Octadecyltrichlorosilane Monolayer Research Articles

Detection of glyphosate residues in agricultural products using liquid-crystal-based sensor exploiting competitive binding of glyphosate and Cu2+ at the aqueous/LC interface and capillary tube test strip

Glyphosate is a widely used herbicide that poses both health and environmental risks. In this study, we propose a liquid crystal (LC)-based assay for glyphosate detection that exploits the unique properties of LC materials. The nematic LC 4-cyano-4′-pentylbiphenyl (5CB) was employed as the sensing material and a self-assembled monolayer of octadecyltrichlorosilane (OTS) was used to modify glass substrates. The assay involved strong competition for coordination with Cu2+ for glyphosate, resulting in changes in the LC texture. By monitoring and analyzing the optical images of the LC film using polarizing microscopy, we detected and quantified the glyphosate concentrations. The proposed assay demonstrated high sensitivity and selectivity toward glyphosate in the detection range of 1–300 nM with a limit of detection of 0.26 nM. Moreover, the assay successfully applied to analyze glyphosate in spiked samples, including tap water, soil, and cabbage, and satisfactory recovery rates were achieved. Based on this detection principle, capillary tube test strips were developed for on-site applications. The detection thresholds of the test strips were controlled by varying the Cu2+ concentration. The developed LC-based assay is a rapid and reliable glyphosate detection method with potential applications in environmental monitoring and food safety.

Ecofriendly Transfer Printing for Biodegradable Electronics Using Adhesion Controllable Self‐Assembled Monolayers

AbstractThe biodegradable electronics are on the rise, not just due to their role in medical implants, but also because of their eco‐friendly attributes. A variety of methods, including transfer printing, have been employed to integrate inorganic electronics onto biodegradable polymer substrates. However, the use of expensive materials, multiple intermediary steps, and labor‐intensive procedures can undermine their environment‐friendly benefits. Here, a straightforward yet efficient fabrication method is introduced for creating high‐performance biodegradable electronic devices. This method leverages the controlled adhesion between the biodegradable device and substrate using self‐assembled monolayers of octadecyltrichlorosilane. Mechanical and thermal analyses based on scratch tests and time‐domain thermoreflectance quantify the adhesion by adjusting the packing density of octadecyltrichlorosilane. Controlled adhesion allows the photolithography process without delamination while facilitating easy delamination during transfer printing. The authors demonstrate the direct fabrication of electronics consisted of inorganic materials (Mg, Zn, SiO2, Si nanomembrane) on wafers and transfer‐printing onto polymer substrates via a single transfer step. This streamlined approach enables wafer‐scale fabrication of biodegradable electronics, highlighting its potential for mass manufacturing. Pilot conceptual demonstration of mass‐produced edible hydration sensors and their application in salivation measurement through in vivo model show the potential capability of proposed fabrication method in the use of practical level.

Structural Study of Diketopyrrolopyrrole Derivative Thin Films: Influence of Deposition Method, Substrate Surface, and Aging.

We report the morphology and microstructure of n-dialkyl side-chain-substituted thiophene DPP end-capped with phenyl groups (Ph-TDPP-Ph) thin films and compare the influence of deposition method and substrate surface using thermally oxidized Si and graphene substrates as well as monolayer graphene surfaces with an underlying self-assembled octadecyltrichlorosilane monolayer, complemented by an aging study of spin-coated films over a 2 weeks aging period. A distinct difference in morphology was observed between spin-coated and vacuum-deposited thin films, which formed a fiber-like morphology and a continuous layer of terraced grains, respectively. After an initial film evolution, all combinations of deposition method and substrate type result in well-ordered thin films with almost identical crystalline phases with slight variations in crystallinity and mosaicity. These findings point toward strong intermolecular forces dominating during growth, and the templating effect observed for other oligomer films formed on graphene is consequently ineffective for this material type. Upon aging of spin-coated films, a noticeable evolution involving two different morphologies and crystalline phases were observed. After several days, the thin film evolved into a more stable crystal phase and a fiber-like morphology. Moreover, slight variation in optical spectra were elucidated on the basis on density functional theory calculations. These results demonstrate that thin-film properties of DPP derivatives can be tailored by manipulating the film formation process.

Defect Mapping and Densification in Self-Assembled Monolayers of Octadecyltrichlorosilane on SiO<sub>2</sub>

Self-assembled monolayers (SAMs) can be used for surface functional control to assist with pattern collapse prevention and as a protective layer to enable Area Selective Deposition (ASD). To be successful, these applications require the formation of a high-density, defect-free, so-called well-packed SAM at the nm scale. In this paper, we describe a method to map the nm scale defects of octadecyltrichlorosilane (ODTS) SAMs using a post-etching AFM analysis of the surface of the substrate and used this technique to develop a process to form high-density, defect-free SAM layer at the nm scale. This was achieved by optimizing the water concentration in the solvent for the precursor solution and annealing after SAM formation.

Functional hydrophobic coating for phosphogypsum via stoichiometric silanization, hydrophobic characterization, microstructure analysis, and durability evaluation

Gypsum is a typical healthful, eco-type, and energy-saving material. However, because of poor water resistance, its applications were limited. Therefore, this paper reports on a one-step stoichiometry-controlled reaction method for the preparation of long-chain silicones based on micro/nano-layered siloxane aggregates generated in a low-cost solvent. In this study, self-assembled monolayers of octadecyltrichlorosilane were prepared on the surface of β-hemihydrate phosphogypsum (β-HPG) samples using n-hexane and dichloroethane, tested for contact angle, mechanical properties, softening coefficient, analysed for hydrophobicity and durability. The results show that the water droplet surface is stable with a maximum contact angle of 144.70 ± 1.1°, the softening coefficient is 0.92 and the water absorption rate is reduced to 1.1 %. The surface remained well hydrophobic when rubbed 12 times with 600 grit sandpaper under a pressure of 4.4 KPa. The above results show that this hydrophobic coating has a promising application in the protection of large gypsum products.

Controlling Lengthscales in Water-Solvent Induced Self-Organized Dewetting of Thin Polystyrene Films by Modulating the Surface Properties of the Substrate

We report here a facile method of modulating the lengthscales of self-organized dewetting of polystyrene thin films by varying the extent of silane grafting on the substrate. The self-assembled monolayers (SAM) of octadecyltrichlorosilane (OTS) were grafted on glass substrates by exposing them to different doses of OTS vapors in a controlled, low pressure environment. Measurement of water contact angles on the modified glass surfaces showed that the contact angles could be continuously increased from 40° to 70° by increasing the time of exposure to the OTS vapors from a few minutes to several hours. Polystyrene (PS) thin films were spin coated on the modified glass substrates and water-solvent mixture induced dewetting of the PS thin films was carried out, where the dewetting kinetics depended on the spreadability of water on the surface. We observed a reduction in the length scales of the dewetting, i.e. the wavelength of instability (λ) and droplet size (d), by increasing the extent of OTS exposure. The λ for a 50 nm thick PS film decreased from 12 to 4 µm while the droplet diameter (d) also decreased, from 2.5 to 1.6 µm.

Temporal and chirp effects of laser pulses on the spectral line shape in sum-frequency generation vibrational spectroscopy.

Assignment and interpretation of the sum-frequency generation vibrational spectra (SFG-VS) depend on the ability to measure and understand the factors affecting the SFG-VS spectral line shape accurately and reliably. In the past, the formulation of the polarization selection rules for SFG-VS and the development of the sub-wavenumber high-resolution broadband SFG-VS (HR-BB-SFG-VS) have provided solutions for many of these needs. However, despite these advantages, HR-BB-SFG-VS have not been widely adopted. The majority of SFG measurements so far still relies on the picosecond (ps) scanning SFG-VS or the conventional broadband SFG-VS (BB-SFG-VS) with the spectral resolution around (mostly above) 10cm-1, which also results in less ideal spectral line shape in the SFG spectra due to the temporal and chirp effects of the laser pulses used in experiment. In this study, the temporal and the chirp effects of laser pulses with different profiles in the SFG experiment on the measured SFG-VS spectral line shape are examined through spectral simulation. In addition, the experimental data of a classical model system, i.e., octadecyltrichlorosilane monolayer on glass, obtained from the ps scanning SFG-VS, the BB-SFG-VS, and the HR-BB-SFG-VS measurements are directly compared and examined. These results show that temporal and chirp effects are often significant in the conventional BB-SFG-VS, resulting in line shape distortions and peak position shifts besides spectral broadening. Such temporal and chirp effects are less significant in the ps scanning SFG-VS. For the HR-BB-SFG-VS, spectral broadening and temporal and chirp effects are insignificant, making HR-BB-SFG-VS the choice for accurate and reliable measurement and analysis of SFG-VS.

Simulation and analysis of slip flow of water at hydrophobic silica surfaces of nanometer slit pores

Water flow in nanopores is controlled fundamentally by pore wettability and interfacial water features. In the research herein reported, Molecular dynamics (MD) was used to simulate water flow in nanometer slit pores of silica surfaces with variable wetting characteristics. Compared to Couette flow, the simulated slit-pores of the talc (001) and octadecyltrichlorosilane (OTS) monolayer surfaces exhibited water flow enhancement and a positive slip length at the interface, whereas water flow velocity at the quartz (001) and amorphous silica surfaces was zero, adhering to the no slip condition. More intensive interactions between the interfacial water and hydrophilic silica surfaces were confirmed by MD simulation and sum-frequency vibrational spectroscopy (SFVS) results. A water exclusion zone of approximately 3 Å was found at the hydrophobic silica surfaces by quantitative MD interfacial water analysis and validated by SFVS. This exclusion zone dimension was similar in magnitude to the slip length (4–5 Å) as determined from simulated water flow in hydrophobic silica slit pores. The simulated slip lengths at the hydrophobic surfaces (0.2–1 nm) were significantly less than the experimental slip lengths (>40 nm) reported in the literature. In the case of the experimental results, this difference appears to be due to nanobubbles expected to be present at hydrophobic surfaces.

Formation and tribological properties of octacosanoic acid monomolecular Langmuir–Blodgett films

ABSTRACT Tribological properties of monomolecular Langmuir–Blodgett (LB) films of octacosanoic acid (OCA) fabricated on silicon substrates by horizontal precipitation (HP) method are studied. The wear resistance of OCA coatings was studied and compared with the stability of both octadecanoic acid (OA) and octadecyltrichlorosilane (OTS) monolayers. It was found that OCA films increase the wear stability of silicon surfaces by 7.5 and 27 times as compared to OA and OTS monolayers, and reduce the coefficient of friction of an initial surface from 0.25 to 0.07. Monomolecular OCA films can be used for the protection of silicon micro-electro-mechanical systems from wear and friction.

Magnetic Particle Self-Assembly at Functionalized Interfaces.

We study the assembly of magnetite nanoparticles in water-based ferrofluids in wetting layers close to silicon substrates with different functionalization without and with an out-of-plane magnetic field. For particles of nominal sizes 5, 15, and 25 nm, we extract density profiles from neutron reflectivity measurements. We show that self-assembly is only promoted by a magnetic field if a seed layer is formed at the silicon substrate. Such a layer can be formed by chemisorption of activated N-hydroxysuccinimide ester-coated nanoparticles at a (3-aminopropyl)triethoxysilane functionalized surface. Less dense packing is reported for physisorption of the same particles at a piranha-treated (strongly hydrophilic) silicon wafer, and no wetting layer is found for a self-assembled monolayer of octadecyltrichlorosilane (strongly hydrophobic) at the interface. We show that once the seed layer is formed and under an out-of-plane magnetic field further wetting layers assemble. These layers become denser with time, larger magnetic fields, higher particle concentrations, and larger moment of the nanoparticles.

Van der Waals Epitaxy of Horizontally Orientated Bismuth Iodide/Silicon Heterostructure for Nonvolatile Resistive‐Switching Memory with Multistate Data Storage

AbstractThe film quality of insulators significantly affects performance of resistive random‐access memories (RRAMs), particularly in current leakage and degradation. In this study, a facile and practical method is employed to achieve the van der Waals epitaxy of bismuth iodide (BiI3) on silicon by using a self‐assembled monolayer of octadecyltrichlorosilane (OTS) as a buffer layer. The BiI3layer is compact and has high crystallinity, a pinhole‐free, and compact surface; every BiI3crystal is horizontally aligned with OTS–Si substrate. The RRAMs with the Si++/OTS/BiI3/Au structure exhibit excellent resistive switching properties with a very high on/off ratio of 109, long‐term stability for data retention, high endurance in write–erase cycles, and multistate information storage capacity. The crystal orientation, anisotropic carrier transport, morphology, deposition rate, and roughness considerably influence the resistive switching results. These are thoroughly investigated by analyzing the current–voltage characteristics at various temperatures, scanning electron microscope, atomic force microscope, X‐ray photoemission spectroscopy, and X‐ray diffraction patterns. It is proposed that the resistive switching mechanisms is caused by the iodine ion migration, which changes the valence charge of bismuth. This leaves a partially formed conductive metallic bismuth filament in the BiI3layer under the electrical field that enables multistate data storage.

Mixed hybrid bilayer lipid membranes on mechanically polished titanium surface

Mixed self-assembled monolayers of octadecyltrichlorosilane (OTS) and methyltrichlorosilane (MTS) were deposited via simple silanization procedure on a mechanically polished titanium surface. The monolayers act as molecular anchors for mixed hybrid bilayer lipid membranes (mhBLM) which were accomplished via vesicle fusion. A variation of the MTS concentration in silanization solutions significantly affects properties of mhBLMs composed of a 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) and cholesterol (Chol). The bilayers become less insulating following an increase of the MTS content. On the other hand, an increase of the MTS concentration provides flexibility of the mhBLM membranes necessary for the functional reconstitution of membrane proteins. The optimal molar ratio of MTS in silanization solution is 40% providing anchors for intact mhBLMs as confirmed by their specific capacitance of 0.86 μF cm−2. We found that the bilayers containing 40% (mol) of cholesterol bind cholesterol dependent pneumolysin (PLY). However, we did not observe functional reconstitution of PLY. While α-hemolysin almost fully disrupts mhBLMs assembled from 100% diphytanoyl. An important advantage of the titanium/OTS/MTS molecular anchor systems is their ability of repetitive regeneration of phospholipid bilayers without losing functional properties as demonstrated in the current study. This creates a possibility for the multiple-use phospholipid membrane biosensors which have a potential of decreasing the cost of such electrochemical/electroanalytical devices.

A Facile Preparation of Transparent Ultrahydrophobic Glass via TiO2/Octadecyltrichlorosilane (ODTS) Coatings for Self‐Cleaning Material

AbstractA facile strategy was developed to fabricate transparent ultrahydrophobic glass. First, TiO2 films were deposited uniformly on untreated glass substrate after heating aqueous peroxotitanate thin films at 120 °C for 1 h followed by octadecyltrichlorosilane (ODTS) modification. The as‐fabricated surfaces were then possessed ultrahydrophobic properties because of the combination of the rough surface topography of TiO2 and low surface energy due to ODTS monolayer. It was found that the water contact angle and sliding angle of the as‐prepared coatings were about 146° and 7°, respectively. Besides, these coatings showed excellent self‐cleaning performance compared to untreated glass in order to remove dirt particles with water droplets. It is believed that the current method could lead as low‐cost and effective way to fabricate a very promising material for commercial and industrial coatings applications.

Micropatterning and Alignment of Skeletal Muscle Myoblasts Using Microflowed Plasma Process

ObjectivesThe primary objective of the study was to optimize micropatterning environments using the microchannel flowed plasma process for controlling the orientation and behaviour of skeletal muscle cells. We have studied the cellular patterning and alignment of skeletal myoblast cells on the various micropattern widths developed on glass substrates. Materials and MethodsIn this method, we have utilized the microchannel flowed plasma process to create micropatterned self-assembled monolayers of octadecyltrichlorosilane and 3-aminopropyltrichlorosilane for creating cell adhesive widths of 20, 200 and 1000 microns on the glass substrates. The micropatterned substrates were characterized by using fluorescein 5(6)-isothiocyanate. Thereafter, the substrates were used to culture and pattern C2C12 and primary rat skeletal muscle cells. Further, we have studied the spatiotemporal variation in the orientation of the cells by using bright field and fluorescence microscopy. The microscopic images were analysed by using orientation order parameter and orientation distribution analysis. ResultsFITC based characterization of micropatterns reveals that the adopted process for micropatterning can effectively create cell adhesive widths with dimensions comparable to the diameter of myofiber. Microscopic observations and the orientation order parameter analysis reveal the precise alignment and specific orientation of myoblasts along the designated cell adhesive widths that closely mimics the physiological scenario. Both the cells showed immediate alignment within smaller cell adhesive widths of 20 and 200 μm. Actin cytoskeletal staining and its orientation distribution analysis of micropattrned C2C12 cells emphasises the influence of micropatterned environment on cytoskeletal actin orientation. ConclusionThis study corroborates the alignment of the myoblasts using surface cues facilitated by changing surface chemistry of the glass substrates. The study promotes the application of a simple micropatterning technique as a useful tool to regulate the orientation and behaviour of skeletal muscle cells. Also, the study emphasizes the role of spatial topography created by surface modification and its effect on cell adhesion and communication of alignment information across the micropatterns. The microchannel flowed plasma process could be applied to selectively pattern different adherent cell types, which could prove to be a useful platform for the exploration of various cellular processes.

Organic field effect transistors (OFETs) of poly(p-phenylenevinylene) fabricated by chemical vapor deposition (CVD) with improved hole mobility

Abstract This study demonstrates organic field effect transistors (OFETs) of chemical vapor deposited poly(p-phenylenevinylene) (PPV). The optical and electrical properties of the films are reported. It is found that the grain sizes of the film can be engineered by surface treatment of the oxide of the Si/SiO2 substrate in the transistor with a self assembled monolayer (SAM) of octadecyltrichlorosilane (OTS). The enhancement of domain sizes of the grains with surface treatment leads to an increase in hole mobility to 1.4 × 10−4 cm2/V s, which is 1000 times higher than that reported for solution processed PPV field effect transistors. A comparison of the hole mobility between CVD grown PPV films and those reported for PPV and its derivatives, grown by spin coating or drop casting, shows that CVD provides an optimized alternative for growth of devices. It is shown that a low annealing temperature of 180 °C is enough to achieve polymerization. Film deposition by CVD has the advantage that up-scaling, with a fine control on the film thickness, is possible without compromising on the electrical/morphological properties. A vacuum based method of polymer deposition opens up the prospect of hybrid devices based on small molecules and polymers.

Selective-area ALD for positively and negatively charged layers into the ion-beam track-etched conical pores in polyethylene terephthalate

This paper presents the strategy of selective-area growing of a positively-charged layer of Al2O3 and the negatively-charged layer of HfO2 on ion beam track-etched polyethylene terephthalate (PET) nanotubes through the thermal atomic layer deposition (T-ALD) technique. We used the self-assembled monolayer of octadecyl trichlorosilane (OTS-SAMs) on the surface to serve as a passivation layer and then selectively deposited the Al2O3 and HfO2 in the nanotubes. The influence of the dipping time of the substrates in the OTS solution and the experimental conditions on the roughness and the thickness of the OTS monolayer have been investigated. X-ray photoelectron spectroscopy (XPS) was used to analyze the composition of the ALD Al2O3 and HfO2 films. Atomic force microscope (AFM) and scanning electron microscope (SEM) were employed to study the morphologies before and after the ALD of Al2O3 and HfO2. The I-V characteristics of the film confirmed the surface charge polarities in the nanotubes, i.e. the positively-charged Al2O3 and negatively-charged HfO2, in the electrically-neutral solution. The results will aid surface modification and functionalization of PET by nanotubes.

Nanoscale Patterning of Colloidal Nanocrystal Films for Nanophotonic Applications Using Direct Write Electron Beam Lithography.

The small size of colloidal nanocrystal quantum dots (QDs) leads to a variety of unique optical properties that are well-suited to nanophotonics, including bright, tunable photoluminescence (PL). However, exploring the properties of solid QD assemblies at the nanoscale has proven challenging because of the limitations in the nanoscale QD patterning methods. Generally, the precise placement of QD solids is difficult to achieve, especially for tall structures with multiple QD layers, and when it is achieved the patterns often cannot withstand the further processing steps required for final device construction. Direct electron beam lithography of QDs has emerged as a straightforward patterning process that does not require ligand exchange and results in structures that retain bright PL. Here, we demonstrate that direct patterning QD films on substrates treated with a self-assembled monolayer of octadecyltrichlorosilane allows us to create feature sizes as thin as 30 nm with heights of multiple layers and characterize the pattern resolution, robustness, and placement accuracy. These structures withstand sonication in a variety of solvents, and the structures are placed within 20 nm of their intended location nearly 100% of the time. We further show how this patterning method can be applied to nanophotonics by measuring the complex refractive index of the QD materials to model the absorption and scattering cross sections of QD structures of various sizes and shapes. These simulations reveal that edge effects arising from the finite shape of the QD nanostructure lead to substantial absorption enhancement when compared to an equivalent volume region taken from a continuous QD film. Finally, we explore more complex structures by patterning QD arrays, multilayer QD structures, and QD disks inside plasmonic resonators.

Air‐Stable Symmetric Ambipolar Field‐Effect Transistors Based on Reduced Graphene Oxide‐OTS Self‐Assembled Monolayer Heterostructure

AbstractGraphene has attracted great interest in the past decade due to its unique band structure and physical properties such as quantum electronic transport, extremely high mobility, high elasticity and optical properties. Graphene is generally obtained by mechanical exfoliation, epitaxial growth, chemical vapor deposition and chemical synthesis approaches, wherein the reduction of graphene oxide (GO) is a practical approach to synthesize large‐scale graphene. Via reduction, highly conductive reduced graphene oxide (RGO) can be obtained, which has electrical and optical properties analogous to those of graphene. However, Field‐effect transistors (FETs) based RGO typically exhibit p‐type in ambient rather than the ambipolar behavior of intrinsic graphene, due to the doping effect induced by substrate and the air. Meanwhile, large hysteresis accompanies with the p‐type transistor. Here, a self‐assembled monolayer (SAM) of octadecyltrichlorosilane (OTS)‐RGO heterostructure is developed, in which RGO is sandwiched between OTS SAMs. The heterostructure passivates the RGO device and eliminates the doping of graphene from the surroundings. The obtained RGO FETs exhibit air‐stable symmetric ambipolar behavior with Dirac point at 0 V gate voltage and negligible hysteresis. This approach will also be applicable to pristine graphene and other two‐dimensional materials to obtain the intrinsic properties under ambient conditions, thereby promoting the research and applications of two‐dimensional materials.

Protective molecular passivation of black phosphorus

Black phosphorus is a fascinating layered material, with extraordinary anisotropic mechanical, optical and electronic properties. However, the sensitivity of black phosphorus to oxygen and moisture poses significant challenges for technological applications of this unique material. Here, we report a viable solution that overcomes degradation of few-layer black phosphorus by passivating the surface with self-assembled monolayers of octadecyltrichlorosilane that provide long-term stability in ambient conditions. Importantly, we show that this treatment does not cause any undesired carrier doping of the bulk channel material, thanks to the emergent hierarchical interface structure. Our approach is compatible with conventional electronic materials processing technologies thus providing an immediate route toward practical applications in black phosphorus devices.

Fabrication of plasmonic cavity arrays for SERS analysis

The plasmonic cavity arrays are ideal substrates for surface enhanced Raman scattering analysis because they can provide hot spots with large volume for analyte molecules. The large area increases the probability to make more analyte molecules on hot spots and leads to a high reproducibility. Therefore, to develop a simple method for creating cavity arrays is important. Herein, we demonstrate how to fabricate a V and W shape cavity arrays by a simple method based on self-assembly. Briefly, the V and W shape cavity arrays are respectively fabricated by taking KOH etching on a nanohole and a nanoring array patterned silicon (Si) slides. The nanohole array is generated by taking a reactive ion etching on a Si slide assembled with monolayer of polystyrene (PS) spheres. The nanoring array is generated by taking a reactive ion etching on a Si slide covered with a monolayer of octadecyltrichlorosilane before self-assembling PS spheres. Both plasmonic V and W cavity arrays can provide large hot area, which increases the probability for analyte molecules to deposit on the hot spots. Taking 4-Mercaptopyridine as analyte probe, the enhancement factor can reach 2.99 × 105 and 9.97 × 105 for plasmonic V cavity and W cavity array, respectively. The relative standard deviations of the plasmonic V and W cavity arrays are 6.5% and 10.2% respectively according to the spectra collected on 20 random spots.