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Abstract The rational design of surfaces at the molecular level is essential toward realizing many engineering applications. However, molecular‐scale defects affect processes such as triboelectrification, scaling, and condensation. These defects are often detectable via contact angle hysteresis (CAH) measurements. Liquid‐like surfaces exhibit extremely low CAH (≤5°) and rely on the use of highly flexible molecular species such as long‐chain alkyls or siloxanes. Their low glass transition temperatures lead to the so‐termed self‐smoothing behavior, reducing sensitivity to defects formed during fabrication. However, utilizing rigid molecular species such as perfluoroalkyl chains often results in higher hysteresis (10° to 60°) as defects are not self‐smoothed after fabrication. Consequently, state‐of‐the‐art perfluoroalkylated surfaces often show sub‐optimal interfacial properties. Here, a customizable chemical vapor deposition process creates molecularly‐thick, low‐defect surfaces from trichloro(1H,1H,2H,2H‐perfluorooctyl)silane. By implementing moisture‐exposure controls, highly homogenous surfaces with root‐mean‐square roughness below 1 nm are fabricated. CAH is achieved down to ≈4° (average: 6°), surpassing the state‐of‐the‐art by ≈5°. Reduction of CAH (26° to 6°) results in condensation suppression, decreasing surface droplet density by one order and surface droplet coverage by 40%. This work guides the synthesis of high‐quality surfaces from tri‐functional perfluoroalkylsilanes with liquid‐like properties despite their molecular rigidity.

Abstract Self‐assembled monolayers (SAMs) are a class of quasi‐2D materials adhesive to the substrate by chemisorption. Due to their transparency, diversity, stability, sensitivity, selectivity, and great potential in surface passivation, SAMs have been extensively investigated and applied in various functional devices, particularly in organic field effect transistors (OFETs). Among all the processing methods, kinetic‐driven spin‐coating is frequently used for the SAM preparation due to its high efficiency and low cost. However, the importance of SAM quality and its relationship to device performance has not been studied in detail, hindering the new SAM development and device optimization. In this study, SAMs prepared by kinetic‐driven spin‐coating are carefully investigated in terms of their surface morphology, density, and regularity, and proposed a correlation model between chemical structure and SAM quality. Additionally, the prepared SAMs are utilized as auxiliary layers on dielectrics and analyzed their effects on OFET properties. Through these investigations, a sequential relationship is established between chemical structure, SAM quality, and device performance, which can provide efficient feedback for system optimization.

Abstract 2D transition metal dichalcogenides (TMDCs) are atomically‐thick semiconductors with great potential for next‐generation optoelectronic applications, such as transistors and sensors. Their large surface‐to‐volume ratio makes them energy‐efficient but also extremely sensitive to the physical‐chemical surroundings. The latter must be carefully considered when predicting the electronic behavior, such as their energy level alignment, which ultimately affects the charge carrier injection and transport in devices. Here, local doping is demonstrated and thus adjusting the opto‐electronic properties of monolayer TMDCs (WSe2 and MoS2) by chemically engineering the surface of the supporting substrate. This is achieved by decorating the substrate by microcontact printing with patterns of two different self‐assembled monolayers (SAMs). The SAMs posses distinct molecular dipoles and dielectric constants, significantly influencing the TMDCs electronic and optical properties. By analyzing (on various substrtates), it is confirmed that these effects arise solely from the interaction between SAMs and TMDCs. Understanding the diverse dielectric environments experienced by TMDCs allows for a correlation between electronic and optical behaviours. The changes primarily involve alteration in the electronic band gap width, which can be calculated using the Schottky‐Mott rule, incorporating the dielectric screening of the TMDCs surroundings. This knowledge enables accurate prediction of the (opto‐)electronic behavior of monolayer TMDCs for advanced device design.

Abstract The surface functionalization by self‐assembled monolayers (SAMs) favors well‐packed organic semiconductor growth and reduces interfacial traps, which assists in developing high‐performance organic thin‐film transistors (OTFTs). Herein, the conventional SAM growth from the vapor phase is ameliorated and systematically studied. With 1H,1H,2H,2H‐Perfluorodecyltrichlorosilane as an example, it is found that deposition temperature of no less than 120 °C and deposition pressure of up to 0.02 bar is preferred for SAM deposition without morphological defects. The optimized SAMs are ultrasmooth with a surface roughness of 0.09 nm and can be escalated to wafer scale. It is verified that the growth condition is universal for other trichlorosilane species. Finally, it is shown that the OTFTs with defect‐free SAMs can achieve an average mobility of 1.79 cm2 V−1 s−1 using dinaphtho(2,3‐b:2′,3′‐f)thieno(3,2‐b)thiophene as the active layer, which is 2.06 times to the devices with defective SAMs and paces up the large‐area and high‐performance organic electronics.

Self-assembled monolayers (SAMs) as hole-collecting materials have made remarkable progress in inverted perovskite solar cells (PSCs). However, the incomplete coverage of SAMs and the non-intimate interface contact between perovskite/SAMs usually cause inferior interface characteristics and significant energy losses at the heterojunction interface. Herein, a post-assembled chelating molecular bridge strategy using 5-(9H-carbazol-9-yl)isophthalicacid (CB-PA) is developed to modify the perovskite/SAMs buried interface. It is found that CB-PA can be chemically coupled with MeO-2PACz through π-π stacking between carbazole groups, and chelate with perovskite by forming double C═O···Pb bonds, thus constructing a bridge-connected interface to promote carrier extraction. Simultaneously, the post-assembled CB-PA can fill the voids of MeO-2PACz to form dense hybrid SAMs, resulting in uniform surface potential and improved interface contact. Moreover, CB-PA treatment also tends to induce the oriented crystallization of perovskite films, passivate interface defects, and release lattice stress at the buried interface. Consequently, the CB-PA-based inverted PSCs achieve a champion efficiency of 25.27% with superior operational stability, retaining ≈94% of their initial efficiency after maximum power point (MPP) tracking (65 °C) for 1000 h with ISOS-L-2I protocol. This work provides an innovative strategy to address the buried interface challenges for high-performance inverted PSCs., (© 2025 Wiley‐VCH GmbH.)

Aromatic linker-constructed self-assembled monolayers (Ar-SAMs) with enlarged dipole moment can modulate the work function of indium tin oxide (ITO), thereby improving hole extraction/transport efficiency. However, the specific role of the aromatic linkers between the polycyclic head and the anchoring groups of SAMs in determining the performance of perovskite solar cells (PSCs) remains unclear. In this study, we developed a series of phenothiazine-based Ar-SAMs to investigate how different aromatic linkers could affect molecular stacking, the regulation of substrate work function, and charge carrier dynamics. When served as hole-selective layers (HSLs) in PSCs and monolithic perovskite/silicon tandem solar cells (P/S-TSCs), we found that the Ar-SAM with naphthalene linker along the 2,6-position axis (β-Nap) could form dense and highly ordered HSLs, enhancing interfacial interactions and favoring optimal energy level alignment with the perovskite films. Using this strategy, the optimized wide-band gap PSCs achieved an impressive power conversion efficiency (PCE) of 21.86 % with negligible hysteresis, utilizing a 1.68 eV perovskite. Additionally, the encapsulated devices demonstrated enhanced stability under damp-heat conditions (ISOS-D-2, 50 % RH, 65 °C) with a T 91 of 1000 hours. Notably, the fabricated P/S-TSCs, based on solution-processed micron-scale textured silicon heterojunction (SHJ) solar cells, achieved an efficiency of 28.89 % while maintaining outstanding reproducibility. This strategy holds significant promise for developing aromatic linking groups to enhance the hole selectivity of SAMs., (© 2024 Wiley-VCH GmbH.)

Carbazole-based self-assembled monolayers (SAMs) are widely used in inverted perovskite solar cells (PSCs). However, the biased intermolecular assembly of SAM molecules, and the lack of Lewis-basic heteroatoms to efficiently tune the crystallinity of perovskites and passivate the interface defects still limited the further improvement of the efficiency and stability for PSCs involving carbazole-based SAMs. Herein, a novel 3,6-dithiophene carbazole-based SAM molecule (named CzTh) is designed via the substituent engineering strategy, which is demonstrated to effectively solve the obstacles. The theory and experiment find that the introduction of thiophene regulated SAMs with the carbazole core in terms of surface wettability for precursor solvent, energy level alignment, the crystallization of perovskite films and defects passivation, which is attributed to dipole moment changes, and the Lewis base property of S atom. Consequently, the PSCs with CzTh achieved enhanced power conversion efficiency (PCE) and excellent air stability, compared to the commercial SAMs (Me-4PACz). As an "one-stone-three-birds" design strategy for SAMs, the "thiophene-substitution" effectively tunes the perovskite crystallization, passivates the defects, and enhances the hole injection at the perovskite/SAMs interface of inverted PSCs., (© 2025 Wiley‐VCH GmbH.)

Self-assembled monolayers (SAMs) play a critical role in modifying the buried interface of perovskite solar cells (PVSCs) by modulating the crystallization dynamics of perovskites and adjusting energy level alignment between perovskite layer and electrode. The integration of p-type SAMs has driven the power conversion efficiency (PCE) of inverted p-i-n structured PVSCs to a world record efficiency of 26.7%. However, in PVSCs with traditional n-i-p structures, n-type SAMs have not yet achieved comparable breakthroughs. Therefore, to unlock the full potential of n-type SAMs, this review provides a comprehensive summary of their molecular structures, deposition methods, and passivation mechanisms. Recent advances in various n-type SAMs, including fullerene-based, naphthalene imide-based, benzene-based SAMs, and SAMs with other structures have been discussed in detail. Finally, future research directions and their associated challenges are outlined to guide efforts toward realizing the full potential of n-type SAMs in PVSCs., (© 2025 Wiley‐VCH GmbH.)

Helicobacter pylori chronic infection is the highest risk factor for the development of gastric cancer, being this Gram-negative bacterium classified as carcinogenic. The mounting resistance of H. pylori to antibiotics calls for innovative therapeutic strategies. Here, the proof-of-concept studies that support the development of a "trojan horse" therapeutic strategy based on cholesterol-grafted nanoparticles (Chol-NP) to counteract H. pylori infection are depicted. The bacterium ability to specifically recognize and bind to surface grafted cholesterol is demonstrated by its adhesion to cholesterol(Chol)-functionalized self-assembled monolayers (SAMs) on gold substrates (2D Chol-SAMs) in a concentration dependent manner, with optimal Chol-SAMs prepared with 25% Chol-polyethylene glycol (PEG)-thiol in solution (75% tetra(ethylene glycol)-thiol). These results further show that cholesterol functionalized gold nanoparticles (3D Chol-SAMs, Chol-NP) eradicate H. pylori at a minimum bactericidal concentration of 125 µg mL -1 . Chol-NP kill H. pylori through internalization and membrane rupture, as observed by transmission electron microscopy (TEM). Chol-NP are cytocompatible (human gastric adenocarcinoma (AGS) cell line), non-hemolytic and innocuous to bacteria representative of the gut microbiota (Escherichia coli and Lactobacillus acidophilus). This study supports the further development of cholesterol functionalized biomaterials as an advanced and targeted treatment for H. pylori infection., (© 2025 The Author(s). Advanced Healthcare Materials published by Wiley‐VCH GmbH.)

The significant contact resistance at the metal-semiconductor interface is a well-documented issue for organic thin-film transistors (OTFTs) that hinders device and circuit performance. Here, this issue is tackled by developing three new thiol carbazole-based self-assembled monolayer (SAM) molecules, namely tBu-2SCz, 2SCz, and Br-2SCz, and utilizing them as carrier-selective injection interlayers. The SAMs alter the work function of gold electrodes by more than 1 eV, making them suitable for use in hole and electron-transporting OTFTs. Scanning tunneling microscopy analysis indicates that 2SCz and Br-2SCz form highly ordered molecular rows, resulting in work function values of 4.86 and 5.48 eV, respectively. The latter value is higher than gold electrodes modified by the commonly used pentafluorobenzenethiol (≈5.33 eV), making Br-2SCz promising for hole injection. Conversely, tBu-2SCz appears disordered with a lower work function of 4.52 eV, making it more suitable for electron injection. These intriguing properties are leveraged to demonstrate hole- and electron-transporting OTFTs with improved operating characteristics. All-organic complementary inverters are finally demonstrated by integrating p- and n-channel OTFTs, showcasing the potential of this simple yet powerful contact work function engineering approach. The present study highlights the versatility of thiol carbazole SAMs as carrier injecting interlayers for OTFTs and integrated circuits., (© 2024 The Author(s). Advanced Materials published by Wiley‐VCH GmbH.)

In recent years, self-assembled monolayers (SAMs) anchored on metal oxides (MO) have greatly boosted the performance of inverted (p-i-n) perovskite solar cells (PVSCs) by serving as hole-selective contacts due to their distinct advantages in transparency, hole-selectivity, passivation, cost-effectiveness, and processing efficiency. While the intrinsic monolayer nature of SAMs provides unique advantages, it also makes them highly sensitive to external pressure, posing a significant challenge for long-term device stability. At present, the stability issue of SAM-based PVSCs is gradually attracting attention. In this minireview, we discuss the fundamental stability issues arising from the structural characteristics, operating mechanisms, and roles of SAMs, and highlight representative works on improving their stability. We identify the buried interface stability concerns in three key aspects: 1) SAM/MO interface, 2) SAM inner layer, and 3) SAM/perovskite interface, corresponding to the anchoring group, linker group, and terminal group in the SAMs, respectively. Finally, we have proposed potential strategies for achieving excellent stability in SAM-based buried interfaces, particularly for large-scale and flexible applications. We believe this review will deepen understanding of the relationship between SAM structure and their device performance, thereby facilitating the design of novel SAMs and advancing their eventual commercialization in high-efficiency and stable inverted PVSCs., (© 2024 Wiley-VCH GmbH.)

Carbazole-based self-assembled molecules (SAMs) are widely applied in inverted perovskite solar cells (iPSCs) due to their unique molecular properties. However, the symmetrical structure of the carbazole-based SAMs makes it difficult to finely regulate their performance, which impedes the further enhancement of the efficiency and stability of iPSCs. This work demonstrates that by constructing an asymmetric carbazole core, 9H-thieno[2',3' : 4,5]thieno[3,2-b]indole) (TTID), the key properties of SAM molecules can be effectively regulated. It has been confirmed that the hybrid thieno[2,3-b]thiophene unit of this asymmetric core governs the energy level, the surface wettability, and the defect passivation capability of the SAMs, while the substituent of core has a greater impact on the molecular dipole and device stability. The synergistic effects from thieno[2,3-b]thiophene and fluorine lead to the KF-derived iPSC demonstrating a certified power conversion efficiency (PCE) of 25.17 % and excellent operational stability. This hybrid design concept offers a promising approach for the further structural modification of SAMs in iPSCs., (© 2024 Wiley-VCH GmbH.)

The integration of perovskites with mature silicon platform has emerged as a promising approach in the development of efficient on-chip light sources and high-brightness displays. However, the performance of Si-based green perovskite light-emitting diodes (PeLEDs) still falls significantly short compared to their red and near-infrared counterparts. In this study, it is revealed that the high work function Au, widely employed in Si-based top-emission PeLEDs as the reflective bottom electrode, exhibits considerably lower reflectivity in the green spectrum than in the longer wavelengths. Consequently, Ag electrode is introduced to replace Au to enhance the green light reflectivity, and the ultrathin MoO 3 and self-assembled monolayers (SAMs) are sequentially deposited for surface modification. These results indicate that the MoO 3 layer removes the energy barrier at Ag/polymer hole transport layer interface, enhancing the hole injection efficiency; while the SAMs firmly anchor onto the MoO 3 layer, effectively preventing interfacial defect formation. Benefited from this organic/inorganic dual-layer modification strategy, Si-based green PeLEDs with an impressive peak external quantum efficiency of 18.2% and a maximum brightness of 81931 cd m -2 are successfully fabricated, on par with those of the red and near-infrared counterparts. This achievement marks an advancement in developing high-performance Si-based PeLEDs with full-spectrum output., (© 2024 Wiley‐VCH GmbH.)

The Blue electroluminescence (EL) with high brightness and spectral stability is imperative for full-color perovskite display technologies meeting the Rec. 2020 standard. However, deep-blue perovskite light-emitting diodes (PeLEDs) lag behind their green- or red-emitting counterparts in brightness, quantum efficiency, and operational stability. Additionally, the Cl - /Br - mixed-halide perovskites with wide bandgap typically designed for deep-blue emitters are prone to degradation quickly under high operating bias due to low energy for halide migrations and vacancies formation, posing a significant challenge to spectral/operative stabilities. To address these issues, high-performance deep-blue PeLEDs are demonstrated by tuning the interface properties with Br-2ETP, a self-assembled monolayer (SAM) molecule engineered for a high dipole moment. The Br-2EPT-based hole-injecting interface facilitates favorable energy level alignment between indium tin oxide and the deep-lying valence band of the perovskite layer, suppressing the hole-injecting barrier and non-radiative charge recombination. Excellent perovskite film morphologies are observed at the top and buried surfaces by Br-2EPT, improving the balance of carrier injection for light emission efficiency. Consequently, the devices exhibit deep-blue electroluminescence at 457 nm, with an external quantum efficiency of 6.56% and spectral/operative stabilities., (© 2024 Wiley‐VCH GmbH.)

Triphenylamine-based Y-shaped organic sensitizers, specifically TPA-MN (1), TPA-CA (2), TPAT-MN (3), and TPAT-CA (4), are synthesized and utilized as p-type self-assembled monolayers (SAMs) for tin-based perovskite solar cells (TPSCs). These SAMs are developed using low-cost starting materials, primarily from triphenylamine (TPA) components. An extensive analysis is conducted to examine the crystalline, morphological, thermal, optical, electrochemical, and optoelectronic characteristics of SAMs 1-4, and the results are compared. A two-step method is employed to successfully develop tin perovskite layers on all four SAM surfaces. The resulting devices demonstrates PCE in the following order: TPAT-CA (8.1%) > TPAT-MN (6.1%) > TPA-MN (5.0%) > TPA-CA (4.2%). The TPAT-CA molecule, which contains a thiophene spacer, performed better than the other three SAMs in terms of rapid hole extraction rate, high hole mobility, and retarded charge recombination. Consequently, SAM TPAT-CA exhibited the highest device performance with excellent stability over time, retaining ≈90% from the beginning values after storage for 3000 h. The innovative Y-shaped SAMs describe in this study, characterized by their simple and efficient design, have the potential to contribute significantly to the advancement of perovskite photovoltaics, particularly in the development of cost-effective TPSC technology., (© 2024 The Author(s). Small published by Wiley‐VCH GmbH.)

Abstract Artificial receptor‐based protein assays have various attractive features such as a long‐term stability, a low‐cost production process, and the ease of tuning the target specificity. However, such protein sensors are still immature compared with conventional immunoassays. To enhance the application potential of synthetic sensing materials, organic field‐effect transistors (OFETs) are some of the suitable platforms for protein assays because of their solution processability, durability, and compact integration. Importantly, OFETs enable the electrical readout of the protein recognition phenomena of artificial receptors on sensing electrodes. Thus, we believe that OFETs functionalized with artificial protein receptors will be a powerful tool for the on‐site analyses of target proteins. In this Minireview, we summarize the recent progress of the OFET‐based protein assays including the rational design strategies for devices and sensing materials.

Abstract Tethered‐liquid perfluorocarbon (TLP) coatings show promise for blood‐contacting medical device applications to reduce blood adhesion and delay thrombosis. However, their fabrication and longevity under external fluid flow is not well characterized. A vapor phase silanization reaction leading to the formation of tethered‐perfluorocarbon (TP) layers containing large bumpy aggregates, 300 ± 200 nm thick, on top of an underlying 35 ± 15 nm thick uniform coating is reported. The vapor phase method compares favorably to the well‐established liquid phase deposition to reproducibly create slippery coatings on silicon and polystyrene with very low water sliding angles (2° ± 1°), without the need to control humidity conditions. The TP layer retains perfluorinated lubricants up to 20 000 s–1, using a cone‐and‐plate rheometer, with the higher viscosity lubricant perfluoroperhydrophenanthrene being more resistant to depletion than perfluorodecalin. TLP infused with either of the lubricants effectively reduces adhesion of fibrin from human whole blood relative to TP and control hydrophilic and hydrophobic surfaces. The combination of highly fluorinated TP coatings grafted from the vapor phase to create nanoscale structured surfaces infused with higher viscosity lubricant may be the most suitable combination for clinical applications of liquid‐infused surfaces to reduce thrombosis in blood‐contacting medical devices under flow.

The photovoltaic performance of inverted perovskite solar cells (PSCs) relies on effectively managing the interface between the hole extraction layer and the light-absorbing perovskite layer. In this study, we have synthesised (4-(3,6-bis(methylthio)-9H-carbazol-9-yl)butyl)phosphonic acid (MeS-4PACz), which forms a self-assembled monolayer (SAM) on the fluorine-doped tin oxide (FTO) electrode. The molecule's methylthio substituents generate a favourable interfacial dipole moment and interact with the perovskite layer. This interaction results in well-aligned energy levels among the FTO/SAM/perovskite layers, promoting efficient hole extraction and significantly reducing carrier recombination losses. Additionally, the methylthio groups passivate iodide vacancies and interact with Pb 2+ ions of the perovskite, reducing defect-induced trap states and enhancing the crystalline growth of the perovskite layer. Consequently, inverted PSCs incorporating MeS-4PACz achieve a power conversion efficiency of 25.13 %, along with outstanding photostability., (© 2024 Wiley-VCH GmbH.)

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 (>10 3 ), 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., (© 2024 Wiley‐VCH GmbH.)

Abstract Gaining control over the grafting geometry is critically important for any application of surface‐supported single‐molecule magnets (SMMs) in data storage, spintronics, and quantum information science. Here, tetrairon(III) SMMs with a propeller‐like structure are functionalized with thioacetyl‐terminated alkyl chains to promote chemisorption on gold surfaces from solution and to evaluate differences in adsorption geometry and magnetic properties as a function of chain length. The prepared monolayers are investigated using X‐ray absorption techniques with linearly and circularly polarized light to extract geometrical and magnetic information, respectively. All derivatives remain intact and form partially oriented monolayers on the gold surface. A ligand‐field analysis of the observed X‐ray natural linear dichroism shows that the threefold molecular axis is invariably biased toward the surface normal, in agreement with ab initio calculations. This preferential orientation is most pronounced in monolayers of the shortest‐chain derivative, which are further studied with an ultralow temperature X‐ray magnetic circular dichroism setup operating down to 350 mK. The isothermal field sweeps with the magnetic field at normal incidence show an open hysteresis loop below 1 K, while measurements at different incidence angles prove the magnetic anisotropy of the monolayers.

Three functionalized thienopyrazines (TPs), TP-MN (1), TP-CA (2), and TPT-MN (3) were designed and synthesized as self-assembled monolayers (SAMs) deposited on the NiOx film for tin-perovskite solar cells (TPSCs). Thermal, optical, electrochemical, morphological, crystallinity, hole mobility, and charge recombination properties, as well as DFT-derived energy levels with electrostatic surface potential mapping of these SAMs, have been thoroughly investigated and discussed. The structure of the TP-MN (1) single crystal was successfully grown and analyzed to support the uniform SAM produced on the ITO/NiOx substrate. When we used NiOx as HTM in TPSC, the device showed poor performance. To improve the efficiency of TPSC, we utilized a combination of new organic SAMs with NiOx as HTM, the TPSC device exhibited the highest PCE of 7.7 % for TP-MN (1). Hence, the designed NiOx/TP-MN (1) acts as a new model system for the development of efficient SAM-based TPSC. To the best of our knowledge, the combination of organic SAMs with anchoring CN/CN or CN/COOH groups and NiOx as HTM for TPSC has never been reported elsewhere. The TPSC device based on the NiOx/TP-MN bilayer exhibits great enduring stability for performance, retaining ~80 % of its original value for shelf storage over 4000 h., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Porous aromatic frameworks (PAFs) show promising potential in anionic conduction due to their high stability and customizable functionality. However, the insolubility of most PAFs presents a significant challenge in their processing into membranes and subsequent applications. In this study, continuous PAF membranes with adjustable thickness were successfully created using liquid-solid interfacial polymerization. The rigid backbone and the stable C-C coupling endow PAF membrane with superior chemical and dimensional stabilities over most conventional polymer membranes. Different quaternary ammonium functionalities were anchored to the backbone through flexible alkyl chains with tunable length. The optimal PAF membrane exhibited an OH - conductivity of 356.6 mS ⋅ cm -1 at 80 °C and 98 % relative humidity. Additionally, the PAF membrane exhibited outstanding alkaline stability, retaining 95 % of its OH - conductivity after 1000 hours in 1 M NaOH. To the best of our knowledge, this is the first application of PAF materials in anion exchange membranes, achieving the highest OH - conductivity and exceptional chemical/dimensional stability. This work provides the possibility for the potential of PAF materials in anionic conductive membranes., (© 2024 Wiley-VCH GmbH.)

The hole-transporting material (HTM), poly (3,4-ethylene dioxythiophene) poly(styrene sulfonate) (PEDOT : PSS), is the most widely used material in the realization of high-efficiency organic solar cells (OSCs). However, the stability of PEDOT : PSS-based OSCs is quite poor, arising from its strong acidity and hygroscopicity. In addition, PEDOT : PSS has an absorption in the infrared region and high highest occupied molecular orbital (HOMO) energy level, thus limiting the enhancement of short-circuit current density (J sc ) and open-circuit voltage (V oc ), respectively. Herein, two asymmetric self-assembled molecules (SAMs), namely BrCz and BrBACz, were designed and synthesized as HTM in binary OSCs based on the well-known system of PM6 : Y6, PM6 : eC9, PM6 : L8-BO, and D18 : eC9. Compared with BrCz, BrBACz shows larger dipole moment, deeper work function and lower surface energy. Moreover, BrBACz not only enhances photon harvesting in the active layer, but also minimizes voltage losses as well as improves interface charge extraction/ transport. Consequently, the PM6 : eC9-based binary OSC using BrBACz as HTM exhibits a champion efficiency of 19.70 % with a remarkable J sc of 29.20 mA cm -2 and a V oc of 0.856 V, which is a record efficiency for binary OSCs so far. In addition, the unencapsulated device maintains 95.0 % of its original efficiency after 1,000 hours of storage at air ambient, indicating excellent long-term stability., (© 2024 Wiley‐VCH GmbH.)

In the last two decades, perchlorate salts have been identified as environmental pollutants and recognized as potential substances affecting human health. We describe self-assembled monolayers (SAMs) of novel semiaza-bambus[6]urils (semiaza-BUs) equipped with thioethers or disulfide (dithiolane) functionalities as surface-anchoring groups on gold electrodes. Cyclic voltammetry (CV) with Fe(CN) 6 3-/4- as a redox probe, together with X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and ellipsometry, were employed to characterize the interactions at the interface between the anchoring groups and the metal substrate. Data showed that the anion receptors' packing on the gold strongly depends on the anchoring group. As a result, SAMs of BUs with lipoic amide side chains show a concentration-dependent layer thickness. The BU SAMs are extremely stable on repeated electrochemical potential scans and can selectively recognize perchlorate anions. Our electrochemical impedance spectroscopy (EIS) studies indicated that semiaza-BU equipped with the lipoic amide side chains binds perchlorate (2-100 mM) preferentially over other anions such as F - , Cl - , I - , AcO - , H 2 PO 4 - , HPO 4 2- , SO 4 2- , NO 2 - , NO 3 - , or CO 3 2- . The resistance performance is 10 to 100 times more efficient than SAMs containing all other tested anions., (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

The combined effects of compact TiO 2 (c-TiO 2 ) electron-transport layer (ETL) are investigated without and with mesoscopic TiO 2 (m-TiO 2 ) on top, and without and with an iodine-terminated silane self-assembled monolayer (SAM), on the mechanical behavior, opto-electronic properties, photovoltaic (PV) performance, and operational-stability of solar cells based on metal-halide perovskites (MHPs). The interfacial toughness increases almost threefold in going from c-TiO 2 without SAM to m-TiO 2 with SAM. This is attributed to the synergistic effect of the m-TiO 2 /MHP nanocomposite at the interface and the enhanced adhesion afforded by the iodine-terminated silane SAM. The combination of m-TiO 2 and SAM also offers a significant beneficial effect on the photocarriers extraction at the ETL/MHP interface, resulting in perovskite solar cells (PSCs) with power-conversion efficiency (PCE) of over 24% and 20% for 0.1 and 1 cm 2 active areas, respectively. These PSCs also have exceptionally long operational-stability lives: extrapolated T80 (duration at 80% initial PCE retained) is ≈18 000 and 10 000 h for 0.1 and 1 cm 2 active areas, respectively. Postmortem characterization and analyses of the operational-stability-tested PSCs are performed to elucidate the possible mechanisms responsible for the long operational-stability., (© 2023 Wiley-VCH GmbH.)

Self-assembled monolayers (SAMs) of N-heterocyclic olefins (NHOs) have been prepared on Au(111) and their thermal stability, adsorption geometry, and molecular order were characterized by X-ray photoelectron spectroscopy, polarized X-ray absorption spectroscopy, scanning tunneling microscopy (STM), and density functional theory (DFT) calculations. The strong σ-bond character of NHO anchoring to Au induced high geometrical flexibility that enabled a flat-lying adsorption geometry via coordination to a gold adatom. The flat-lying adsorption geometry was utilized to further increase the surface interaction of the NHO monolayer by backbone functionalization with methyl groups that induced high thermal stability and a large impact on work-function values, which outperformed that of N-heterocyclic carbenes. STM measurements, supported by DFT modeling, identified that the NHOs were self-assembled in dimers, trimers, and tetramers constructed of two, three, and four complexes of NHO-Au-adatom. This self-assembly pattern was correlated to strong NHO-Au interactions and steric hindrance between adsorbates, demonstrating the crucial influence of the carbon-metal σ-bond on monolayer properties., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Beyond their CO 2 emittance when burned as fuels, hydrocarbons (HCs) serve as omnipresent raw materials and commodities. No matter if as liquid oil spills or the endless amounts of plastic roaming the oceans, HCs behave as persistent pollutants with water as main carrier to distribute. Even if their general chemical structure [-(CH 2 ) n -] is quite simple, the endless range of n leads to contaminations of different appearances and properties. A water remediation method based on superparamagnetic iron oxide nanoparticles (SPIONs) modified with self-assembled monolayers of alkyl phosphonic acid derivatives is presented. These molecules enable the SPIONs to non-covalently bind HCs, independently from the molecular weight, size and morphology. The attractive interaction is mainly based on hydrophobic and Coulomb interaction, which allows recycling of the SPIONs. The superparamagnetic core allows a simple magnetic collection and separation from the water phase which makes it a promising addition to wastewater treatment. Agglomerates of collected plastic "waste" even exhibit superior adsorption properties for crude oil, another hydrocarbon waste which gives these collected wastes a second life. This upcycling approach combined with presented recycling methods enables a complete recycling loop., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Slippery covalently-attached liquid surfaces (SCALS) with low contact angle hysteresis (CAH, <5°) and nanoscale thickness display impressive anti-adhesive properties, similar to lubricant-infused surfaces. Their efficacy is generally attributed to the liquid-like mobility of the constituent tethered chains. However, the precise physico-chemical properties that facilitate this mobility are unknown, hindering rational design. This work quantifies the chain length, grafting density, and microviscosity of a range of polydimethylsiloxane (PDMS) SCALS, elucidating the nanostructure responsible for their properties. Three prominent methods are used to produce SCALS, with characterization carried out via single-molecule force measurements, neutron reflectometry, and fluorescence correlation spectroscopy. CO 2 snow-jet cleaning was also shown to reduce the CAH of SCALS via a modification of their grafting density. SCALS behavior can be predicted by reduced grafting density, Σ, with the lowest water CAH achieved at Σ≈2. This study provides the first direct examination of SCALS grafting density, chain length, and microviscosity and supports the hypothesis that SCALS properties stem from a balance of layer uniformity and mobility., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Self-assembled monolayers (SAMs) offer the advantage of facile interfacial modification, leading to significant improvements in device performance. In this study, we report the design and synthesis of a new series of carboxylic acid-functionalized porphyrin derivatives, namely AC-1, AC-3, and AC-5, and present, for the first time, a strategy to exploit the large π-moiety of porphyrins as a backbone for interfacing the indium tin oxide (ITO) electrode and perovskite active layer in an inverted perovskite solar cell (PSC) configuration. The electron-rich nature of porphyrins facilitates hole transfer and the formation of SAMs, resulting in a dense surface that minimizes defects. Comprehensive spectroscopic and dynamic studies demonstrate that the double-anchored AC-3 and AC-5 enhance SAMs on ITO, passivate the perovskite layer, and function as conduits to facilitate hole transfer, thus significantly boosting the performance of PSCs. The champion inverted PSC employing AC-5 SAM achieves an impressive solar efficiency of 23.19 % with a high fill factor of 84.05 %. This work presents a novel molecular engineering strategy for functionalizing SAMs to tune the energy levels, molecular dipoles, packing orientations to achieve stable and efficient solar performance. Importantly, our comprehensive investigation has unraveled the associated mechanisms, offering valuable insights for future advancements in PSCs., (© 2023 Wiley-VCH GmbH.)

Better control of molecule-electrode coupling (Γ) to minimize leakage current is an effective method to optimize the functionality of molecular diodes. Herein we embedded 5 isomers of phenypyridyl derivatives, each with an N atom placed at a different position, in two electrodes to fine-tune Γ between self-assembled monolayers (SAMs) and the top electrode of EGaIn (eutectic Ga-In terminating in Ga 2 O 3 ). Combined with electrical tunnelling results, characterizations of electronic structures, single-level model fittings, and DFT calculations, we found that the values of Γ of SAMs formed by these isomers could be regulated by nearly 10 times, thereby contributing to the leakage current changing over about two orders of magnitude and switching the isomers from resistors to diodes with a rectification ratio (r + =|J(+1.5 V)/J(-1.5 V)|) exceeding 200. We demonstrated that the N atom placement can be chemically engineered to tune the resistive and rectifying properties of the molecular junctions, making it possible to convert molecular resistors into rectifiers. Our study provides fundamental insights into the role of isomerism in molecular electronics and offers a new avenue for designing functional molecular devices., (© 2023 Wiley-VCH Verlag GmbH.)

Chiral molecules have recently received renewed interest as highly efficient sources of spin-selective charge emission known as chiral-induced spin selectivity (CISS), which potentially offers a fascinating utilization of organic chiral materials in novel solid-state spintronic devices. However, a practical use of CISS remains far from completion, and rather fundamental obstacles such as (i) external controllability of spin, (ii) function durability, and (iii) improvement of spin-polarization efficiency have not been surmounted to date. In this study, these issues are addressed by developing a self-assembled monolayer (SAM) of overcrowded alkene (OCA)-based molecular motor. With this system, it is successfully demonstrated that the direction of spin polarization can be externally and repeatedly manipulated in an extremely stable manner by switching the molecular chirality, which is achieved by a formation of the covalent bonds between the molecules and electrode. In addition, it is found that a higher stereo-ordering architecture of the SAM of OCAs tailored by mixing them with simple alkanethiols considerably enhances the efficiency of spin polarization per a single OCA molecule. All these findings provide the creditable feasibility study for strongly boosting development of CISS-based spintronic devices that can simultaneously fulfill the controllability, durability, and high spin-polarization efficiency., (© 2023 The Authors. Small published by Wiley-VCH GmbH.)

Patterned, ultra-thin surface layers can serve as templates for positioning nanoparticlesor targeted self-assembly of molecular structures, for example, block-copolymers. This work investigates the high-resolution, atomic force microscopebased patterning of 2 nm thick vinyl-terminated polystyrene brush layers and evaluates the line broadening due to tip degradation. This work compares the patterning properties with those of a silane-based fluorinated self-assembled monolayer (SAM), using molecular heteropatterns generated by modified polymer blend lithography (brush/SAM-PBL). Stable line widths of 20 nm (FWHM) over lengths of over 20000 µm indicate greatly reduced tip wear, compared to expectations on uncoated SiO x surfaces. The polymer brush acts as a molecularly thin lubricating layer, thus enabling a 5000 fold increase in tip lifetime, and the brush is bonded weakly enough that it can be removed with surgical accuracy. On traditionally used SAMs, either the tip wear is very high or the molecules are not completely removed. Polymer Phase Amplified Brush Editing is presented, which uses directed self-assembly to amplify the aspect ratio of the molecular structures by a factor of 4. The structures thus amplified allow transfer into silicon/metal heterostructures, fabricating 30 nm deep, all-silicon diffraction gratings that could withstand focused high-power 405 nm laser irradiation., (© 2023 The Authors. Small published by Wiley-VCH GmbH.)

Self-assembled monolayers (SAMs) are an important element of modern nanotechnology and surface functionalization. However, their application is still limited because they are easily removed from the surface of the object in corrosive environments. Crosslinking would make SAMs more resistant to the corrosive environment they are exposed to. In this work, how to strongly crosslink SAMs made of non-toxic and biodegradable fatty acids on metal surfaces using ionizing radiation has been demonstrated for the first time. The crosslinked nanocoatings are stable over time and have significantly improved properties compared to SAMs. Thus, crosslinking opens up the possibility of using SAMS in a variety of different systems and on different materials for surface functionalization to achieve stable and durable surface properties such as biocompatibility or selective reactivity., (© 2023 Wiley-VCH GmbH.)

Herein, a new ternary strategy to fabricate efficient and photostable inverted organic photovoltaics (OPVs) is introduced by combining a bulk heterojunction (BHJ) blend and a fullerene self-assembled monolayer (C 60 -SAM). Time-of-flight secondary-ion mass spectrometry - analysis reveals that the ternary blend is vertically phase separated with the C 60 -SAM at the bottom and the BHJ on top. The average power conversion efficiency - of OPVs based on the ternary system is improved from 14.9% to 15.6% by C 60 -SAM addition, mostly due to increased current density (J sc ) and fill factor -. It is found that the C 60 -SAM encourages the BHJ to make more face-on molecular orientation because grazing incidence wide-angle X-ray scattering - data show an increased face-on/edge-on orientation ratio in the ternary blend. Light-intensity dependent J sc data and charge carrier lifetime analysis indicate suppressed bimolecular recombination and a longer charge carrier lifetime in the ternary system, resulting in the enhancement of OPV performance. Moreover, it is demonstrated that device photostability in the ternary blend is enhanced due to the vertically self-assembled C 60 -SAM that successfully passivates the ZnO surface and protects BHJ layer from the UV-induced photocatalytic reactions of the ZnO. These results suggest a new perspective to improve both performance and photostability of OPVs using a facial ternary method., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Intermolecular charge transport is one of the essential modes for modulating charge transport in molecular electronic devices. Supermolecules are highly promising candidates for molecular devices because of their abundant structures and easy functionalization. Herein, we report an efficient strategy to enhance charge transport through pillar[5]arene self-assembled monolayers (SAMs) by introducing cationic guests. The current density of pillar[5]arene SAMs can be raised up to about 2.1 orders of magnitude by inserting cationic molecules into the cavity of pillar[5]arenes in SAMs. Importantly, we have also observed a positive correlation between the charge transport of pillar[5]arene-based complex SAMs and the binding affinities of the pillar[5]arene-based complexation. Such an enhancement of charge transport is attributed to the efficient host-guest interactions that stabilize the supramolecular complexes and lower the energy gaps for charge transport. This work provides a predictive pattern for the regulation of intermolecular charge transport in guiding the design of next generation switches and functional sensors in supramolecular electronics., (© 2023 Wiley-VCH GmbH.)

Particular interest has been focused on modulation of solid-state charge transport (CT) in DNA. Nevertheless, it remains challenging to do so in a sensitive and predictive manner due to the lack of a definite relationship between DNA base pair stacking and DNA CT. The challenges can be mainly attributed to the ill-defined systems, which may lead to ambiguous and even contradictory conclusions. Here, we use DNA hairpins to construct the well-defined self-assembled monolayers. We reveal nearly positive-linear correlations between DNA conformation and CT in the DNA hairpins regulated with metal ion chelation and DNA sequence. The correlations have been confirmed by the solid-state current-voltage characteristics and circular dichroism in solution. The enhanced CT via metal ion chelated DNA hairpins is mainly from the improved DNA energy coupling to electrodes, not the almost unchanged energy barrier when Hg ion-induced DNA conformational switches toward the canonical B-form., (© 2023 Wiley-VCH GmbH.)

This study examines thermoresponse of odd-even effect in self-assembled monolayers (SAMs) of n-alkanethiolates (SC n , n=3-18) formed on template-stripped gold (Au TS ) using macro- and microscopic analytical techniques, contact angle goniometry (CAG) and vibrational sum frequency generation (VSFG) spectroscopy, respectively. Both CAG and VSFG analyses showed that the odd-even effect in liquid-like SAMs (n=3-9) disappeared upon heating at 50-70 °C, indicating that the heating led to increased structural disorder regardless of odd and even carbon numbers. In contrast, the opposite thermoresponse was observed for odd and even SC n molecules in wax- and solid-like SAMs (n=10-18). Namely, temperature-dependent orientational change of terminal CH 3 relative to the surface normal was opposite for the odd and even molecules, thereby leading to mitigated odd-even effect. Our work offers important insights into thermoresponse of supramolecular structure in condensed organic matter., (© 2022 Wiley-VCH GmbH.)

The quest for developing quantum technologies is driven by the promise of exponentially faster computations, ultrahigh performance sensing, and achieving thorough understanding of many-particle quantum systems. Molecular spins are excellent qubit candidates because they feature long coherence times, are widely tunable through chemical synthesis, and can be interfaced with other quantum platforms such as superconducting qubits. A present challenge for molecular spin qubits is their integration in quantum devices, which requires arranging them in thin films or monolayers on surfaces. However, clear proof of the survival of quantum properties of molecular qubits on surfaces has not been reported so far. Furthermore, little is known about the change in spin dynamics of molecular qubits going from the bulk to monolayers. Here, a versatile bottom-up method is reported to arrange molecular qubits as functional groups of self-assembled monolayers (SAMs) on surfaces, combining molecular self-organization and click chemistry. Coherence times of up to 13 µs demonstrate that qubit properties are maintained or even enhanced in the monolayer., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Hole-transporting layers (HTLs) are an essential component in inverted, p-i-n perovskite solar cells (PSCs) where they play a decisive role in extraction and transport of holes, surface passivation, perovskite crystallization, device stability, and cost. Currently, the exploration of efficient, stable, highly transparent and low-cost HTLs is of vital importance for propelling p-i-n PSCs toward commercialization. Compared to their inorganic counterparts, organic HTLs offer multiple advantages such as a tunable bandgap and energy level, easy synthesis and purification, solution processability, and overall low cost. Here, recent progress of organic HTLs, including conductive polymers, small molecules, and self-assembled monolayers, as utilized in inverted PSCs is systematically reviewed and summarized. Their molecular structure, hole-transport properties, energy levels, and relevant device properties and resulting performances are presented and analyzed. A summary of design principles and a future outlook toward highly efficient organic HTLs in inverted PSCs is proposed. This review aims to inspire further innovative development of novel organic HTLs for more efficient, stable, and scalable inverted PSCs., (© 2022 Wiley-VCH GmbH.)

The wide use of copper is limited by its rapid oxidation. Main oxidation mitigation approaches involve alloying or surface passivation technologies. However, surface alloying often modifies the physical properties of copper, while surface passivation is characterized by limited thermal and chemical stability. Herein, we demonstrate an electrochemical approach for surface-anchoring of an N-heterocyclic carbene (NHC) nanolayer on a copper electrode by electro-deposition of alkyne-functionalized imidazolium cations. Water reduction reaction generated a high concentration of hydroxide ions that induced deprotonation of imidazolium cations and self-assembly of NHCs on the copper electrode. In addition, alkyne group deprotonation enabled on-surface polymerization by coupling surface-anchored and solvated NHCs, which resulted in a 2 nm thick NHC-nanolayer. Copper film coated with a NHC-nanolayer demonstrated high oxidation resistance at elevated temperatures and under alkaline conditions., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Self-assembled monolayers (SAMs) are becoming widely utilized as hole-selective layers in high-performance p-i-n architecture perovskite solar cells. Ultrasonic spray coating and airbrush coating are demonstrated here as effective methods to deposit MeO-2PACz; a carbazole-based SAM. Potential dewetting of hybrid perovskite precursor solutions from this layer is overcome using optimized solvent rinsing protocols. The use of air-knife gas-quenching is then explored to rapidly remove the volatile solvent from an MAPbI 3 precursor film spray-coated onto an MeO-2PACz SAM, allowing fabrication of p-i-n devices with power conversion efficiencies in excess of 20%, with all other layers thermally evaporated. This combination of deposition techniques is consistent with a rapid, roll-to-roll manufacturing process for the fabrication of large-area solar cells., (© 2022 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Repeated charge/discharge in aqueous zinc-ion batteries (ZIBs) commonly results in surface corrosion/passivation and dendrite formation on zinc anodes, which is a major challenge for the commercialization of zinc-based batteries. In this work, metallic Zn modified by self-assembled monolayers is described as a viable anode for ZIBs. ω-mercaptoundecanoic acid that is spontaneously adsorbed on Zn (MUDA/Zn) contributes to the simultaneous suppression of side reactions and dendrite formation in ZIBs. Though one-molecular-thick, densely packed alkyl chains prohibit H 2 O and H + from making direct contact with the underlying Zn, and surface carboxylate moieties (-COO - ) effectively repel anionic species (OH - ) in a solution, which renders a Zn anode inert against zincate formation within a wide range of pH. In contrast, the electrostatic attraction between surface-carboxylates and cations increases the concentration of Zn 2+ on the surface of MUDA/Zn to facilitate Zn plating/stripping with less overpotentials. The high concentration of Zn 2+ also results in an increased number of nucleation sites, which enhances the lateral growth of Zn with no formation of dendrites. As a result, MUDA/Zn shows excellent stability during prolonged Zn plating/stripping within a wide range of pH. The advantageous properties of MUDA/Zn are also retained in full-cells coupled with δ-MnO 2 cathodes., (© 2022 Wiley-VCH GmbH.)

Small scratches and abrasion cause damage to packaging coatings. Albeit often invisible to the human eye, such small defects in the coating may ultimately have a strong negative impact on the whole system. For instance, gases may penetrate the coating and consequently the package barrier, thus leading to the degradation of sensitive goods. Herein, the indicators of mechanical damage in the form of particles are reported, which can readily be integrated into coatings. Shear stress-induced damage is indicated by the particles via a color change. The particles are designed as core-shell supraparticles. The supraparticle core is based on rhodamine B dye-doped silica nanoparticles, whereas the shell is made of alumina nanoparticles. The alumina surface is functionalized with a monolayer of a perylene dye. The resulting core-shell supraparticle system thus contains two colors, one in the core and one in the shell part of the architecture. Mechanical damage of this structure exposes the core from the shell, resulting in a color change. With particles integrated into a coating lacquer, mechanical damage of a coating can be monitored via a color change and even be related to the degree of oxygen penetration in a damaged coating., (© 2022 The Authors. Small published by Wiley-VCH GmbH.)

Prelithiation can replenish active Li into the battery to compensate the Li consumption due to the formation of solid electrolyte interphase (SEI) on the electrode surface, therefore improving the energy density of Li-ion batteries (LIBs), especially for batteries using electrode materials with low initial Coulombic efficiency (ICE). However, practical prelithiation in LIBs is a challenge since most lithiated compounds with high specific capacity are unstable and industrially incompatible. Herein, an effective prelithiation strategy is demonstrated by using a lithium-carbon (Li-C) microsphere composite. These Li-C microspheres are passivated by a self-assembled monolayer of octadecylphosphonic acid, which suppresses the reaction between Li and commonly used slurry solvent 1-methyl-2-pyrrolidinone (NMP). After the addition of passivated Li-C into the NMP-based graphite slurry, the ICE of the graphite||Li half-cell boosts from 88.5% to 100.5%. In a 4.5 V LiCoO 2 (LCO)||graphite full-cell, the supplementary Li source avoids excessive delithiation of LCO, thus suppressing the destructive phase transformation at high delithiation potential. As a result, the prelithiated LCO||graphite full-cell presents an initial discharge capacity of 201 mAh g -1 and the capacity retention after 100 cycles increases by 7.1 %. This work provides a practical approach for developing high energy density and long cycle life LIBs., (© 2021 Wiley-VCH GmbH.)