Self-assembled Monolayers Research Articles

Electron transfer kinetics in ferrocene-terminated self-assembled monolayers: The effect of ferrocene surface coverage variation

Electron transfer kinetics in ferrocene-terminated self-assembled monolayers: The effect of ferrocene surface coverage variation

The Role of Self-Assembly Monolayers (SAM) on Schottky Diode Performance

This study investigates the electrical and charge transport properties of Schottky diodes with a p-Si/TiO2/SAM/Al structure, incorporating the self-assembly monolayers (SAMs) 4", 4""-[biphenyl-4,4" diylbis(phenylimino)]dibiphenyl-4-carboxylic acid (MZ187) onto a titanium dioxide (TiO2) layer synthesized via the sol-gel method. The impact of the MZ187 molecule on diode performance was evaluated based on parameters such as the barrier height (∅b), ideality factor (n), and series resistance (Rs). Experimental results reveal that the MZ187 monolayers on TiO2 substantially enhanced diode performance, reducing the n from 3.7 for the control diode to 2.7 for the MZ187-modified diode. The Rs was also significantly reduced, while the ∅b increased. The rectification ratio increased from 1.3x102 for the control diode to 2.2x103 for the MZ187 modified diode. These improvements are attributed to the ability of MZ187 molecules to minimize interface states (Nss) and improve surface quality. These findings underscore the critical role of SAMs in optimizing Schottky diode performance and demonstrate how the MZ187 molecule enhances diode efficiency by altering interface properties. The effectiveness of SAM coatings in enhancing Schottky diode performance makes a significant contribution to the field of nanoelectronics. This research paves the way for future studies on the use of SAMs in various nano electronic applications and offers promising potential for improving the performance and reliability of these technologies.

Self-Assembly of Mycolic Acid in Water: Monolayer or Bilayer.

The enduring pathogenicity of Mycobacterium tuberculosis can be attributed to its lipid-rich cell wall, with mycolic acids (MAs) being a significant constituent. Different MAs' fluidity and structural adaptability within the bacterial cell envelope significantly influence their physicochemical properties, operational capabilities, and pathogenic potential. Therefore, an accurate conformational representation of various MAs in aqueous media can provide insights into their potential role within the intricate structure of the bacterial cell wall. We have carried out MD simulations of MAs in an aqueous solution and shed light on various structural properties such as thickness, order parameters, area-per-MAs, conformational changes, and principle component (PC) in the single-component and mixture MAs monolayer. The different conformational populations in the monolayer were estimated using the distance-based analysis between the function groups represented as W, U, and Z conformations that lead to the fold of the MAs chain in the monolayer. Additionally, we have also simulated the mixture of alpha-MA (α-MA or AMA), methoxy-MA (MMA), and keto-MA (KMA) with 50.90% AMA, 36.36% MMA, and 12.72% KMA composition. The thickness of the MAs monolayer was observed to range from 5 to 7 nm with an average 820 kg/m3 density for α-MA, MMA, and KMA quantitative agreement with experimental results. The mero chain (long chain), consisting of a functional group at the proximal and distal positions, tends to fold and exhibit a more disordered phase than the short chain. The keto-MA showed the greatest WUZ total conformations (35.32%) with decreasing trend of eZ > eU > aU > aZ folds in both single component and mixture. Our results are in quantitative agreement with the experimental observations. The sZ folds show the lowest conformational probability in monolayer assembly (0.75% in a single component and 1.1% in a mixture). However, eU and aU folds are most probable for AMA and MMA. One striking observation is the abundance of MA conformers beyond the known WUZ convention because of the wide range distribution of intramolecular distances and change in dihedral angles. From a thermodynamic perspective, all mycolic acid monolayers in this study within the microsecond-long simulation, MA molecules self-assembled, and the self-assembled monolayer was found to be stable. The conformation of MAs corresponding to lower free energy minima in the monolayer gives rise to tighter packing and a highly dense self-assembly. Such a highly packed assembly shows higher resistance for drug permeability. Therefore, we concluded that the monolayer formed by AMA will be more densely packed and may cause more resistance for the drug molecules.

Selective On-Surface Metalation and Uncommon Reordering of Self-Assembled Macrocyclic Biquinazoline Ligands on Ag(111).

The macrocyclic biquinazoline ligand, H-Mabiq, presents a central and a peripheral site for the coordination of metal ions, making the adsorption on solid surfaces promising for the creation of self-assembled bimetallic two-dimensional platforms. Here, we apply an on-surface metalation strategy under ultra-high vacuum conditions to guide the synthesis of metalated species and study sequential metalation patterns. We find that cobalt (as well as iron) metalation on the Ag(111) surface preferentially occurs at the macrocyclic centre without further metal coordination to the peripheral site. Nevertheless, starting from a densely packed, self-assembled H-Mabiq monolayer, the modification of the central cavity by Co is accompanied by an unusual, metalation-induced phase transformation which gives evidence of modified lateral / interfacial interactions. The selective metalation of one molecular site opens up an on-surface route to create bimetallic networks incorporating select metal ions at different locations.

High-Security Data Encryption Enabled by DNA Multi-Strand Solid-Phase Hybridization and Displacement in Inkjet-Printed Microarrays.

Multicolor fluorescent encryption systems that respond to specific stimuli have drawn widespread attention to data storage and encryption due to their low cost and facile data access. However, existing encryption systems are limited by encryption materials, restricting their encryption depth. This study uses DNA molecules as encryption materials that offer exceptional specificity and encryption depth within sequences. With inkjet-printed microarrays on a solid-phase interface, a multicolor fluorescent data storage system based on DNA hybridization and strand displacement is developed, achieving an encryption system with high encryption depth and flexibility. DNA strands, modified with different fluorescent labels, are delivered onto solid-phase interfaces containing a DNA self-assembled monolayer (SAM) via inkjet printing, forming multicolor fluorescent data microarrays. Data storage and encryption are achieved through the hybridization of fluorescent DNA strands for data presentation and interference with the DNA SAM at the interface between the solid phase and droplets. Interference DNA strands can be removed by DNA strand displacement for decryption. The encryption depth of this system is determined by the design of the DNA sequences and the combination of multiple DNA strands, showcasing its outstanding encryption ability. Meanwhile, high-throughput inkjet printing accelerates the data writing process, further enhancing the system efficiency. With DNA solid-phase reaction in inkjet-printed microarrays, this system provides a scalable and robust strategy for high-depth and efficient data encryption.

Capillary Wave-Assisted Colloidal Assembly.

The self-assembly of nanoparticle colloids into large-area monolayers with long-range order is a grand challenge in nanotechnology. Using acoustic energy, i.e., acoustic annealing, to improve the crystal quality of self-assembled colloidal monolayers is a new solution to this challenge, but the characterization of the capillary waves driving the annealing process is lacking. We use a laser Doppler vibrometer and optical diffraction to uncover the frequency-dependent effects of capillary waves on the real-time self-assembly of submicrometer diameter polystyrene nanospheres at an air-water interface. Our study unambiguously demonstrates that low-frequency, e.g., sub-100 Hz, capillary waves are key to improving the long-range order of colloidal monolayers on an air-water interface. Furthermore, we demonstrate how a simple immersion transducer can generate capillary waves and how transducer placement and design affect vibrational spectra. Lastly, we show that frequency-shift keying of a high-frequency focused transducer provides a straightforward method of exciting low-frequency capillary waves that are effective at forming colloidal monolayers with excellent crystal quality, exhibited by grains over 3.5 cm2.

Self‐Assembled Monolayers for Highly Efficient All‐Polymer Solar Cells Sequentially Processed from Hydrocarbon Solvent

AbstractAll‐polymer solar cells (all‐PSCs), comprising polymer donors and polymerized small‐molecule acceptors (PSMAs), hold significant promise for industrial production owing to their superior device efficiencies and stability. However, the lower molecular weights and weaker crystallinity of PSMAs lead to low electron mobility, while achieving high efficiencies in all‐PSCs typically rely on the use of the highly volatile chloroform. These challenges have been addressed through the development of self‐assembled monolayers (SAMs) as a novel interfacial layer, offering improved transparency, stability, sensitivity and surface passivation. This research investigates SAMs, specifically 2PACz, as a hole transporting layer (HTL) in all‐PSCs, employing a sequential processing strategy with toluene solvent to mitigate the aforementioned challenges. This study achieves highly efficient 2PACz‐based all‐PSC cells at 19.19% (certificated at 18.51%), which is a new record for all‐PSCs by non‐halogen solvents. Compared to PEDOT:PSS‐based solar cells, the improved performance of 2PACz‐based devices can be attributed to enlarged charge carrier mobility, prolonged carrier lifetime, and constrained recombination traps. Good generality of 2PACz as HTL is observed for PM6:PYF‐T‐o and PM6:PJ1‐γ systems as 2PACz‐based devices outperform PEDOT:PSS counterparts. These results demonstrate that SAMs are a promising candidate for hole transport engineering in high‐performance all‐PSCs.

Self-Assembled Monolayer Materials with Multifunction for Antimony Selenosulfide Solar Cells

Self-Assembled Monolayer Materials with Multifunction for Antimony Selenosulfide Solar Cells

Electrochemical capacitance-based aptasensor for HER2 detection.

The overexpression of Human Epidermal Growth Factor Receptor 2 (HER2) protein is specifically related to tumor cell proliferation in breast cancers. Its presence in biological serum samples indicates presence or progression of cancer, becoming a promise biomarker. However, their detection needs a simple and high accuracy platform. In this study, we report the develop and optimization of a simple highly sensitive electrochemical platform for HER2. Gold electrode surface was modified with a self-assembled monolayer composed by DNA aptamer, 6-(ferrocenyl) hexanethiol and 6-mercapto-1-hexanethiol. Electrochemical impedance spectroscopy was used to quantify the changes in capacitance on the interface due to the presence ferrocene, whether acting as a redox charge or its behavior under different HER2 concentration in PBS and undiluted human serum. As a result, the approach allows detection of HER2 with a limit of detection of 3.61 pg/mL, 12.28 nF sensitivity per decade and a linear range from 1 pM to 1 [Formula: see text]M in serum. This electrochemical aptasensor can be applied to different arrays for aptamer screening and has a significant importance to interaction study of biological systems.

Transforming Polymers: Innovative Physical and Chemical Modification Techniques for Advanced Functional Applications

Abstract: Polymer modification encompasses a diverse array of techniques aimed at enhancing the physical and chemical properties of polymers, thereby expanding their applicability across various fields. Physical modification methods include self-assembled monolayers, radiation-induced surface modifications, UV irradiation, γ-irradiation, and laser-induced surface modifications. These techniques primarily focus on altering surface properties and enhancing characteristics such as strength, toughness, and thermal stability through non-chemical means. Chemical modification methods, on the other hand, involve reactions that change the polymer’s chemical structure. Common chemical reactions used in polymer modification include PEGylation, conjugation, wet chemical oxidation treatments, and plasma treatments. These processes introduce new functional groups, improve compatibility with other materials, and tailor properties like solubility, adhesion, and biodegradability. Despite the significant advancements in polymer modification techniques, challenges such as maintaining polymer integrity, controlling modification precision, and ensuring scalability persist. This review provides a comprehensive overview of both physical and chemical polymer modification methods, discussing their mechanisms, applications, and the challenges involved, thereby highlighting their critical role in the development of advanced materials for industrial, biomedical, and environmental applications.

Investigating Benzoic Acid Derivatives as Potential Atomic Layer Deposition Inhibitors Using Nanoscale Infrared Spectroscopy

Area-selective atomic layer deposition (AS-ALD) is a technique utilized for the fabrication of patterned thin films in the semiconductor industry due to its capability to produce uniform and conformal structures with control over thickness at the atomic scale level. In AS-ALD, surfaces are functionalized such that only specific locations exhibit ALD growth, thus leading to spatial selectivity. Self-assembled monolayers (SAMs) are commonly used as ALD inhibiting agents for AS-ALD. However, the choice of organic molecules as viable options for AS-ALD remains limited and the precise effects of ALD nucleation and exposure to ALD conditions on the structure of SAMs is yet to be fully understood. In this work, we investigate the potential of small molecule carboxylates as ALD inhibitors, namely benzoic acid and two of its derivatives, 4-trifluoromethyl benzoic acid (TBA), and 3,5-Bis (trifluoromethyl)benzoic acid (BTBA) and demonstrate that monolayers of all three molecules are viable options for applications in ALD blocking. We find that the fluorinated SAMs are better ALD inhibitors; however, this property arises not from the hydrophobicity but the coordination chemistry of the SAM. Using nanoscale infrared spectroscopy, we probe the buried monolayer interface to demonstrate that the distribution of carboxylate coordination states and their evolution is correlated with ALD growth, highlighting the importance of the interfacial chemistry in optimizing and assessing ALD inhibitors.

A Brief Review on Self-Assembled Monolayers in Organic Solar Cells: Progress, Challenges, and Future Prospects

A Brief Review on Self-Assembled Monolayers in Organic Solar Cells: Progress, Challenges, and Future Prospects

Carboxylate-Terminated Electrode Surfaces Improve the Performance of Electrochemical Aptamer-Based Sensors.

Electrochemical aptamer-based (EAB) sensors are a molecular measurement platform that enables the continuous, real-time measurement of a wide range of drugs and biomarkers in situ in the living body. EAB sensors are fabricated by depositing a thiol-modified, target-binding aptamer on the surface of a gold electrode, followed by backfilling with an alkanethiol to form a self-assembled monolayer. And while the majority of previously described EAB sensors have employed hydroxyl-terminated monolayers, a handful of studies have shown that altering the monolayer headgroup can strongly affect sensor performance. Here, using 4 different EAB sensors, we show that the mixed monolayers composed of mixtures of 6-carbon hydroxyl-terminated thiols and varying amounts of either 6- or 8-carbon, carboxylate-terminated thiols lead to improved EAB sensor performance. Specifically, the use of such mixed monolayers enhances the signal gain (the relative change in the signal seen upon target addition) for all tested sensors, often by several fold, both in buffer and whole blood at room temperature or physiological temperatures. Moreover, these improvements in gain are achieved without significant changes in the aptamer affinity or the stability of the resulting sensors. In addition to proving a ready means of improving EAB sensor performance, these results suggest that exploration of the chemistry of the electrode surface employed in such sensors could prove to be a fruitful means of advancing this unique in vivo sensing technology.

Strong Hydrophobic Interaction of High Molecular Weight Chitosan in Aqueous Solution.

Chitosan is a versatile bioactive polysaccharide in various industries, such as pharmaceuticals and environmental applications, owing to its abundance, biodegradability, biocompatibility, and antibacterial properties. To effectively harness its potential for various purposes, it is crucial to understand the mechanisms of its interaction in water. This study investigates the interactions between high molecular weight (HMW, >150 kDa) chitosan and four different functionalized self-assembled monolayers (SAMs) at three different pHs (3.0, 6.5, and 8.5) using a surface forces apparatus (SFA). We report that HMW chitosan exhibits the strongest adhesion to methyl-terminated SAM (CH3-SAM) at all pHs, showing potential for strong hydrophobic interactions against other molecules containing hydrophobic moieties. Noting that hydrogen bonding has been considered the dominating interaction mechanism of chitosan, the consequence of this study provides valuable insights into its applications in developing chitosan-based eco-friendly materials.

Molecular ferroelectric self-assembled interlayer for efficient perovskite solar cells

The interfacial molecular dipole enhances the photovoltaic performance of perovskite solar cells (PSCs) by facilitating improved charge extraction. However, conventional self-assembled monolayers (SAMs) face challenges like inadequate interface coverage and weak dipole interactions. Herein, we develop a strategy using a self-assembled ferroelectric layer to modify the interfacial properties of PSCs. Specifically, we employ 1-adamantanamine hydroiodide (ADAI) to establish robust chemical interactions and create a dipole layer over the perovskite. The oriented molecular packing and spontaneous polarity of ferroelectric ADAI generate a substantial interfacial dipole, adjusting band bending at the anode, reducing band misalignment, and suppressing charge recombination. Consequently, our formamidinium lead iodide-based conventional PSC achieves efficiencies of 25.13% (0.06 cm2) and 23.5% (1.00 cm2) while exhibiting enhanced stability. Notably, we demonstrate an impressive efficiency of 25.59% (certified at 25.36%) in a 0.06 cm2 area for the inverted champion device, showcasing the promise of ferroelectric SAMs for PSCs performance enhancement.

Prof. George Whitesides’ Contributions to Self-Assembled Monolayers (SAMs): Advancing Biointerface Science and Beyond

Prof. George Whitesides’ pioneering contributions to the field of self-assembled monolayers (SAMs) have profoundly influenced biointerface science and beyond. This review explores the development of SAMs as highly organized molecular structures, focusing on their role in advancing surface science, biointerface research, and biomedical applications. Prof. Whitesides’ systematic investigations into the effects of SAMs’ terminal group chemistries on protein adsorption and cell behavior culminated in formulating “Whitesides’ Rules”, which provide essential guidelines for designing bioinert surfaces. These principles have driven innovations in anti-fouling coatings for medical devices, diagnostics, and other biotechnological applications. We also discuss the critical role of interfacial water in SAM bioinertness, with studies demonstrating its function as a physical barrier preventing protein and cell adhesion. Furthermore, this review highlights how data science and machine learning have expanded the scope of SAM research, enabling predictive models for bioinert surface design. Remarkably, Whitesides’ Rules have proven applicable not only to SAMs but also to polymer-brush films, illustrating their broad relevance. Prof. Whitesides’ work provides a framework for interdisciplinary advancements in material science, bioengineering, and beyond. The enduring legacy of his contributions continues to inspire innovative approaches to addressing challenges in biomedicine and biotechnology.

Gypsum heterogenous nucleation pathways regulated by surface functional groups and hydrophobicity

Gypsum (CaSO4·2H2O) plays a critical role in numerous natural and industrial processes. Nevertheless, the underlying mechanisms governing the formation of gypsum crystals on surfaces with diverse chemical properties remain poorly understood due to a lack of sufficient temporal-spatial resolution. Herein, we use in situ microscopy to investigate the real-time gypsum nucleation on self-assembled monolayers (SAMs) terminated with −CH3, −hybrid (a combination of NH2 and COOH), −COOH, −SO3, −NH3, and −OH functional groups. We report that the rate of gypsum formation is regulated by the surface functional groups and hydrophobicity, in the order of −CH3 > −hybrid > −COOH > −SO3 ≈ − NH3 > − OH. Results based on classical nucleation theory and molecular dynamics simulations reveal that nucleation pathways for hydrophilic surfaces involve surface-induced nucleation, with ion adsorption sites (i.e., functional groups) serving as anchors to facilitate the growth of vertically oriented clusters. Conversely, hydrophobic surfaces involve bulk nucleation with ions near the surface that coalesce into larger horizontal clusters. These findings provide new insights into the spatial and temporal characteristics of gypsum formation on various surfaces and highlight the significance of surface functional groups and hydrophobicity in governing gypsum formation mechanisms, while also acknowledging the possibility of alternative nucleation pathways due to the limitations of experimental techniques.

Donor-Interacting Arylated Carbazole Self-Assembled Monolayer Enables Highly Efficient and Stable Organic Photovoltaics.

Carbazole-derived self-assembled monolayers (SAMs) are promising materials for hole-extraction layer (HEL) in conventional organic photovoltaics (OPVs). Here, a SAM Cbz-2Ph derived from 3,6-diphenylcarbazole is demonstrated. The large molecular dipole moment of Cbz-2Ph allows the modulation of electrode work function to facilitate hole extraction and maximize photovoltage, thus improving the OPV performance. Additionally, the flanking aryls of Cbz-2Ph help establish CH-π interactions for forming a dense and well-organized SAM HEL and exhibit stronger van der Waals interactions with the donor PM6 than acceptor BTP-eC9. The stronger SAM-donor interactions modulate the PM6 distribution in PM6:BTP-eC9 bulk-heterojunction film, leading to PM6 enrichment near HEL to facilitate efficient hole extraction to the ITO anode in conventional p-i-n OPVs. Consequently, binary PM6:BTP-eC9-based devices incorporating the Cbz-2Ph HEL demonstrate an impressive efficiency of 19.18%. These cells also showcase excellent operational stability, with a T80 lifetime of ≈1260 h at the maximum power point, over 10 times longer than those using the traditional PEDOT:PSS HEL (T80 ≈96h). Furthermore, the universal applicability of Cbz-2Ph as a HEL is evident through its successful implementation in PM6:BTP-eC9:L8-BO-F-based ternary devices and PM6:BTP-eC9-based printed OPV devices, achieving a PCE of 19.30% and 16.96%, respectively.

Binding Kinetics of Self-Assembled Monolayers of Fluorinated Phosphate Ester on Metal Oxides for Underwater Aerophilicity.

The term "aerophilic surface" is used to describe superhydrophobic surfaces in the Cassie-Baxter wetting state that can trap air underwater. To create aerophilic surfaces, it is essential to achieve a synergy between a low surface energy coating and substrate surface roughness. While a variety of techniques have been established to create surface roughness, the development of rapid, scalable, low-cost, waste-free, efficient, and substrate-geometry-independent processes for depositing low surface energy coatings remains a challenge. This study demonstrates that fluorinated phosphate ester, with a surface tension as low as 15.31 mN m-1, can form a self-assembled monolayer on metal oxide substrates within seconds using a facile wet-chemical approach. X-ray photoelectron spectroscopy was used to analyze the formed self-assembled monolayers. Using nanotubular morphology as a rough substrate, we demonstrate the rapid formation of a superhydrophobic surface with a trapped air layer underwater.

SERS Detection of Hydrophobic Molecules: Thio-β-Cyclodextrin-Driven Rapid Self-Assembly of Uniform Silver Nanoparticle Monolayers and Analyte Trapping.

High-sensitivity and repeatable detection of hydrophobic molecules through the surface-enhanced Raman scattering (SERS) technique is a tough challenge because of their weak adsorption and non-uniform distribution on SERS substrates. In this research, we present a simple self-assembly protocol for monolayer SERS mediated by 6-deoxy-6-thio-β-cyclodextrin (β-CD-SH). This protocol allows for the rapid assembly of a compact silver nanoparticle (Ag NP) monolayer at the oil/water interface within 40 s, while entrapping analyte molecules within hotspots. The proposed method shows general applicability for detecting hydrophobic molecules, exemplified as Nile blue, Nile red, fluconazole, carbendazim, benz[a]anthracene, and bisphenol A. The detection limits range from 10-6to 10-9 M, and the relative standard deviations (RSDs) of signal intensity are less than 10%. Moreover, this method was used to investigate the release behaviors of a hydrophobic pollutant (Nile blue) adsorbed on the nanoplastic surface in the water environment. The results suggest that elevated temperatures, increased salinities, and the coexistence of fulvic acid promote the release of Nile blue. This simple and fast protocol overcomes the difficulties related to hotspot accessibility and detection repeatability for hydrophobic analytes, holding out extensive application prospects in environmental monitoring and chemical analysis.