Architecture Design and Interface Engineering of Self-assembly VS_(4)/rGO Heterostructures for Ultrathin Absorbent

The employment of microwave absorbents is highly desirable to address the increasing threats of electromagnetic pollution.Importantly,developing ultrathin absorbent is acknowledged as a linchpin in the design of lightweight and flexible electronic devices,but there are remaining unprecedented challenges.Herein,the self-assembly VS_(4)/rGO heterostructure is constructed to be engineered as ultrathin microwave absorbent through the strategies of architecture design and interface engineering.The microarchitecture and heterointerface of VS_(4)/rGO heterostructure can be regulated by the generation of VS_(4) nanorods anchored on rGO,which can effectively modulate the impedance matching and attenuation constant.The maximum reflection loss of 2VS_(4)/rGO40 heterostructure can reach−43.5 dB at 14 GHz with the impedance matching and attenuation constant approaching 0.98 and 187,respectively.The effective absorption bandwidth of 4.8 GHz can be achieved with an ultrathin thickness of 1.4 mm.The far-reaching comprehension of the heterointerface on microwave absorption performance is explicitly unveiled by experimental results and theoretical calculations.Microarchitecture and heterointerface synergistically inspire multi-dimensional advantages to enhance dipole polarization,interfacial polarization,and multiple reflections and scatterings of microwaves.Overall,the strategies of architecture design and interface engineering pave the way for achieving ultrathin and enhanced microwave absorption materials.

The Effects of Contact Interface on the Friction Characteristics of Self-assembly Monolayers

The effects of different contact interfaces on the friction characteristics of OTS self-assembled monolayers were investigated by a universal micro-tribometer in different sliding velocities. The results indicate that there exist lower friction coefficients between OTS SAMs and Ti, Ni and Cu films deposited on GCr15 steel balls than those between OTS SAMs and GCr15 steel ball. The friction coefficient between OTS SAMs and Ti film is the largest, and the friction coefficient between OTS SAMs and Cu film is the least in these three films, which depends on the intrinsic characteristics of the materials. The friction coefficients between OTS SAMs and GCr15 steel ball and three nanometer films increase with the sliding velocity increasing, which can be explained by the relaxation characteristics of OTS molecules.

Role of self-assembled molecules’anchoring groups for surface defect passivation and dipole modulation in inverted perovskite solar cells

Inverted perovskite solar cells have gained prominence in industrial advancement due to their easy fabrication,low hysteresis effects,and high stability.Despite these advantages,their efficiency is currently limited by excessive defects and poor carrier transport at the perovskite-electrode interface,particularly at the buried interface between the perovskite and transparent conductive oxide(TCO).Recent efforts in the perovskite community have focused on designing novel self-assembled molecules(SAMs)to improve the quality of the buried interface.However,a notable gap remains in understanding the regulation of atomic-scale interfacial properties of SAMs between the perovskite and TCO interfaces.This understanding is crucial,particularly in terms of identifying chemically active anchoring groups.In this study,we used the star SAM([2-(9H-carbazol-9-yl)ethyl]phosphonic acid)as the base structure to investigate the defect passivation effects of eight common anchoring groups at the perovskite-TCO interface.Our findings indicate that the phosphonic and boric acid groups exhibit notable advantages.These groups fulfill three key criteria:they provide the greatest potential for defect passivation,exhibit stable adsorption with defects,and exert significant regulatory effects on interface dipoles.Ionized anchoring groups exhibit enhanced passivation capabilities for defect energy levels due to their superior Lewis base properties,which effectively neutralize local charges near defects.Among various defect types,iodine vacancies are the easiest to passivate,whereas iodine-substituted lead defects are the most challenging to passivate.Our study provides comprehensive theoretical insights and inspiration for the design of anchoring groups in SAMs,contributing to the ongoing development of more efficient inverted perovskite solar cells.

SELF-ASSEMBLED QUANTUM DOTS ON AU AND THE INTERFACE FLUORESCENCE

In this paper,amino capped CdSe/ZnS quantum dots(QDs)were immobilized on the 11-mercaptoundecanoic acid(MUA)self-assembled Au surface(SAM/Au)by 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride(EDC).Atomic force microscopy(AFM),fluorescence imaging and electrochemistry were employed to characterize the surface.The results showed that CdSe/ZnS QDs were immobilized on the surface of SAM/Au successfully.Based on this method,the fluorescence of the QDs on the SAM/Au was monitored on-line.

Host–Guest Molecular Recognition at Liquid–Liquid Interfaces

Host–guest molecular recognition at the liquid–liquid interface endows the interface with unique properties,including stimuli-responsiveness and self-regulation,due to the dynamic and reversible nature of non-covalent interactions.Increasing research efforts have been put into the preparation of supramolecular interfacial systems such as films and microcapsules by integrating functional components(e.g.,colloidal particles,polymers)at the interface,providing tremendous opportunities in the areas of encapsulation,delivery vehicles,and biphasic reaction systems.In this review,we summarize recent progress in supramolecular interfacial systems assembled by host–guest chemistry,and provide an overview of the fabrication process,functions,and promising applications of the resultant constructs.

Self-assembly at Liquid-Liquid Interface: A New SERS Substrate for Analytical Sensing

As a highly powerful and sensitive tool,surface enhanced Raman scattering(SERs)has attracted extensive attention in quantification analysis.However,the strong dependence of SERS signal on the detailed local nanostructure makes quantitative SERS analysis suffer from difficulties in controlling the uniformity of nanoscale hot spots and the inefficiency of placing the targeted molecules in prefabricated hot spots.

Length-dependent alignment of large-area semiconducting carbon nanotubes self-assembly on a liquid–liquid interface

Aligned arrays of semiconducting carbon nanotubes(s-CNTs)with high homogenous density and orientation are urgently needed for high-performance carbon-based electronics.Herein,a length-controlled approach using combined technologies was developed to regulate the s-CNT length and reduce the length distribution.The impact of different lengths and length distributions was studied during aligned self-assembly on a liquid–liquid confined interface was investigated.The results show that short s-CNTs with a narrow distribution have the best alignment uniformity over the large scale.The optimized and aligned s-CNT array can reach a density as high as 100 CNTs·μm−1 on a 4-inch wafer.The field-effect transistor(FET)performance of these optimized s-CNT arrays was 64%higher than arrays without length-control.This study clarified that rational control of s-CNTs with desired length and length distribution on the aligned self-assembly process within the liquid–liquid confined interface.The results illustrate a solid foundation for the application of emerging carbon-based electronics.

Mesoporous polymers:soft-template self-assembly synthesis and applications

Mesoporous polymers combine the advantages of polymer materials(abundant polar functional groups,lightweight,flexibility,and processability)and mesoporous structures(high specific surface area,adjustable pore structure,and large pore volume);hence,they have great application potential in sensing,adsorption,catalysis,energy storage,biomedicine,etc.Currently,developing advanced synthetic strategies for mesoporous polymers and investigating their intrinsic applications have become hot research topics.Soft-template-based self-assembly is regarded as a promising approach for synthesizing mesoporous polymers.This work reviews recent progress in the synthetic strategy for producing various mesoporous polymers using soft-template selfassembly,focusing on the synthesis of conductive polymers,phenol-based polymers,and resin-based polymers and their potential applications.Finally,perspectives on future applications of mesoporous polymers,along with a few challenges that need to be resolved,are also discussed in this review.

Temperature-regulated self-assembly of lipids at free bubbles interface:A green and simple method to prepare micro/nano bubbles

Micro/nanobubbles play an essential role in ultrasound-based biomedical applications.Here,a green and simple method to fabricate micro/nanobubbles was developed by the temperature-regulated self-assembly of lipids in the presence of free bubbles.The self-assembly mechanism of lipids interacting with gas-water interfaces was investigated,and the ultrasound imaging of the obtained lipid-encapsulated bubbles(LBs)was further confirmed.Above the phase transition temperature(Tm),fluid lipids transform from vesicles to micelles,and further assemble to the free bubbles interface to be a compressed monolayer,resulting in lipid shelled microbubbles.Cooling below 7m induces the lipid shell to glassy state and stables the LBs.Moreover,increasing the 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy(polyethylene glycol)-2000](DSPE-PEG2K)content in lipids formulation can further manipulate the shell curvature and reduce the LBs size into nanobubbles.LBs with diameters of 1.68±0.11 pm,704±7 nm and 208±6 nm were successfully prepared.The in vitro and in vivo ultrasound imaging results showed that all of the LBs had excellent echogenicity.The nanosized LBs revealed elongated imaging duration time and greater microvascular details for the liver tissue.Avoiding the organic solvent and complicated multiple preparation process,this method has great potential in construction of various multifunctional micro/nanobubbles with size control for theranostic applications.

Self-assembly of nanoparticles at solid-liquid interface for electrochemical capacitors

Self-assembly of nanoparticles at solid-liquid interface could be promising to realize the assembled functions for various applications,such as rechargeable batteries,supercapacitors,and electrocatalysis.This review summarizes the self-assembly of the nanoparticles at solid-liquid interface according to the different driving forces of assembly,including hydrophilic-hydrophobic interactions,solvophobic and electrostatic interaction.To be specific,the self-assembly can be divided into the following two types:surfactant-assisted self-assembly and direct self-assembly of Janus particles(inorganic and amphiphilic copolymer-inorganic Janus nanoparticles).Using the emulsion stabilized by nanoparticles as the template,the self-assembly constructed by the interaction of the nanostructure unit(including metal,metal oxide,and semiconductor,etc.)not only possesses the characteristic of nanostructure unit,but also exhibits the excellent assembly performance in electrochemistry aspect.The application of these assemblies in the area of electrochemical capacitors is presented.Finally,the current research progress and perspectives toward the self-assembly of nanoparticles at stabilized solid-liquid interface are proposed.

Natural interface-mediated self-assembly of graphene-isolatednanocrystals for plasmonic arrays construction and personalized information acquisition

As Interface mediated self-assembly of nanocrystals provide excellent strategy for sensing,catalysis or photonics,the construction of innovative interfaces and development of versatile strategies for nanocrystal synthesis are urgently needed.Herein,latent fingerprints(LFPs),the most common markers for human identity,are used as naturally accessible interface for organization of graphene isolated nanocrystals(GINs).Excitingly,the selective adsorption of GINs on lipidic ridge provides a universal approach for the in-situ construction of the plasmonic arrays.Such system with intrinsic chrominance and Raman signal enables the high resolution colorimetric and surfaced-enhanced Raman spectroscopy(SERS)dual-mode imaging,which can detail the structures of the LFPs from 1st to 3rd level even the LFPs are shielded.Furthermore,the interface can be constructed on diverse materials by a simple finger-pressing process and the densely packed arrays can serve as superior SERS substrate for label-free,non-invasive acquisition of molecule information especially residues in LFPs.The combination of chemical composition with detailed structures efficiently recognizes the human identity and could help link it to a crime scene.Overall,the LFPs can act as natural platform for interface mediated localized assembly and personalized information acquisition for forensic science or precise medicine.

Engineering the Morphologies of Block Copolymer Particles from the Confined Self-assembly within Emulsion Droplets

Block copolymers(BCPs)can automatically assemble into various regulated nanoparticles when they are confined within the emulsion droplet be-cause of the structural frustration of polymer chains and the soft template effect of the oil/water interface.In the past few years,great efforts have been made to regulate the morphologies of the resulting BCP particles.In this review article,various strategies for tuning oil/water interfacial prop-erties to engineer the as-formed BCP particles were summarized.Then,the comprehensive scenarios of the applications of the resulting BCP parti-cles were discussed.Finally,the future tendency and challenge of the self-assembly of BCPs confined in emulsion droplet were suggested.

Self-assembled monolayer enabling improved buried interfaces in blade-coated perovskite solar cells for high efficiency and stability

Despite the rapidly increased power conversion efficiency(PCE)of perovskite solar cells(PVSCs),it is still quite challenging to bring such promising photovoltaic technology to commercialization.One of the challenges is the upscaling from small-sized lab devices to large-scale modules or panels for production.Currently,most of the efficient inverted PVSCs are fabricated on top of poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine](PTAA),which is a commonly used hole-transporting material,using spin-coating method to be incompatible with large-scale film deposition.Therefore,it is important to develop proper coating methods such as blade-coating or slot-die coating that can be compatible for producing large-area,high-quality perovskite thin films.It is found that due to the poor wettability of PTAA,the blade-coated perovskite films on PTAA surface are often inhomogeneous with large number of voids at the buried interface of the perovskite layer.To solve this problem,self-assembled monolayer(SAM)-based hole-extraction layer(HEL)with tunable headgroups on top of the SAM can be modified to provide better wettability and facilitate better interactions with the perovskite coated on top to passivate the interfacial defects.The more hydrophilic SAM surface can also facilitate the nucleation and growth of perovskite films fabricated by blade-coating methods,forming a compact and uniform buried interface.In addition,the SAM molecules can also be modified so their highest occupied molecular orbital(HOMO)levels can have a better energy alignment with the valence band maxima(VBM)of perovskite.Benefitted by the high-quality buried interface of perovskite on SAM-based substrate,the champion device shows a PCE of 18.47%and 14.64%for the devices with active areas of 0.105 cm^(2) and 1.008 cm^(2),respectively.In addition,the SAM-based device exhibits decent stability,which can maintain 90%of its initial efficiency after continuous operation for over 500 h at 40℃ in inert atmosphere.Moreover,the SAM-based perovskite mini-module exhibits a PCE of 14.13%with an aperture area of 18.0 cm^(2).This work demonstrates the great potential of using SAMs as efficient HELs for upscaling PVSCs and producing high-quality buried interface for large-area perovskite films.

Odd-even effects in the structure and properties of aryl-substituted aliphatic self-assembled monolayers

Self-assembled monolayers(SAMs)represent an important tool in context of nanofabrication and molecular engineering of surfaces and interfaces.The properties of functional SAMs depend not only on the character of the tail groups at the SAM-ambient interface,but are also largely defined by their structure.In its turn,the latter parameter results from a complex interplay of the structural forces and a variety of other factors,including so called odd-even effects,viz.dependence of the SAM structure and properties on the parity of the number(odd or even)of individual building blocks in the backbone of the SAM constituents.The most impressive manifestation of the odd-even effects is the structure of aryl-substituted alkanethiolate SAMs on Au(111)and Ag(111),in which,in spite of the fact that the intermolecular interaction is mostly determined by the aryl part of the monolayers,one observes a pronounced dependence of molecular inclination and,consequently,the packing density of the SAM-forming molecules on the parity of number of methylene units in the alkyl linker.Here we review the properties of the above systems as well as address fundamental reasons behind the odd-even effects,including the existence of a so-called bending potential,which is frequently disregarded in analysis of the structure-building forces.The generality of the odd-even effects in SAMs is additionally supported by the recent data for SAMs on GaAs,scanning tunneling microscopy data for SAMs on Ag(111),and the data for the monolayers with selenolate and carboxyl anchoring groups on Au(111)and Ag(111).The implications of these effects in terms of the control over the packing density and orientation of the tail groups at the SAM-ambient interface,structural perfection,polymorphism,temperature-driven phase transitions,and SAM stability toward such factors as ionizing radiation,exchange reaction,and electrochemical desorption are discussed.These implications place the odd-even effects as an important tool for the design of functional SAMs in context of specific applications.

Molecular recognition of sulfonatocalixarene with organic cations at the self-assembled interface：a thermodynamic investigation

A microcalorimetric study on molecular recognition of p-sulfonatocalix[4]arene derivatives at selfassembled interface in comparison with in bulk water was performed,inspired by the dramatic change in physicochemical characteristics from bulk water to interface.A total of six cationic molecules were screened as model guests,including ammonium（NH_4~＋）,guanidinium（Gdm~＋）.N,N＇-dimethyl-1,4-diazabicyclo[2.2.2]octane（DMDABCO^（2＋））,tropylium（Tpm~＋）,N-methyl pyridinium（N-mPY＊） and methyl viologen（MV^（2＋））.The complexation with NH_4~＋.Gdm~＋ and DMDABCO2＊ is pronouncedly enhanced when the recognition process moved from bulk water to interface,whereas the complexation stabilities with Tpm~＋,N-mPY~＋ and MV2＊ increase slightly or even decrease to some extent.A more interesting phenomenon arises from the NH_4~＋/Gdm~＋ pair that the thermodynamic origin at interface differs definitely from each other although with similar association constants.The results were discussed in terms of differential driving forces,electrostatic,hydrogen bond as well as π-stacking interactions,originating from the unique physicochemical features of interfaces,mainly the polarity and dielectric constant.

Precisely installing gold nanoparticles at the core/shell interface of micellar assemblies of triblock copolymers

Two reduction-cleavable ABA triblock copolymers possessing two disulfide linkages,PMMA-ssPMEO3MA-ss-PMMA and PDEA-ss-PEO-ss-PDEA were synthesized via facile substitution reactions from homopolymer precursors,where PMMA,PMEO3MA,PDEA,and PEO represent poly（methyl methacrylate）,poly（tri（ethylene glycol） monomethyl ether methacrylate,poly（2-（diethylamino）ethyl methacrylate）,and poly（ethylene oxide）,respectively.Spherical micelles were obtained through supramolecular self-assembly of these two triblock copolymers in aqueous solutions.The resultant micelles with abundant disulfide bonds could serve as soft templates and precisely accommodate gold nanoparticles in the core/shell interface as a result of the formation of Au-S bonds.

Facile fabrication of porous pure and Ag nanoparticle-doped poly(4-vinylpyridine) films at the liquid-liquid interfaces

We reported an interfacial self-assembly of regularly layered porous poly（4-vinylpyridine） （P4VP） films at the interfaces of water-chloroform or -dichloroethane. The porous diameters were in the range from hundred nanometers to several micrometers. It was revealed that formation of such kind of porous materials was solvent dependent. Moreover, cyclic Ag nanoparticles could be grown in the porous P4VP films to form Ag-P4VP nanohybrids under radiation.

Modeling of highly efficient drug delivery system induced by self-assembly of nanocarriers: A density functional study

Owing to the importance of drug delivery in cancer or other diseases' therapy, the targeted drug delivery (TDD) system has been attracting enormous interest. Herein, we model the TDD system and design a novel rod-like nanocarrier by using the coarse grained model-based density functional theory, which combines a modified fundamental measure theory for the excluded-volume effects, Wertheim's first-order thermodynamics perturbation theory for the chain connectivity and the mean field approximation for van der Waals attraction. For comparison, the monomer nanocarrier TDD system and the no nanocarrier one are also investigated. The results indicate that the drug delivery capacity of rod-like nanocarriers is about 62 times that of the no nanocarrier one, and about 6 times that of the monomer nanocarriers. The reason is that the rod-like nanocarriers would self-assemble into the smectic phase perpendicular to the membrane surface. It is the self-assembly of the rod-like nanocarriers that yields the driving force for the targeted delivery of drugs inside the cell membrane. By contrast, the conventional monomer nanocarrier drug delivery system lacks the driving force to deliver the drugs into the cell membrane. In short, the novel rod-like nanocarrier TDD system may improve the drug delivery efficiency. Although the model in this work is simple, it is expected that the system may provide a new perspective for cancer targeted therapy.

Tuning the inhomogeneous charge transport in ZnO interfaces for ultrahigh on/off ratio top-gated field-effect-transistor arrays

The interface between oxide/oxide layers shows an inhomogeneous charge transport behavior,which reveals a high conductivity owing to interface-doped.One typical example is the hetero-interface between ZnO film and other wide band gap oxides(e.g.,Al_(2)O_(3),TiO_(2),and HfO_(2)).It is thus quite evident that the ZnO/other oxides hetero-interface contains high density electron carriers effectively screening the gate-induced electric field.Thus,an extremely weak gate modulation in ZnO film was showed,resulting in very low on/off ratio of 1.69 in top-gate field-effect-transistor(TG-FET)configuration.So,to extend the usage of ZnO TG-FET is not quite possible toward further practical application.Herein,we clarified the correlation of inhomogeneous region in oxide/oxide hetero-junction by systematically study.Our work suggests that a self-assembly of molecules(SAM)buffer layer is suitable for tuning the inhomogeneous charge transport in ZnO film,which not only reduces the interface trap density,but also effectively enhances the gate electric field modulation at the hetero-interface.We further report the robust fabrication of TG-FET arrays based on ZnO thin film,using an ultra-thin alkylphosphonic acid molecule monolayer as buffer layer.Our device demonstrates a pronounced ultrahigh on/off ratio of≥10^(8),which is 8-order of magnitude higher than that of a device without buffer layer.For the highly reliable arrays,our device exhibits a high yield of over 93%with an average on/off ratio of^10^(7) across the entire wafer scale,mobility(18.5 cm^(2)/(V·s)),an extended bias-stressing(~2,000 s)and long-stability(~150 days)under ambient conditions.

Enhancing the performance of organic solar cells by modification of cathode with a self-assembled monolayer of aromatic organophosphonic acid

We use a single-molecule self-assembled layer of an aromatic organophosphonic acid(2PACz) to modify the cathode interface layer in inverted organic solar cells(OSCs). The modified OSCs not only have an obvious improvement in power conversion efficiency(PCE), but also demonstrate greatly enhanced air stability. Ultraviolet photoelectron spectroscopy shows that the work function of cathode interlayer after modification by 2PACz is more suitable for electron extraction. In addition, the surface energy is reduced without affecting the film deposition, which will be beneficial to reduce the interfacial traps. As a result,the PCE of OSCs based on the PBDB-T:IT-M system is increased, and its stability in air is greatly improved(remaining 88% of its initial PCE after 555 h in air). Therefore, we provide a new strategy for constructing high-performance non-fullerene OSCs with enhanced air stability.