strains.

Electrochemical grafting assisted modification of graphite surface by 3,4,5-trimethoxybenzenediazonium based monolayer

A conventional route to create such nanoscale electronic devices using the autonomous ordering and assembly of organic molecules on atomically well-defined surfaces has been proposed. However, these thin films are unstable in realistic environments due to weak interaction between the organic molecules and crystal surfaces. Therefore, enhancing the interfacial interaction between them is assigned as the key approach to extend the scope of application of these promising monolayer thin films. In this work, we demonstrate the formation of an organic monolayer, namely 3,4,5-trimethoxy diazonium (3,4,5-TMD), on a Highly Ordered Pyrolytic Graphite (HOPG) electrode by using the power of electrochemical method. The structural properties at the nano scale as well as the bonding nature between 3,4,5-TMD adlayer and HOPG electrode at the interface were investigated by a combination of cyclic voltammetry (CV), atomic force spectroscopy (AFM) and Raman spectroscopy. As a result, the 3,4,5-TMD molecules covalently bond to carbon atoms located at the HOPG interface for forming a monolayer with its thickness of 0.92 ± 0.02 nm. This finding opens a partway to apply the electrochemical grafting for covalent functionalization of 2D materials on HOPG and other metallic surfaces.

Rapid Self‐Assembly Process at Air/Water Confined Interface for Highly Aligned Crystalline Polymeric Semiconductor Films

AbstractHighly aligned aggregation state structures have great significance for effective charge‐carrier transport in organic semiconductors. Several methods have been developed to provide organic semiconducting molecules with highly oriented aggregation state structure; among these, using a water surface to form organic semiconductor films is a widely implemented strategy, wherein solutions are spread on the surface of water. However, common techniques of film formation on water surfaces generally result in a nonuniform orientation of the film owing to the isotropic spread process of droplets on the water surface. In this study, a spatially confined air/water interfacial assembly method is proposed to obtain uniformly aligned monolayer and multilayer poly(diketopyrrolopyrrole‐thieno[3,2‐b]thiophene) thin films with controlled thickness. The structural and morphological characterizations obtained using atomic force microscopy, high‐resolution transmission electron microscopy, and grazing incidence wide‐angle X‐ray scattering indicates the crystalline structure of the thin films and high alignment of the molecular chains. The maximum mobility of the thin films reaches up to 2.06 and 0.5 cm2 V−1 s−1 in the parallel and perpendicular direction, respectively, indicating apparent anisotropic electrical properties. Furthermore, an inverter based on these thin films exhibits a voltage gain of up to 70, demonstrating the potential of applying the proposed technique to logic circuits.

Real-space BCS-BEC crossover in FeSe monolayers

The quantum many-body states in the Bardeen-Cooper-Schrieffer--Bose-Einstein condensation (BCS-BEC) crossover regime are of long-lasting interest. Here we report direct spectroscopic evidence of BCS-BEC crossover in real space in a FeSe monolayer thin film by using spatially resolved scanning tunneling spectra. The crossover is driven by the shift of band structure relative to the Fermi level. The theoretical calculation based on a two-band model qualitatively reproduces the measured spectra in the whole crossover range. In addition, the Zeeman splitting of the quasiparticle states is found to be consistent with the characteristics of a condensate. Our work paves the way to study the exotic states of BCS-BEC crossover in a two-dimensional crystalline material at the atomic scale.

An innovative method for controlled synthesis of bicomponent monolayer films obtained by reduction of diazonium.

This study presents a novel method based on the electrochemical co-reduction of two aryldiazonium salts, enabling the synthesis of controlled two-component monolayer thin films on carbon in a single step. By introducing a 12-carbon alkyl chain as a spacer between the aryldiazonium function and the functional group, precise control over film thickness and composition was achieved. The alkyl chain effectively standardizes the reduction potential, enabling the equalization of reactivity and precise stoichiometric control. Experimental results from spectroscopic, electrochemical, and X-ray photoelectron spectroscopy analyses validate the effectiveness of the method in controlling the composition of the mixed layers.

Scaling of quantum interference from single molecules to molecular cages and their monolayers

The discovery of quantum interference (QI) is widely considered as an important advance in molecular electronics since it provides unique opportunities for achieving single-molecule devices with unprecedented performance. Although some pioneering studies suggested the presence of spin qubit coherence and QI in collective systems such as thin films, it remains unclear whether the QI can be transferred step-by-step from single molecules to different length scales, which hinders the application of QI in fabricating active molecular devices. Here, we found that QI can be transferred from a single molecule to their assemblies. We synthesized and investigated the charge transport through the molecular cages using 1,3-dipyridylbenzene (DPB) as a ligand block with a destructive quantum interference (DQI) effect and 2,5-dipyridylfuran (DPF) as a control building block with a constructive quantum interference (CQI) effect using both single-molecule break junction and large area junction techniques. Combined experiments and calculations revealed that both DQI and CQI had been transferred from the ligand blocks to the molecular cages and the monolayer thin film of the cages. Our work introduced QI effects from a ligand to the molecular cage comprising 732 atoms and even their monolayers, suggesting that the quantum interference could be scaled up within the phase-coherent distance.

Enhancing the fracture resistance of hydrogels by regulating the energy release rate via bilayer designs: Theory and experiments

Hydrogels are becoming increasingly attractive for various practical applications owing to significant improvements in their fracture resistance over the past two decades. Notably, almost all existing methods for enhancing the fracture resistance of hydrogels aim to increase the fracture toughness Γ through multiscale material design. However, engineering the toughness of hydrogels at the material level often requires material-specific, complicated, or expensive synthesis processes. According to the fracture condition G=Γ, reducing the energy release rate G under given mechanical loads is an alternative way to enhance the fracture resistance. Little efforts, however, have been made to use this approach to enhance the fracture resistance of soft materials such as hydrogels so far, largely due to their highly nonlinear and deformable behavior. This paper formulates a theory for studying the fracture of monolayer and bilayer hydrogel thin films and proposes a structure-based strategy for enhancing the fracture resistance of hydrogels by constructing hydrogel films adhered to underlying stretchable substrates. Through both theoretical analysis and experimental validations, we demonstrate that the strategy exhibits several unique advantages: even a thin and compliant substrate can enhance the fracture resistance of hydrogel films by several folds, and make the fracture resistance of hydrogel films independent of the crack length and the hydrogel size – which dramatically affects the fracture behavior of monolayer hydrogels. The underlying mechanism lies in that the stretchable substrates can effectively constrain the crack opening displacements and reduce the energy release rate G for crack propagation in the hydrogel film. Moreover, the influence of experimentally-observed interfacial delamination on the fracture resistance of substrate-supported hydrogels is also investigated. The present work unveils a first-of-its-kind “structural-toughening” strategy for improving the fracture resistance of hydrogels by structurally regulating the energy release rate.

Deciphering the structure-photoluminescence correlation at small-tilt-angle grain boundaries in monolayer WS2

Grain boundaries (GBs) frequently emerge in a CVD-grown large-scale transition metal dichalcogenides monolayer thin film, which affect the electronic and optical properties of the material. Photoluminescence (PL) can be easily quenched/enhanced at GBs, which are, however, merely investigated in relatively large tilt angles (θ>14°) in previous research. Here, we experimentally examine the PL properties of monolayer WS2 GBs with tilt angles as small as a few degrees. Contrary to conventional wisdom, we find that PL intensity remains intact by the GBs when their tilt angles θ≤8°. The abnormal PL behavior is elucidated by a detailed structure analysis on the dislocation cores. For a small tilt angle, the strain fields introduced by the defective cores are sparsely distributed without mutual coupling, and the chemical stoichiometry along the GBs preserves very well. These two key structural features of the small-tilt-angle GBs allow excitons to diffuse transparently across the GB, leading to a neglectable influence on the optical and electronic properties, as verified by our first-principle simulations. The PL invariant of the small-tilt-angle GBs sheds light on the future development of CVD-grown wafer-scale techniques and their optical applications.

Morphology and Electrical Characteristics of Single-Walled Carbon Nanotubes Film Prepared by Air Brush Technique

This study is to investigate the morphology and electrical characteristics of single-wall carbon nanotubes (SWCNTs) thin film deposition using air brush technique. A deposition setup consisting of a conventional artist air brush was developed and used to deposit SWCNT thin films and therefore the resulting film’s characteristics need to be investigated to gauge its suitability in producing uniform monolayer. The SWCNTs used were synthesized via Direct Injection Pyrolytic Synthesis (DIPS) method, with diameters ranging from 0.8 to 3 nm. The substrate was deposited using an airbrush with varying nozzle to study its effect to the resulting SWCNTs thin films’ characteristics. Subsequently, scanning electron microscope (SEM) were used to inspect the morphology and surface topography, and followed by preliminary electrical measurements. The result shows that good dispersion promotes uniform distribution of SWCNTs over large area of glass substrate. Moreover, the electrical measurement revealed that at 1 V, best morphology produced highest current at a nozzle distanceof 10 mm (15.3 μA) and the lowest current at a nozzle height of 4 mm (3.24 μA). From the results presented, it is demonstrated that conventional artist airbrush setup can be effectively used to deposit monolayer thin film of SWCNT with high degree of uniformity. This research is necessary for the process of depositing-controlled CNT thin film network, which can influence the material characteristics and performance of the variety of CNT-based device applications.

Dielectric, piezoelectric and magnetic behavior of CoFe2O4/BNT–BT0.08 monolayer thin films composites

We report in this paper on the monolayer composites thin films that have the magnetic spinel CoFe2O4 and the piezoelectric perovskite BNT-BT0.08 as constituent phases. Composite thin films of CoFe2O4 and BNT-BT0.08, with molar ratios of 0.5:1, 1:1 and 1.5:1, have been deposited by spin coating method from a sol precursor, mixture type, of CoFe2O4 and BNT-BT0.08. The monolayer thin films, deposited on Si/SiO2/TiO2/Pt substrate, were characterized using selected methods, such as: X-ray diffraction, scanning electron microscopy, atomic force microscopy/piezoelectric force microscopy, dielectric spectroscopy, and vibrating sample magnetometer. X-ray diffraction demonstrated the two phases: cubic CoFe2O4 and rhombohedral BNT-BT0.08. Furthermore, the Si/SiO2/TiO2/Pt/BNT-BT0.08/CoFe2O4 monolayers show a simultaneous enhancement of both the magnetization and coercivity with the increase of the magnetic phase, accompanied by a decrease of the dielectric constant. The obtained results reveal that the investigated monolayer structures present superior properties compared to those of bilayer composites.

Comparative Study on the Direct Current Electrical Conduction in Monolayer and Bilayer Plasma Polymerized Thin Films

A comparative study on the nature of direct current electrical conduction in the monolayer and bilayer plasma polymerized thin films has been discussed in this article. The plasma polymerized pyrrole (PPPy) monolayer, plasma polymerized N,N,3,5-tetramethylaniline (PPTMA) monolayer and plasma polymerized pyrrole-N,N,3,5-tetramethylaniline (PPPy-PPTMA) bilayer thin films were deposited at room temperature onto glass substrates by using a parallel plate capacitively coupled glow discharge reactor. The current density-voltage (J-V) characteristics and the conductivity-voltage (σ-V) characteristics have been studied to analyze the direct current conduction mechanism in PPPy, PPTMA monolayer and PPPy-PPTMA bilayer thin films. The observed results have been presented in this paper. The J-V and σ-V characteristics of PPPy and PPTMA monolayer thin films of different thicknesses indicated an increase in electrical conduction and also an increase in conductivity in the films of lower thicknesses. It is also observed that PPTMA thin films are more conductive than that of PPPy thin films. As a result the PPPy-PPTMA bilayer thin films of different thicknesses and different deposition time ratios indicated an increase in conductivity as the proportion of PPTMA is increased in the films. In addition to that, from the J-V and σ-V characteristics of PPPy, PPTMA and PPPy-PPTMA thin films of same thickness, it is observed that the current conduction and the conductivity in the bilayer thin films is less compared to the monolayer thin films. This unusual result has been explained by studying ideal and real bilayer thin films. It is also seen that in the low voltage region, the current conduction obeys Ohm’s law while the charge transport phenomenon appears to be the space charge limited conduction (SCLC) in the higher voltage regions.

Effect of different precursors on morphology of CVD synthesized MoSe2

Transition metal dichalcogenides (TMD's) have emerged as a very appealing candidate for useful implementations in optoelectronics and electronics devices. In two-dimensional TMD's materials, in bulk MoSe2 has an indirect bandgap of 1.1 eV as well as in monolayer MoSe2 has a direct bandgap of 1.5 eV. Due to bandgap tunability and notable interaction of light over a wide bandwidth ranging from infrared to ultraviolet wavelength, MoSe2 possesses suitable property for optoelectronics devices. Chemical Vapor Deposition (CVD) represents an attractive approach for the growth of MoSe2 monolayer or bulk thin films and nanoflakes. MoSe2 has synthesized through CVD method and its structural properties have been studied by varying the growth temperature. Further the role of seeding promoter during the synthesis of MoSe2 through CVD and its effects on crystalline size has been discussed. XRD has been used to examine the crystalline size of synthesized MoSe2 sample and found that the synthesized MoSe2 nanoflakes/films crystalline has sized up to 4–5 µm without any seeding promoter. We have changed the growth temperature from 750 °C to 820 °C, keeping the pressure constant, in result, a slight change in the crystalline size of MoSe2 is observed. Further when NaCl has used as a seeding promoter, the crystalline size has reduced and observed to be 0.48 µm. Nevertheless, we have also illuminated the morphology of MoSe2 nanoflakes/films and discussed the associated growth parameters during CVD process.

Valley polarization of trions in monolayer MoSe2 interfaced with bismuth iron garnet

Interfacing atomically thin van der Waals semiconductors with magnetic substrates enables additional control on their intrinsic valley degree of freedom and provides a promising platform for the development of novel valleytronic devices for information processing and storage. Here we study circularly polarized photoluminescence in heterostructures of monolayer MoSe2 and thin films of ferrimagnetic bismuth iron garnet (BIG). We observe strong emission from charged excitons with circular polarization opposite to that of the pump and demonstrate contrasting response to left and right circularly polarized excitation, associated with finite out-of-plane magnetization in the substrate. We propose a theoretical model accounting for magnetization-induced imbalance of charge carriers in the two valleys of MoSe2, as well as for valley-switching scattering from B to A excitons and fast formation of trions with extended valley relaxation times, which shows excellent agreement with the experimental data. Our results establish monolayer MoSe2 interfaced with BIG as a promising system for valley control of charged excitons.

Coating of Conducting and Insulating Threads with Porous MOF Particles through Langmuir-Blodgett Technique.

The Langmuir-Blodgett (LB) method is a well-known deposition technique for the fabrication of ordered monolayer and multilayer thin films of nanomaterials onto different substrates that plays a critical role in the development of functional devices for various applications. This paper describes detailed studies about the best coating configuration for nanoparticles of a porous metal-organic framework (MOF) onto both insulating or conductive threads and nylon fiber. We design and fabricate customized polymethylmethacrylate sheets (PMMA) holders to deposit MOF layers onto the threads or fiber using the LB technique. Two different orientations, namely, horizontal and vertical, are used to deposit MIL-96(Al) monolayer films onto five different types of threads and nylon fiber. These studies show that LB film formation strongly depends on deposition orientation and the type of threads or fiber. Among all the samples tested, cotton thread and nylon fiber with vertical deposition show more homogenous monolayer coverage. In the case of conductive threads, the MOF particles tend to aggregate between the conductive thread’s fibers instead of forming a continuous monolayer coating. Our results show a significant contribution in terms of MOF monolayer deposition onto single fiber and threads that will contribute to the fabrication of single fiber or thread-based devices in the future.

Data-driven assessment of chemical vapor deposition grown MoS2 monolayer thin films

Growth of high quality two-dimensional transition metal dichalcogenide monolayers with the desired microstructure and morphology is critical for enabling key technological solutions. This is a non-trivial problem because the processing space is vast and lack of a priori guidelines impedes rapid progress. A machine learning approach is discussed that leverages the data present in published growth experiments to predict growth performance in regions of unexplored parameter space. Starting from the literature data on MoS2 thin films grown using chemical vapor deposition (CVD), a database is manually constructed. Unsupervised and supervised machine learning methods are used to learn from the compiled data by extracting trends that underlie the formation of MoS2 monolayers. Design rules are uncovered that establish the phase boundaries classifying monolayers from other possible outcomes, which offers future guidance of CVD experiments.

Unconventional Superconductivity Induced by Suppressing an Iron-Selenium-Based Mott Insulator CsFe4−xSe4

There are several FeSe based superconductors, including the bulk FeSe, monolayer FeSe thin film, intercalated KxFe2-ySe2 and Li1-xFexOHFeSe, etc. Their normal states all show metallic behavior. The key player here is the FeSe layer which exhibits the highest superconducting transition temperature in the form of monolayer thin film. Recently a new FeSe based compound, CsFe4-xSe4 with the space group of Bmmm was found. Interestingly the system shows a strong insulator-like behavior although it shares the same FeSe planes as other relatives. Density functional theory calculations indicate that it should be a metal, in sharp contrast with the experimental observations. Here we report the emergence of unconventional superconductivity by applying pressure to suppress this insulator-like behavior. At ambient pressure, the insulator-like behavior cannot be modeled as a band insulator, but can be described by the variable-range-hopping model for correlated systems. Furthermore, the specific heat down to 400 mK has been measured and a significant residual coefficient gamma_0=C/T|T->0 is observed, which contrasts the insulator-like state and suggests some quantum freedom of spin dynamics. By applying pressure the insulator-like behavior is gradually suppressed and the system becomes a metal, finally superconductivity is achieved at about 5.1 K. The superconducting transition strongly depends on magnetic field and applied current, indicating a fragile superfluid density. Our results suggest that the superconductivity is established by diluted Cooper pairs on top of a strong correlation background in CsFe4-xSe4.

Forensic Investigation and Comparison of Blood Sample Referring to Thalassemia

Identification of an individual is one of the significant features of forensic investigation. The present study was conducted to study the difference between normal and thalassemic blood. The study was conducted on 40 blood samples aim to compare control and disease wet blood samples by using different methods of microscopy. The comparison was done based on the morphology of the RBCs and red blood cell count. A (monolayer) thin blood film is prepared on a slide with a wet blood sample and observed under a compound microscope. Red blood cell count is performed with the help of Neubauer’s chamber. Observation shows the changes in the morphology of red blood cells in the thalassemic population as compared to the control population, moreover based on total RBCs count the number red blood cell count found higher in the thalassemic population as compared to the control. Both morphology and Count significantly differed from the control population. Thus, the present method can be used in the daily routine at forensic science casework.

Close-Packed Ultrasmooth Self-assembled Monolayer of CsPbBr3 Perovskite Nanocubes.

The use of colloidal self-assembly to form the complex multiscale patterns in many optoelectronic devices has been a long-standing dream of the nanoscience community. While great progress has been made using charged colloids in polar solvents, controlled assembly from nonpolar solvents is much more challenging. The major challenge is colloidal clustering caused by strong van der Waals (vdW) attraction between long-chain surface capping ligands passivating the surface of nanocrystals. Such clustering degrades ordering in packing during the self-assembly process. While ligand exchange to provide colloidal stability in polar phases is often an option, this is not the case for the exciting new class of halide perovskites due to the material’s solubility in essentially all polar solvents. Here, we report surface-functionalized self-assembly of luminescent CsPbBr3 perovskite nanocubes by partially replacing long-chain oleyl groups (18 carbon chain) with short-chain thiocyanate (SCN–). This enables the fabrication of ultrasmooth monolayer thin films of nanocubes with a root-mean-square (RMS) roughness of around 4 Å. This ultrasmooth large area self-assembled layer could act as high-efficiency optoelectronic devices like solar cells, light-emitting diodes (LEDs), transistors, etc. We correlate our experimental results with simulations, providing detailed predictions for lattice constants with chain conformations showing reduced free energy for cubes grafted with short-chain thiocyanate compared to long-chain oleyl groups, thus facilitating better self-assembly.