Self-assembled Monolayers Research Articles

Symmetry-Broken Electronic State of CsPbBr3 Cubic Perovskite Nanocrystals.

The development of densely packed, self-assembled perovskite nanocrystals (PeNCs) with a favorable transition dipole moment (TDM) orientation is crucial for their application in solution-processable electronic devices. In this study, we fabricated anisotropic CsPbBr3 PeNCs with a symmetry-broken electronic state on quartz substrates modified by 3-aminopropyltrimethoxysilane (APS). Densely packed and self-assembled monolayers of cubic PeNCs were formed on the substrates by using a dip coating technique. The angle-dependent absorption and photoluminescence (PL) spectra confirmed that the PeNC monolayer on the APS-treated substrate exhibited anisotropic electronic states in the in-plane and out-of-plane directions of the substrate. In contrast, when the quartz substrate was modified with the long alkyl silane coupling agent, octadecyltrimethoxysilane, the absorption and PL spectra exhibited no angular dependence, indicating the absence of anisotropy. Experimental and simulated results confirmed the presence of vertical TDMs in the densely packed PeNCs on the APS-treated substrate, which could be attributed to the effect of the amino groups of the APS on the facet of the cubic PeNCs facing the quartz substrate. Hence, surface chemical modifications of the substrate can aid in the precise control of the symmetry of the electronic states and TDM orientation in cubic PeNCs. These findings can promote the development of densely packed, high-coverage PeNC films with a controllable TDM orientation for applications in electronic devices such as solar cells, sensors, and light-emitting diodes.

Self-assembled monolayers: a journey from fundamental tools for understanding interfaces to commercial sensing technologies

Self-assembled monolayers were first described in the 1980s and have now become ubiquitous in many interfacial technologies. In this account, we discuss different self-assembled monolayer systems, outlining their positives and negatives. We then overview other researchers’ work and our own group’s journey in using self-assembled monolayers to develop new concepts in sensing and addressing general challenges faced by many types of sensors. Finally, we reflect on some of the challenges monolayer chemistry needs to address to facilitate further use of this powerful surface chemistry in commercial devices.

Optimization of Charge Extraction and Interconnecting Layers for Highly Efficient Perovskite/Organic Tandem Solar Cells with High Fill Factor.

Perovskite/organic tandem solar cells (POTSCs) have garnered significant attention due to their potential for achieving high photovoltaic (PV) performance. However, the reported power conversion efficiencies (PCEs) and fill factors (FFs) are still subpar due to the challenges associated with charge extraction in the organic bulk-heterojunction (BHJ) and significant energy losses in the interconnecting layers (ICLs). Here, a quaternary organic BHJ blend is developed to enhance the charge extraction in the organic subcell, contributing to an increased FF of ≥78% under 1 sun illumination and even more under lower illumination intensities. Meanwhile, energy losses in the ICLs are reduced via the incorporation of a self-assembly monolayer (SAM), (4-(3,6-Dimethyl-9H-carbazol-9-yl)butyl)phosphonic acid (Me-4PACz), in organic BHJ to form a MoOx/SAM interface and the thorough control of the MoOx thickness to suppress parasitic absorption. The resultant POTSCs achieve a remarkable PCE of 25.56% (certified: 24.65%), with a record FF of 83.62%, which is among the highest PCEs of POTSCs and the highest FF of all types of perovskite-based tandem solar cells (TSCs) till now. This work proves the optimization of charge extraction and ICLs are effective strategies to promote the performance of POTSCs to surpass other solution-processed perovskite-based TSCs in the near future.

Sequence-Controlled Electrochemical Immobilization of Catalyst-Photosensitizer Oligomers for Tuning Photoelectrochemical Behaviors.

Immobilizing catalysts and photosensitizers on an electrode surface is crucial in interfacial energy conversion. However, their combination for optimizing catalytic performance is an unpredictable challenge. Herein, we report that catalyst and photosensitizer monomers are selectively grafted one-by-one addition onto the electrode surface by interfacial electrosynthesis to achieve composition and sequence-controlled oligomer photoelectrocatalytic monolayers. This electrosynthesis relies on the oxidative coupling reaction of carbazole and the reductive coupling reaction of vinyl on the catalyst and photosensitizer monomers, and it initiates on self-assembled monolayers and propagates with alternating positive and negative potentials. Each addition and completion of the target monomer can be quantitatively identified and monitored by optical and electrical responses and their linear coefficients as a function of reaction steps. The resulting composition and sequence-controlled monolayers exhibit tuning electrocatalytic behaviors including water splitting and CO2 reduction, indicating an efficient way to optimize the electro- and photocatalytic functions and performance of molecular materials.

Flexible Crossbar Molecular Devices with Patterned EGaIn Top Electrodes for Integrated All-Molecule-Circuit Implementation.

Here, a unique crossbar architecture is designed and fabricated, incorporating vertically integrated self-assembled monolayers in electronic devices. This architecture is used to showcase 100 individual vertical molecular junctions on a single chip with a high yield of working junctions and high device uniformity. The study introduces a transfer approach for patterned liquid-metal eutectic alloy of gallium and indium top electrodes, enabling the creation of fully flexible molecular devices with electrical functionalities. The devices exhibit excellent charge transport performance, sustain a high rectification ratio (>103), and stable endurance and retention properties, even when the devices are significantly bent. Furthermore, Boolean logic gates, including OR and AND gates, as well as half-wave and full-wave rectifying circuits, are successfully implemented. The unique design of the flexible molecular device represents a significant step in harnessing the potential of molecular devices for high-density integration and possible molecule-based computing.

Enhanced Buried Interface Engineering for Efficient Inverted Perovskite Solar Cells Fabricated via Vapor-Solid Reaction.

Vapor-deposited inverted perovskite solar cells utilizing self-assembled monolayer (SAM) as hole transport material have gained significant attention for their high efficiencies and compatibility with silicon/perovskite monolithic tandem devices. However, as a small molecule, the SAM layer suffers low thermal tolerance in comparison with other metal oxide or polymers, rendering poor efficiency in solar device with high-temperature (> 160°C) fabricating procedures. In this study, a dual modification approach involving AlOx and F-doped phenyltrimethylammonium bromide (F-PTABr) layers is introduced to enhance the buried interface. The AlOx dielectric layer improves the interface contact and prevents the upward diffusion of SAM molecules during the vapor-solid reaction at 170°C, while the F-PTABr layer regulates crystal growth and reduces the interfacial defects. As a result, the AlOx/F-PTABr-treated perovskite film exhibits a homogeneous, pinhole-free morphology with improved crystal quality compared to the control films. This leads to a champion power conversion efficiency of 21.53% for the inverted perovskite solar cells. Moreover, the encapsulated devices maintained 90% of the initial efficiency after 600h of ageing at 85°C in air, demonstrating promising potential for silicon/perovskite tandem application.

Stable and sustainable perovskite solar modules by optimizing blade coating nickel oxide deposition over 15 × 15 cm2 area

Perovskite solar cells have rapidly advanced, achieving over 26% power conversion efficiency on the laboratory scale. However, transitioning to large-scale production remains a challenge due to limitations in conventional fabrication methods like spin coating. Here, we introduce an optimized blade coating process for the scalable fabrication of large-area (15 cm × 15 cm) perovskite solar modules with a nickel oxide hole transport layer, performed in ambient air and utilizing a non-toxic solvent system. Self-assembled monolayers between the nickel oxide and perovskite layer improve the uniformity and morphology of the perovskite film. Perovskite solar modules with a 110 cm2 active area achieve a power conversion efficiency of 12.6%. Moreover, encapsulated modules retained 84% of their initial efficiency after 1,000 hours at 85 °C in air (ISOS-T-1). This study demonstrates progress in the large-scale production of perovskite solar cells that combine efficiency with long-term stability.

Adhesion Strength Enhancement of Butyl Rubber and Aluminum Using Nanoscale Self-Assembled Monolayers of Various Silane Coupling Agents for Vibration Damping Plates.

In this paper, we enhance the adhesion strength of butyl rubber-based vibrational damping plates using nanoscale self-assembled monolayers of various silane coupling agents. The silane coupling agents used to chemically modify the plate's aluminum surface include 3-aminopropyltriethoxysilane (APTES), (3-glycidyloxypropyl) triethoxysilane (GPTES), 3-mercaptopropyltrimethoxysilane (MPTMS), and 3-(triethoxysilyl)propyl isocyanate (ICPTES). The modified surfaces were analyzed using Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS), and the enhancement in adhesion strength between the rubber and aluminum was estimated through T-Peel tests. As a result, MPTMS showed the highest enhancement in adhesion strength, of approximately 220% compared to the untreated sample, while GPTES, ICPTES, and APTES resulted in adhesion strength enhancements of approximately 200%, 150%, and 130%, respectively.

Asymmetric Self-Assembled Monolayer as Hole Transport Layer Enables Binary Organic Solar Cells Based on PM6: Y6 with Over 19% Efficiency

Asymmetric Self-Assembled Monolayer as Hole Transport Layer Enables Binary Organic Solar Cells Based on PM6: Y6 with Over 19% Efficiency

Counterion Loss from Charged Surface-Bound Complexes Drives the Formation of Loosely Packed Monolayers.

The functionality of multicomponent self-assembled monolayers (SAMs) can be severely diminished by the segregation of like components into nanoscale domains, a process that maximizes favorable short-range intermolecular interactions. Here, we explore the use of a modular family of sulfur-functionalized metal bis(terpyridine) complexes ([M(tpy-R)2]2+(PF6-)2) to prepare mixed SAMs, considering that the comparable structure, dimensions, and ionic composition of these species should render them interchangeable within the adsorbed surface layer. While surface voltammetry experiments show that these SAMs do exhibit compositions representative of their assembly solutions, they also suggest, in line with previous reports, that adjacent complexes in the monolayer are separated by a gap of ∼ 1 nm. Remarkably, X-ray photoelectron spectroscopy studies reveal no F 1s peak features that would confirm the proliferation of PF6- counterions on the surface. We propose that the loosely packed structure of these SAMs results from the loss or exchange of PF6- counterions, which introduces significant repulsive Coulomb interactions between the adsorbed 2+ charged complexes. The hypothesis is supported by an electrostatic model which indicates that these complexes should form close-packed SAMs if mobile counterions are present. First-principles calculations demonstrate that complex-counterion binding interactions are weakened by charge transfer to the gold substrate, suggesting that this may play an important role in the formation of such low-coverage SAMs. Together, this study raises important questions regarding the assembly, organization, and composition of charged SAMs and highlights new opportunities in the design of multicomponent monolayer assemblies with free volume, for example, to facilitate surface-based reactions or support molecular switches.

Correcting Edge Defects in Self-Assembled Monolayers through Thermal Annealing.

Self-assembled monolayers (SAMs) are emerging as platform technology for a myriad of applications, yet they still possess varied spatial stability and predictability issues as their properties are heavily dependent on subtle structural features. Reducing entropy within such a system serves as one of many potential solutions to increase order and therefore coherence/precision in measured properties. Here we explore controlled thermal annealing to improve edge disorders in SAMs and significantly reduce data variance. Using both odd- and even-numbered n-alkanethiol SAMs on Au, we observe statistically significant difference in the contact angles between edge and center. Thermal annealing at 40°C significantly narrows differences between edges and centre of the SAM, albeit with significant reduction in the parity dependent odd-even effect. This study provides a pathway to improve SAMs consistency through minimal external perturbation as reflected by the minimization of odd-even effect as SAMs become increasingly ordered.

Integration of Self-Assembled Monolayers for Cobalt/Porous Low-k Interconnects

The integration of self-assembled monolayers (SAM) into cobalt (Co)/porous low-dielectric-constant (low-k) dielectric interconnects is studied in terms of electrical characteristics and reliability in this work. Experimental results indicated that SAM derived from 3-aminopropyltrimethoxysilane (APTMS) improved breakdown field, time-dependent dielectric breakdown, and adhesion for Co/porous low-k integrated interconnects. However, the improvement magnitude was not large as compared to SAM in the Cu/porous low-k integration. Therefore, the integration of SAM into Co/porous low-k interconnects has a positive effect; however, in order to further promote the efficiency of SAM for Co/porous low-k interconnects, the option of precursors for the growth of SAM is required.

Importance of Electrostatic Effects for Interpretation of X‐ray Photoemission Spectra of Self‐Assembled Monolayers

AbstractThis paper reviews the relevant work regarding electrostatic effects in X‐ray photoemission from self‐assembled monolayers (SAMs) which are application‐relevant ultrathin molecular films, coupled over a suitable anchoring group to the substrate. Whereas, in most cases, the standard concept of chemical shift is fully sufficient to describe X‐ray photoelectron spectra of these systems, consideration of electrostatic effects is frequently necessary for their proper interpretation. Due to the insulator character of the SAM matrix, decoupled electronically from the substrate, the introduction of a dipolar ´sheet´ at the SAM‐substrate interface or within this matrix creates a potential discontinuity shifting the energy levels above the ´sheet´ with respect to those below it. This shift is reflected then in the matrix‐related spectra, resulting in shifts and splitting of the characteristic photoemission peaks. Several representative examples in this context are provided and discussed in detail. These examples and other relevant literature data underline the importance of electrostatic effects in photoemission and suggest that they should be considered on the equal footing as the chemical shift ones.

Dipole-assisted hole injection for efficient blue quantum dot light-emitting diodes

Quantum dot light-emitting diodes (QLEDs) present commercial potential and application prospects in both lighting and display technologies. Blue quantum dots (QDs) possess a substantial bandgap and a profound valence band. The significant potential barrier between blue quantum dots and the hole transport layer leads to an imbalance in charge transfer, thereby adversely impacting the device performance. Self-assembled monolayers are attractive for carrier transport. Here, a dynamic self-assembly method is introduced, doping [2-(9H-carbazol-9-yl)ethyl]phosphonic acid (2PACz) into Poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) to form electric dipoles at interfaces, realizing better energy level alignment and hole injection rate. The maximum external quantum efficiency rises from 8.77% to 17.26% with 2PACz: PEDOT:PSS strategy, representing a twofold enhancement. This result demonstrates that small molecules undergo dynamic self-assembled bilateral motions during crystallization process, aligning energy levels and passivating interfacial trap states, thereby endowing blue QLEDs with high brightness and high efficiency. This work offers a viable pathway for broader applications of blue QLEDs.

Lateral Electronic Junction of a Single Ultrathin Silicon Induced by Interfacial Dipole of Self-Assembled Monolayer.

Interface engineering is pivotal for enhancing the performance and stability of devices with layered structures, including solar cells, electronic devices, and electrochemical systems. Incorporating the interfacial dipole between the bulk layers effectively modulates the energy level difference at the interface and does not significantly influence adjacent layers overall. However, interfaces can drastically affect adjoining layers in ultrathin devices, which are essential for next-generation electronics with high integrity, excellent performance, and low power consumption. In particular, the interfacial effect is pronounced in ultrathin semiconductors, which have a weak electric field screening effect. Herein, the substantial interfacial impact on the ultrathin silicon is shown, the p- to n-type inversion of the semiconductor solely through the deposition of a self-assembled monolayer (SAM) without external bias. The effects of SAMs with different interfacial dipoles are investigated by using Hall measurement and surface analytic techniques, such as UPS, XPS, and KPFM. Furthermore, the lateral electronic junction of the ultrathin silicon is engineered by the regioselective deposition of SAMs with opposite dipoles, and the device exhibits rectification behavior. When the interfacial dipole of SAM is manipulated, the rectification ratio changes sensitively, and thus the fabricated diode shows potential to be developed as a sensing platform.

Self-Assembly Determines Sign of Seebeck Coefficient in Tunneling Junctions Comprising Monolayers and Bilayers of Fullerenes.

We measured the Seebeck coefficient for junctions comprising self-assembled monolayers and bilayers of the fullerene moiety PTEG-1 on Au using eutectic Ga-In in a controlled anhydrous atmosphere by varying the temperature gradient from -12 to 12 °C, observing a linear response in thermovoltage across the range. The sign of the coefficient was positive for monolayers of PTEG-1, (195 ± 8) μV K-1 and negative for bilayers of PTEG-1, (-209 ± 14) μV K-1, indicating a change from HOMO-mediated to LUMO-mediated charge-transport. Charge-transport is nonresonant tunneling for both monolayers and bilayers, but the former self-assembles with the fullerene cage at the chemisorbed interface while the latter includes a fullerene cage at the physisorbed interface, demonstrating that the physical position of the fullerene cage determines the energetic position of the frontier molecular orbitals of PTEG-1.

Epitaxial Guidance of Adamantyl-Substituted Polythiophenes by Self-Assembled Monolayers.

The anisotropic nature of charge transport through organic materials requires high control over the self-assembly of the organic materials. This is particularly so for conductive polymers, where transport occurs mainly along the polymers' backbone. Herein, we demonstrate the use of self-assembled monolayers (SAMs) to influence the self-assembly of poly(3-adamantylmethylthiophene). We employ two different SAMs, which interact with either the adamantyl- or the thiophene-functionality, respectively, and acquire distinct topologies as compared to the unmodified Au(111) surface. We compare these results with unmodified glass and mica (muscovite) surfaces, which are typically employed in the field of optoelectronics. We prove the usefulness and applicability of epitaxial effects and adamantyl substituents for organic electronics. This presents a viable way toward improved electronic performance for the field as a whole.

Highlighting the impact of blocking monolayers on DNA electrochemical sensors. Theoretical and experimental investigations under flow conditions

A model is proposed to account for the influence of electrode surface modifications in electrochemical DNA sensors operating under flow conditions. With blocking self-assembled monolayers of double-stranded DNA, the performance of the electrochemical transduction signal in the presence of a redox mediator is generally attributed to the rate of long-range electron transfer or to the screening effects of the monolayers due to negatively charged DNA. The originality of this model is here to only consider the influence of non-linear mass transport at the free-remaining sites. The model was tested for the detection of microRNAs (21 nucleotides) by implementing microchannel electrodes in the presence of an equimolar mixture of Fe(CN)63− / Fe(CN)64-. Two operating conditions leading to distinct monolayer structures were investigated using Pt and Au electrodes. The model successfully simulated the voltammograms confirming the apparent decrease in the signal transduction kinetics due to altered mass transport. These results were supported by measurements in electrochemical impedance spectroscopy.

Adsorption of cytochrome c on different self-assembled monolayers: The role of surface chemistry and charge density.

In this work, the adsorption behavior of cytochrome c (Cyt-c) on five different self-assembled monolayers (SAMs) (i.e., CH3-SAM, OH-SAM, NH2-SAM, COOH-SAM, and OSO3--SAM) was studied by combined parallel tempering Monte Carlo and molecular dynamics simulations. The results show that Cyt-c binds to the CH3-SAM through a hydrophobic patch (especially Ile81) and undergoes a slight reorientation, while the adsorption on the OH-SAM is relatively weak. Cyt-c cannot stably bind to the lower surface charge density (SCD, 7% protonation) NH2-SAM even under a relatively high ionic strength condition, while a higher SCD of 25% protonation promotes Cyt-c adsorption on the NH2-SAM. The preferred adsorption orientations of Cyt-c on the negatively-charged surfaces are very similar, regardless of the surface chemistry and the SCD. As the SCD increases, more counterions are attracted to the charged surfaces, forming distinct counterion layers. The secondary structure of Cyt-c is well kept when adsorbed on these SAMs except the OSO3--SAM surface. The deactivation of redox properties for Cyt-c adsorbed on the highly negatively-charged surface is due to the confinement of heme reorientation and the farther position of the central iron to the surfaces, as well as the relatively larger conformation change of Cyt-c adsorbed on the OSO3--SAM surface. This work may provide insightful guidance for the design of Cyt-c-based bioelectronic devices and controlled enzyme immobilization.

Co-adsorbed self-assembled monolayer enables high-performance perovskite and organic solar cells

Self-assembled monolayers (SAMs) have become pivotal in achieving high-performance perovskite solar cells (PSCs) and organic solar cells (OSCs) by significantly minimizing interfacial energy losses. In this study, we propose a co-adsorb (CA) strategy employing a novel small molecule, 2-chloro-5-(trifluoromethyl)isonicotinic acid (PyCA-3F), introducing at the buried interface between 2PACz and the perovskite/organic layers. This approach effectively diminishes 2PACz’s aggregation, enhancing surface smoothness and increasing work function for the modified SAM layer, thereby providing a flattened buried interface with a favorable heterointerface for perovskite. The resultant improvements in crystallinity, minimized trap states, and augmented hole extraction and transfer capabilities have propelled power conversion efficiencies (PCEs) beyond 25% in PSCs with a p-i-n structure (certified at 24.68%). OSCs employing the CA strategy achieve remarkable PCEs of 19.51% based on PM1:PTQ10:m-BTP-PhC6 photoactive system. Notably, universal improvements have also been achieved for the other two popular OSC systems. After a 1000-hour maximal power point tracking, the encapsulated PSCs and OSCs retain approximately 90% and 80% of their initial PCEs, respectively. This work introduces a facile, rational, and effective method to enhance the performance of SAMs, realizing efficiency breakthroughs in both PSCs and OSCs with a favorable p-i-n device structure, along with improved operational stability.