Self-assembled Monolayer Molecules Research Articles

Improving Buried Interface Contact for Inverted Perovskite Solar Cells via Dual Modification Strategy

AbstractThe non‐wetting issue of the self‐assembled monolayer (SAM) layer can complicate subsequent perovskite deposition and impact device efficiency. This study addresses this challenge using a dual approach involving co‐self‐assembly and a buffer layer to enhance the wettability and interfacial contact of the buried perovskite film. A weakly acidic boronic acid derivative, 4‐N, N‐dimethylbenzeneboronic acid hydrochloride (4NPBA), is used to co‐self‐assemble with the regular SAM molecule on ITO and the subsequent FAI buffer layer further increased perovskite film coverage to 89%. This dual buried interface strategy—SAM‐4NPBA/FAI—results in a flat and dense perovskite interface. The optimized device demonstrates a high fill factor of 88.35%, a power conversion efficiency of 25.29%, and retains over 99% of its initial efficiency after 500 h of maximum power point testing.

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.

Improved Molecular Packing of Self-Assembled Monolayer Charge Injectors for Perovskite Light-Emitting Diodes.

Self-assembled monolayers (SAMs) have shown great potential as hole injection materials for perovskite light-emitting diodes due to their low parasitic absorption and ability to adjust energy level alignment. However, the head and anchoring groups on SAM molecules with significant differences in polarity can lead to the formation of micelles in the commonly used alcoholic processing solvent, inhibiting the formation of an intact SAM. In this work, the introduction of methyl groups on carbazole in the phosphonic-acid-based SAM materials is found to facilitate energy level alignment and promote the formation of compact SAMs. The alternative molecular structure also enhances the solvent resistance of poly(9-vinylcarbazole), suppressing interfacial defect densities and nonradiative recombination processes in the emissive perovskites. PeLEDs based on the methyl-containing SAMs exhibit ∼30% enhancement in efficiency. These findings contribute to a better understanding of the design of SAM materials for PeLED applications.

Conjugated linker-boosted self-assembled monolayer molecule for inverted perovskite solar cells

Conjugated linker-boosted self-assembled monolayer molecule for inverted perovskite solar cells

Improving the performance parameters of organic field-effect transistors via alkyl chain length of boronic acid self-assembled monolayers

Interface modification is a promising technique for enhancing electrical parameters of Organic Field Effect Transistor (OFETs). In OFETs, self-assembled monolayer molecules are widely used for treatment dielectric/semiconductor interface layer. Modification of dielectric/semiconductor layer with SAM molecules ensures a variety of potential applications. Boronic acids with four different alkyl chain lengths (Cn-BA; n = 8, 10, 12, 14) molecules were used in this study to treat the Al2O3 dielectric surface in dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]thiophene (DNTT) based OFETs. Treated with SAMs improve the mobility of Al2O3 surfaces for linear and saturation regime and threshold voltages shifted from positive direction. The morphological and electrical characterizations were performed for fabricated OFET. The results show that alkyl-boronic acids SAM molecules open a new perspective for further optoelectronic applications due to its application for oxide surfaces and controllability.

Interfacial Modification of NiOx for Highly Efficient and Stable Inverted Perovskite Solar Cells

AbstractNickel oxide is one of the most promising hole‐transporting materials in inverted perovskite solar cells (PSCs) but suffers from undesired reactions with perovskite which leads to limited device performance and stability. Self‐assembled monolayers (SAMs) are demonstrated to effectively optimize the NiOx/perovskite interface, but the significance of the compactness of the SAM at the interface is less investigated. Here, a series of methoxy‐substituted triphenylamine functionalized benzothiadiazole (TBT) based SAM molecules, TBT‐BA, TBT‐FBA, and TBT‐DBA, with benzoic acid, 2‐fluorobenzoic acid and isophthalic acids as anchoring groups are used to modify NiOx. TBT‐BA with the simplest structure is demonstrated to form the densest SAM on NiOx, thus optimized NiOx/SAM/perovskite interface is achieved with enhanced charge collection and suppressed interfacial reaction and recombination. TBT‐BA can also passivate the perovskite most effectively due to the highest binding energy toward perovskite, thus the corresponding inverted PSCs show the highest PCE of 24.8% and maintain 88.7% of the initial PCE after storage at 60 °C for 2635 h in the glovebox. The work provides important insights into designing SAM molecules for modification transporting layers for efficient and stable PSCs.

Surface functionalization enabling highly effective phase-change heat transfer of R1234yf: A molecular dynamics study

Phase-change heat transfer has been demonstrated to be an effective thermal management approach for high-power electronics and power generators. In this work, we propose a strategy using surface functionalization to enhance the phase-change heat transfer of an environmentally friendly refrigerant, i.e., hydrofluoroolefins (HFO)-based R1234yf. Using molecular dynamics simulations, we find that the evaporation (condensation) heat transfer coefficient (HTC) at self-assembled monolayer (SAM) functionalized gold (Au) surfaces can be increased by ∼7 (∼5) times compared to that at the planar Au surfaces. The improvement in phase-change heat transfer of R1234yf at functionalized Au surfaces arises from the high thermal conductance across functionalized Au/R1234yf interfaces and the strong vibrational couplings between SAM molecules and R1234yf molecules. On the one hand, the introduced SAM layer can increase the interfacial thermal conductance (ITC) between Au and R1234yf owing to the strong bonding between Au and the SAM molecules, as well as the strong vibrational couplings at low-frequency modes (0–6 THz) among Au, SAM, and R1234yf. On the other hand, the thermal energy exchange during the evaporation (condensation) process can be improved by surface functionalization through the vibrational couplings between SAM and R1234yf at high frequency (∼12 and ∼30 THz) regions. This dual vibrational coupling will then allow the SAM layer to work as an intermedia to bridge the vibrations between Au and R1234yf molecules, which in return benefits the phase-change heat transfer. By further characterizing the evaporation and condensation processes, we find that the evaporation rate of R1234yf is increased by ∼50% at most at the wall superheat <70 K when the Au surfaces are functionalized using SAMs. When the wall superheat is above 70 K (i.e., 100 K for the planar Au surface), the evaporation of R1234yf becomes like film evaporation in which clusters of R1234yf molecules move off the surface together, which limits the enhancement (i.e., ∼100% at most) of evaporation HTC at the functionalized Au surfaces. At the same time, the condensation rate at functionalized Au surfaces is found to be increased by 15%–100% compared to that of the planar Au surfaces. By elucidating the mechanisms governing phase-change heat transfer on functionalized surfaces, our results provide an efficient strategy to enhance the cooling efficiency of the HFO refrigerants, which may benefit the design of surfaces with high phase-change heat transfer capabilities.

Double-side 2D/3D heterojunctions for inverted perovskite solar cells.

Defects at the top and bottom interfaces of three-dimensional (3D) perovskite photoabsorbers diminish the performance and operational stability of perovskite solar cells owing to charge recombination, ion migration and electric-field inhomogeneities1-5. Here we demonstrate that long alkyl amine ligands can generate near-phase-pure 2D perovskites at the top and bottom 3D perovskite interfaces and effectively resolve these issues. At the rear-contact side, we find that the alkyl amine ligand strengthens the interactions with the substrate through acid-base reactions with the phosphonic acid group from the organic hole-transporting self-assembled monolayer molecule, thus regulating the 2D perovskite formation. With this, inverted perovskite solar cells with double-side 2D/3D heterojunctions achieved a power conversion efficiency of 25.6% (certified 25.0%), retaining 95% of their initial power conversion efficiency after 1,000 h of 1-sun illumination at 85 °C in air.

Effect of Anode Interfacial Modification by Self-Assembled Monolayers on the Organic Solar Cell Performance.

A series of self-assembled monolayer (SAM)-based benzoic acid derivatives such as 4-[5'-phenyl-2,2'-bitien-5-yl] benzoic acid (ZE-Ph), 4-[5'-(4-fluorophenyl)-2,2'-bitien-5-yl]benzoic acid (ZE-1F), and 4-[5'-(3,5-difluorophenyl)-2,2'-bitien-5-yl]benzoic acid (ZE-2F) were synthesized to use an interlayer between an ITO electrode and a MoO3 thin film layer in an organic solar cell (OSC) having poly-3 hexylthiophene (P3HT): [6,6]-phenyl C61 butyric acid methyl ester (PC61BM) blend. The work function and surface wetting properties of the ITO were tuned by SAM molecules. The power conversion efficiency of fabricated OSC devices was improved compared to that of the control device from 1.93 to 2.20% and 2.22% with ZE-Ph and ZE-1F-modified ITO electrodes, respectively. The short-circuit current density (Jsc) was increased from 6.16 to 7.10 mA/cm2 and 6.94 mA/cm2 with control, ZE-Ph, and ZE-1F-modified solar cells, respectively. The increase in short-circuit current density (Jsc) shows that the hole-transporting properties between ITO and MoO3 were improved by the use of ZE-Ph and ZE-1F compared with that of the ITO/MoO3 electrode configuration. The open-circuit voltage (Voc) of the SAM-modified ITO-based devices was also improved compared with the Voc of unmodified ITO-based devices. These results show that using a monolayer as an interlayer in OSCs is an important strategy to improve the performance of OSCs. All the device parameters were characterized by Kelvin probe force microscopy, cyclic voltammetry, contact angle, and I-V measurements.

Anchoring Charge Selective Self-Assembled Monolayers for Tin-Lead Perovskite Solar Cells.

Self-assembled monolayers (SAMs) have displayed great potential for improving efficiency and stability in p-i-n perovskite solar cells (PSCs). The anchoring of SAMs at the conductiv metal oxide substrates and their interaction with perovskite materials must be rationally tailored to ensure efficient charge carrier extraction and improved quality of the perovskite films. Herein, SAMs molecules with different anchoring groups and spacers to control the interaction with perovskite in the p-i-n mixed Sn-Pb PSCs are selected. It is found that the monolayer with the carboxylate group exhibits appropriate interaction and has a more favorable orientation and arrangement than that of the phosphate group. This results in reduced nonradiative recombination and enhanced crystallinity. In addition, the short chain length leads to an improved energy level alignment of SAMs with perovskite, improving hole extraction. As a result, the narrow bandgap (≈1.25eV) Sn-Pb PSCs show efficiencies of up to 23.1% with an open-circuit voltage of up to 0.89V. Unencapsulated devices retain 93% of their initial efficiency after storage in N2 atmosphere for over 2500 h. Overall, this work highlights the underexplored potential of SAMs for perovskite photovoltaics and provides essential findings on the influence of their structural modification.

Enhancing Surface Modification and Carrier Extraction in Inverted Perovskite Solar Cells via Self-Assembled Monolayers.

Perovskite solar cells (PSCs) have been significantly improved by utilizing an inorganic hole-transporting layer (HTL), such as nickel oxide. Despite the promising properties, there are still limitations due to defects. Recently, research on self-assembled monolayers (SAMs) is being actively conducted, which shows promise in reducing defects and enhancing device performance. In this study, we successfully engineered a p-i-n perovskite solar cell structure utilizing HC-A1 and HC-A4 molecules. These SAM molecules were found to enhance the grain morphology and uniformity of the perovskite film, which are critical factors in determining optical properties and device performance. Notably, HC-A4 demonstrated superior performance due to its distinct hydrophilic properties with a contact angle of 50.3°, attributable to its unique functional groups. Overall, the HC-A4-applied film exhibited efficient carrier extraction properties, attaining a carrier lifetime of 117.33 ns. Furthermore, HC-A4 contributed to superior device performance, achieving the highest device efficiency of 20% and demonstrating outstanding thermal stability over 300 h.

A regulation strategy of self-assembly molecules for achieving efficient inverted perovskite solar cells.

Self-assembled monolayers (SAMs) have been successfully employed to enhance the efficiency of inverted perovskite solar cells (PSCs) and perovskite/silicon tandem solar cells due to their facile low-temperature processing and superior device performance. Nevertheless, depositing uniform and dense SAMs with high surface coverage on metal oxide substrates remains a critical challenge. In this work, we propose a holistic strategy to construct composite hole transport layers (HTLs) by co-adsorbing mixed SAMs (MeO-2PACz and 2PACz) onto the surface of the H2O2-modified NiOx layer. The results demonstrate that the conductivity of the NiOx bulk phase is enhanced due to the H2O2 modification, thereby facilitating carrier transport. Furthermore, the hydroxyl-rich NiOx surface promotes uniform and dense adsorption of mixed SAM molecules while enhancing their anchoring stability. In addition, the energy level alignment at the interface is improved due to the utilization of mixed SAMs in an optimized ratio. Furthermore, the perovskite film crystal growth is facilitated by the uniform and dense composite HTLs. As a result, the power conversion efficiency of PSCs based on composite HTLs is boosted from 22.26% to 23.16%, along with enhanced operational stability. This work highlights the importance of designing and constructing NiOx/SAM composite HTLs as an effective strategy for enhancing both the performance and stability of inverted PSCs.

Efficient Silicon Solar Cells through Organic Self‐Assembled Monolayers as Electron Selective Contacts

AbstractEffective charge carrier‐selective contacts are a crucial component of high‐performance crystalline silicon (c‐Si) solar cells. Organic materials deposited via self‐assembly on the c‐Si surface are promising candidates for simplified, scalable, and cost‐effective processing of charge extraction layers. This study investigates the application of nPACz self‐assembled monolayers (SAMs), based on carbazole and phosphonic acid groups, where n (= 2, 4, or 6) is the aliphatic chain length, to facilitate electron extraction in c‐Si solar cells by tuning the work function of aluminum (Al) at the rear contact. So far, these SAM molecules are mainly applied as the hole‐selective layer in state‐of‐the‐art perovskite and organic solar cells, via anchoring on a metal oxide electrode. Here, by inserting 2PACz between amorphous silicon passivated c‐Si and Al, an electron‐selective contact with a contact resistivity of 65 mΩ cm2 is achieved and a power conversion efficiency of 21.4% with an open‐circuit voltage of 725 mV and a fill factor of 79.2% is demonstrated. Although the 2PACz displays some instability in this study, its initial performance is comparable to those achieved with conventionally used n‐type amorphous silicon. This study highlights the potential of solution‐processable organic SAMs in forming carrier‐selective contacts for c‐Si heterojunction solar cells.

Design of a simple bifunctional system as a self-assembled monolayer (SAM) for inverted tin-based perovskite solar cells

In this work, we functionalized the ITO substrates with a series of self-assembled monolayer (SAM) molecules to improve the hole extraction ability of the electrodes and retard the charge recombination with the devices in an inverted planar p-i-n configuration. Organic molecules with simple structures, namely 4-aminobenzoic acid (AB), 4-(2-aminomethyl)benzoic acid (AM), 4-(2-aminoethyl)benzoic acid (AE), and 4-nitrobenzoic acid (NB) were chosen to functionalize the ITO substrates via simple immersion method to form hole-selective SAM on ITO. The TPSCs were fabricated according to a two-step sequential deposition approach using a co-solvent system, and the AB device was found to exhibit an attractive efficiency of power conversion (PCE) of 7.6 % while the other SAM-based devices showed poorer performance. The AB device also displayed impressive long-term storage stability by maintaining about 80 % of its initial efficiency for over 3500 h without encapsulation, in addition to a long-term (6 h) light-soaking stability, which is superior to the PEDOT: PSS-based device in ambient conditions. The SAM/perovskite interfacial characteristics were studied using UPS, EIS, and TCSPC to understand the energy levels, charge recombination, and hole-extraction nature, respectively, and to support the outstanding performance and stability of the AB device.

Compact Hole-Selective Self-Assembled Monolayers Enabled by Disassembling Micelles in Solution for Efficient Perovskite Solar Cells.

Self-assembled monolayers (SAMs) are widely employed as effective hole-selective layers (HSLs) in inverted perovskite solar cells (PSCs). However, most SAM molecules are amphiphilic in nature and tend to form micelles in the commonly used alcoholic processing solvents. This introduces an extra energetic barrier to disassemble the micelles during the binding of SAM molecules on the substrate surface, limiting the formation of a compact SAM. To alleviate this problem for achieving optimal SAM growth, a co-solvent strategy to disassemble the micelles of carbazole-based SAM molecules in the processing solution is developed. This effectively increases the critical micelle concentration to be above the processing concentration and enhances the reactivity of the phosphonic acid anchoring group to allow densely packed SAMs to be formed on indium tin oxide. Consequently, the PSCs derived from using MeO-2PACz, 2PACz, and CbzNaph SAM HSLs show universally improved performance, with the CbzNaph SAM-derived device achieving a champion efficiency of 24.98% and improved stability.

Weak interaction engineering on thermal transport in metal-organic semiconductor nanocomposites with self-assembled monolayers

The engineering of weak interactions between metals and organic semiconductors is crucial in regulating energy carrier transport within organic semiconductor electronics. In this study, we introduce self-assembled monolayers (SAMs) to improve thermal transport in metal-organic semiconductor nanocomposites. SAM molecules with different terminal groups (-CH3, -COOH, and -C6H5) and chain lengths are utilized to modify the surface of Au nanoparticles with multiple core diameters. The introduction of SAMs significantly boosts the thermal transport of metal-organic semiconductor nanocomposites, which can be attributed to improved vibrational coupling and stronger nonbonding interactions. Furthermore, longer SAM chains broaden the area of van der Waals regions and further strengthen the intermolecular interaction across the interface, reducing the interfacial thermal transport barrier. Additionally, quantum chemistry calculation and evaluations of interfacial adhesion energy indicate that the π-π stacking interaction between TPD and SAM(-C6H5) molecules forms the best interfacial combination of nanoparticles and TPD molecules, resulting the greatest thermal transport characteristics. Finally, free energy calculations demonstrate that the variation of nanoparticle surface topology with the increase of the SAM chain length induces more obvious free energy fluctuation, which leads to tighter connections between TPD and SAM molecules under weak interaction.

Amperometric Detection of NH3 by Aromatic SAM-Modified Graphene

Ammonia (NH <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> ) is a toxic substance resulting in various acute and chronic effects on individuals. NH <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> detection, monitoring methods, and detection tools are desperately needed. In this work, we improved the ammonia sensing capabilities of graphene films deposited by chemical vapor deposition (CVD) by modifying aromatic self-assembled monolayer (SAM) molecules such as 5-[(3-methylphenyl) (phenyl) amino] isophthalic acid (MeIPA) and 5-(diphenyl)amino] isophthalic acid (PhIPA) on amperometric detection method. Morphological investigations of the films were carried out by optical and scanning electron microscopy (SEM). Surface potential was characterized with Kelvin Probe Force Microscopy (KPFM), and vibrational properties were characterized with Raman Spectroscopy. MeIPA modification increased NH <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> uptake by two times compared to unmodified graphene. The results indicated that the SAM modification enhanced NH <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> molecule adsorption and improved its periodic reversible and reproducible response using the amperometric detection system, indicating that SAM molecules might be a feasible probe for ammonia.

Interfacial Molecular Compatibility for Programming Organic-Metal Oxide Superlattices.

Artificially programming a sequence of organic-metal oxide multilayers (superlattices) by using atomic layer deposition (ALD) is a fascinating and challenging issue in material chemistry. However, the complex chemical reactions between ALD precursors and organic layer surfaces have limited their applications for various material combinations. Here, we demonstrate the impact of interfacial molecular compatibility on the formation of organic-metal oxide superlattices using ALD. The effects of both organic and inorganic compositions on the metal oxide layer formation processes onto self-assembled monolayers (SAM) were examined by using scanning transmission electron microscopy, in situ quartz crystal microbalance measurements, and Fourier-transformed infrared spectroscopy. These series of experiments reveal that the terminal group of organic SAM molecules must satisfy two conflicting requirements, the first of which is to promptly react with ALD precursors and the second is not to bind strongly to the bottom metal oxide layers to avoid undesired SAM conformations. OH-terminated phosphate aliphatic molecules, which we have synthesized, were identified as one of the best candidates for such a purpose. Molecular compatibility between metal oxide precursors and the -OHs must be properly considered to form superlattices. In addition, it is also important to form densely packed and all-trans-like SAMs to maximize the surface density of reactive -OHs on the SAMs. Based on these design strategies for organic-metal oxide superlattices, we have successfully fabricated various superlattices composed of metal oxides (Al-, Hf-, Mg-, Sn-, Ti-, and Zr oxides) and their multilayered structures.

Disordered Phase-Assisted Growth of Organic Semiconductor Crystals on Self-Assembled Monolayer Templates.

Achieving high mobility and bias stability is a challenging obstacle in the advancement of organic thin-film transistors (OTFTs). To this end, the fabrication of high-quality organic semiconductor (OSC) thin films is critical for OTFTs. Self-assembled monolayers (SAMs) have been used as growth templates for high-crystalline OSC thin films. Despite significant research progress in the growth of OSC on SAMs, a detailed understanding of the growth mechanism of the OSC thin films on a SAM template is lacking, which has limited its use. In this study, the effects of the structure (thickness and molecular packing) of SAM on the nucleation and growth behavior of the OSC thin films were investigated. We found that disordered SAM molecules assisted in the surface diffusion of the OSC molecules and resulted in a small nucleation density and large grain size of the OSC thin films. Moreover, a thick SAM with disordered SAM molecules on the top was found to be beneficial for the high mobility and bias stability of the OTFTs.

Interfacial modification to anomalously facilitate thermal transport through cathode-separator composite in lithium-ion batteries

Effective thermal management is the key to ensuring lithium-ion batteries (LIBs)’ lifetime and performance. However, the high thermal resistance across the cathode-separator interphase considerably limits the fast heat transfer. Adopting the self-assembled monolayers (SAMs) approach, various organic molecules were selected as the heat controllers to modulate the interfacial thermal conductance (ITC) between the cathode, lithium cobalt oxide (LCO), and the separator, polyethylene (PE). Silane-based SAMs molecules with different groups, including –NH2, –SH, and –CH3, were assembled into the LCO-PE composite’s interphase. Through molecular dynamics (MD) simulations, our results demonstrate SAMs molecules-decorated LCO-PE nanocomposites give a notably improved interfacial heat transfer but are of different magnitude. Such difference mainly results from the different non-bonded interactions and compatibility between SAMs molecules and PE. Of the three SAMs molecules, the assembled 3-aminopropyl trimethoxysilane (APTMS) featuring –NH2 groups improves the ITC the most, about 303.29% in comparison with the pristine interface. Furthermore, these findings help elucidate the underlying mechanisms of how SAMs molecules improve heat transfer across the LCO-PE interphase. Specifically, such enhancement is greatly attributed to the unique SAMs molecules, which build the new heat transfer pathways between LCO and PE, straighten SAMs molecules’ morphology, remove the discontinuities in the temperature field, develop the strong non-bonded interactions between SAMs molecules and PE, and strengthen the coupling vibration of two materials. These investigations provide a new perspective for designing composite’s interphase to mediate the heat transfer and achieve more effective thermal management across the interphase.