Analysis of electrochemical impedance and XRD spectroscopy for complex self-assembled film on silver

Self-assembled monolayers （SAMs） of （3-mercaptopropy） trimethoxysilane （3-MtrF） chemisorbed on silver surfaces were chemically ＂modified by 1-octadecanethiol to form self-assembled mixed-monolayers （SAMM） and the co-polymer of N-vinylcarbazole and methyl methacrylate ester （to form complex selfassembled film （CSAF））. The oxidation resistance of these barriers on silver surfaces and some influential factors concerned processes were analyzed by electrochemical impedance spectroscopy （EIS） in a 10% NaOH aqueous solution at oxidation potential. X-ray diffraction （XRD） spectroscopy shows that the oxidation occurring on the silver surface may be restrained effectively due to the coating barrier, and CSAF（Ⅱ） is the best one. Studies also reveal that oxide processes of bare silver and a series of modified silver electrodes in a 10% NaOH aqueous solution are of more than two relaxation time constants.

FABRICATION AND AFM/FFM STUDIES OF C_(60)-CONTAINING POLYELECTROLYTE SELF-ASSEMBLED FILMS

An initial investigation on the roughness and frictional properties of the self-assembled thin films from polyelectrolytes is presented. Star-shaped C-60-Poly(styrene-maleic anhydride) was successful prepared. The multilayer thin films have been fabricated on mica with diazoresin as the cationic polyelectrolyte and hydrolyzed star-shaped C-60-poly(styrene-maleic anhydride) as the anionic polyelectrolyte via self-assembly technique. The crosslinking structure of the films is formed from the conversion of ionic bond to covalent bond after UV irradiation. AFM/FFM investigations provide insights into the roughness and frictional properties on a microscale. The roughness depends strongly on the number of film layers in the case of C-60-containing films. The frictional forces of the films exhibited a well behaved non-linear relationship in response to the change of applied load. It supports the prediction of enhanced load-bearing property Of C60-containing thin films.

Novel self-assembled films of La-based phosphonate 3-aminopropyltriethoxysilane

Silane coupling reagent (3-aminopropyltriethoxysilane (APTES)) was prepared on single-crystal silicon substrates to form two-dimensional self-assembled monolayer (SAM). The terminal-NH2 groups in the film were in situ phosphorylated to -PO(OH)2 group to endow the film with good chemisorption ability. Then La-based thin films were deposited on phosphorylated APTES-SAM in order to make good use of the chemisorption ability of -PO(OH)2 groups. The thickness of the film was determined with ellipsometer, while phase transformation and surface morphology, surface energy, phase composition were analyzed by means of atomic force microscope (AFM), contact angle measurements and X-ray photoelectron spectroscopy (XPS). The results indicated that the terminal-NH2 groups could be completely transformed into desirable-PO(OH)2 groups after phosphorylation of APTES-SAM. Detailed XPS analysis of the La3+ peaks revealed that lanthanum element existed in the films in different states. As a result, conclusion could be made that lanthanum reacted with -PO(OH)2 groups on the surface of the substrate by chemical bond which would improve the bonding strength between the film and silicon substrate. Since the La-based thin films were well adhered to the silicon substrate, it might find promising application in the surface-modification of single-crystal Si and SiC in microelectromechanical systems (MEMS).

Novel Covalently Linked Self-Assembled Films from a Functional Hyperbranched Conjugated Poly (Phenylene Vinylene)

A new self-assembled films of a functional dendritic molecule, hyperbranched conjugated poly (phenylene vinylene), is obtained through covalent bond linkage. The highly ordered and homogenous molecular films are obtained;and characterized by UV-vis spectra, fluorescent spectra and atomic force microscopy.

STABILITY AND ELECTROCHEMICAL PROPERTIES OF FULL-CONJUGATED SELF-ASSEMBLED FILMS BASED ON POLYANILINE AND ITS ACID-SUBSTITUTED DERIVATES

The stability of full-conjugated self-assembled （SA） multilayer films based on partially doped polyaniline （PANI） as a polycation and poly（o-aminobenzoic acid） （PCAN）, poly（aniline-2-sulfonic acid） （PSAN） as polyanions is investigated in alkali aqueous solutions. The self-assembled PANI-PCAN films keep their stability within 24 h in 1 mol/L NaOH solution,-the PANI-PSAN films, however, maintain the stability for 20 min in the same condition because the solubility of PSAN in alkali solutions is much higher than that of PCAN. The electrochemical properties of the SA films are determined, and the film-CdS composites formed in situ are also reported.

Responding Depth of Photocatalytic Activity of TiO_2 Self-assembled Films

The electrostatically self-assembly method is getting strategically important to prepare multilayer thin films. With careful choice of component materials, this method should allow for the preparation of multilayer thin films with a variety of excellent technological properties. Ti02/PSS multilayer thin films with ordered structure were prepared by electrostatic self-assembly method. UV-Vis-NIR spectrophotometer, X-ray photoelectron spectroscopy (XPS), and atom force microscopy (AFM) were used to characterize the structure and performance of the multilayer films. Because electrostatically self-assembly method allows molecular-level control over the film composition and thickness, this paper studied the responding depth of photocatalytic activity of Ti02 self-assembled films in detail.

Interfacial Modification of NiO_(x)by Self-assembled Monolayer for Efficient and Stable Inverted Perovskite Solar Cells

NiO_(x)as a hole transport material for inverted perovskite solar cells has received great attention owing to its high transparency,low fabrication temperature,and superior stability.However,the mismatched energy levels and possible redox reactions at the NiO_(x)/perovskite interface severely limit the performance of NiO_(x) based inverted perovskite solar cells.Herein,we introduce a p-type self-assembled monolayer between NiO_(x)and perovskite layers to modify the interface and block the undesirable redox reaction between perovskite and NiO_(x)The selfassembled monolayer molecules all contain phosphoric acid function groups,which can be anchored onto the NiOr surface and passivate the surface defect.Moreover,the introduction of self-assembled monolayers can regulate the energy level structure of NiO_(x),reduce the interfacial band energy offset,and hence promote the hole transport from perovskite to NiO_(x)layer.Consequently,the device performance is significantly enhanced in terms of both power conversion efficiency and stability.

Chitosan/Sodium Alginate Multilayer pH-Sensitive Films Based on Layer-by-Layer Self-Assembly for Intelligent Packaging

The abuse of plastic food packaging has brought about severe white pollution issues around the world.Developing green and sustainable biomass packaging is an effective way to solve this problem.Hence,a chitosan/sodium alginate-based multilayer film is fabricated via a layer-by-layer(LBL)self-assembly method.With the help of superior interaction between the layers,the multilayer film possesses excellent mechanical properties(with a tensile strength of 50 MPa).Besides,the film displays outstanding water retention property(blocking moisture of 97.56%)and ultraviolet blocking property.Anthocyanin is introduced into the film to detect the food quality since it is one natural plant polyphenol that is sensitive to the pH changes ranging from 1 to 13 in food when spoilage occurs.It is noted that the film is also bacteriostatic which is desired for food packaging.This study describes a simple technique for the development of advanced multifunctional and fully biodegradable food packaging film and it is a sustainable alternative to plastic packaging.

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.

Factors resisting protein adsorption on hydrophilic/hydrophobic self-assembled monolayers terminated with hydrophilic hydroxyl groups

The hydroxyl-terminated self-assembled monolayer(OH-SAM),as a surface resistant to protein adsorption,exhibits substantial potential in applications such as ship navigation and medical implants,and the appropriate strategies for designing anti-fouling surfaces are crucial.Here,we employ molecular dynamics simulations and alchemical free energy calculations to systematically analyze the factors influencing resistance to protein adsorption on the SAMs terminated with single or double OH groups at three packing densities(∑=2.0 nm^(-2),4.5 nm^(-2),and 6.5 nm^(-2)),respectively.For the first time,we observed that the compactness and order of interfacial water enhance its physical barrier effect,subsequently enhancing the resistance of SAM to protein adsorption.Notably,the spatial hindrance effect of SAM leads to the embedding of protein into SAM,resulting in a lack of resistance of SAM towards protein.Furthermore,the number of hydroxyl groups per unit area of double OH-terminated SAM at ∑=6.5 nm^(-2) is approximately 2 to 3 times that of single OH-terminated SAM at ∑=6.5 nm^(-2) and 4.5 nm^(-2),consequently yielding a weaker resistance of double OH-terminated SAM towards protein.Meanwhile,due to the structure of SAM itself,i.e.,the formation of a nearly perfect ice-like hydrogen bond structure,the SAM exhibits the weakest resistance towards protein.This study will complement and improve the mechanism of OH-SAM resistance to protein adsorption,especially the traditional barrier effect of interfacial water.

Morphological Evolution of Self-Assembled Sodium Dodecyl Sulfate/Dodecyltrimethylammonium Bromide@Epoxy-β-Cyclodextrin Supramolecular Aggregates Induced by Temperature

Bio-based cyclodextrins(CDs)are a common research object in supramolecular chemistry.The special cavity structure of CDs can form supramolecular self-assemblies such as vesicles and microcrystals through weak interaction with guest molecules.The different forms of supramolecular self-assemblies can be transformed into each other under certain conditions.The regulation of supramolecular self-assembly is not only helpful to understand the self-assembly principle,but also beneficial to its application.In the present study,the self-assembly behavior of epoxy-β-cyclodextrin(EP-β-CD)and mixed anionic and cationic surfactant system(sodium dodecyl sulfate/dodecyltrimethylammonium bromide,SDS/DTAB)in aqueous solution was studied.Morphological and particle size characterization found that the SDS/DTAB@EP-β-CD complex,as the basic building unit,self-assembled into worm-like micelles at lower temperatures and vesicles at higher temperatures.Nuclear magnetic resonance(NMR)and Fourier transform infrared spectroscopy(FT-IR)analysis revealed that the driving force for the formation of vesicles and worm-like micelles was the hydrogen bonds between EP-β-CD molecules,while water molecules played an important role in promoting vesicle formation between SDS/DTAB@EP-β-CD units.Herein,the mechanism of the morphologic transformation of SDS/DTAB@EP-β-CD supramolecular aggregates induced by temperature was elucidated by exploring the self-assembly process,which may provide an excellent basis for the development of delivery carriers.

Intelligent responsive self-assembled micro-nanocapsules:Used to delay gel gelation time

In the application of polymer gels to profile control and water shutoff,the gelation time will directly determine whether the gel can"go further"in the formation,but the most of the methods for delaying gel gelation time are complicated or have low responsiveness.There is an urgent need for an effective method for delaying gel gelation time with intelligent response.Inspired by the slow-release effect of drug capsules,this paper uses the self-assembly effect of gas-phase hydrophobic SiO_(2) in aqueous solution as a capsule to prepare an intelligent responsive self-assembled micro-nanocapsules.The capsule slowly releases the cross-linking agent under the stimulation of external conditions such as temperature and pH value,thus delaying gel gelation time.When the pH value is 2 and the concentration of gas-phase hydrophobic SiO_(2) particles is 10%,the gelation time of the capsule gel system at 30,60,90,and 120℃is12.5,13.2,15.2,and 21.1 times longer than that of the gel system without containing capsule,respectively.Compared with other methods,the yield stress of the gel without containing capsules was 78 Pa,and the yield stress after the addition of capsules was 322 Pa.The intelligent responsive self-assembled micronanocapsules prepared by gas-phase hydrophobic silica nanoparticles can not only delay the gel gelation time,but also increase the gel strength.The slow release of cross-linking agent from capsule provides an effective method for prolongating the gelation time of polymer gels.

Surface Enhanced Raman Scattering on Self-assembled Nano Silver Film Prepared by Electrolysis Method

We demonstrate surface enhanced Raman scattering （SERS） detection of self-assembled nano silver film using a low-cost electrolysis strategy at a proper voltage and silver nitrate concentration in electrolyte. The concentration dependence of SERS from crystal violet （CV） molecules adsorbed to silver film was systematically studied. Importantly, the SERS surface enhancement factor of such nano silver film was 603, which was measured by a portable Raman spectrometer. The minimum concentration of detectable CV molecules can be as low as 10^-11 mol/L. The nano silver film prepared by this electrolysis method is an active, stable, cost-effective, and reusable SERS substrate.

Effect of different metal ions in a new kind of functionalized self-assembled films of trinary complexes on its photoinduced electron transfer property

Three new kinds of self-assembled films were first fabricated through a new strategy. These films have Sn4+, Zr4+ and Ce4+ as bridging central ions, 3, 4, 9, 10-perylene tetracarboxylic acid (PTA) as functional molecules and oxalic acid as connecting ligand. All films were characterized by contact angle, UV spectra, X-ray photoelectron spectra (XPS) and cyclic voltammetry. The effects of light intensity, bias voltage, and electron donor on photocurrents of these films were also studied.

Hybrid Self-Assembled Multilayer Films Formed by Alternating Layers of Keggin Polyoxometalates and 1,10DAD

Hybrid self-assembled multilayer films were prepared by alternate adsorption of 1,10-diaminodecane (1,10-DAD) and Keggin polyoxometalates of SiW12O404-, SiW11VO405-, and PMo12O403-, respectively. The films were reproducibly grown at each adsorption cycle as monitored by UV spectroscopy.

Tribological Properties of Rare Earth Self-assembled Nanometer Film

Self-assembled film containing the rare earth (RE) elements was formed on a silicon dioxide substrate, in order to reduce the surface adhesion and the friction force of micro electro-mechanical systems (MEMS). The film thickness was measured as 2nm. The tribological experiment result shows that the friction coefficient of SiO 2 substrate reduces from 0.5 to 0.1 after the formation of RE self-assembled film on its surface. Besides, RE self-assembled film exhibits a high wear resistant ance.

Novel Roles of Metal Ions in Layered Self-assembled Films of Polynuclear Complexes on Their Photoinduced Electron Transfer Properties

Three metal ion bridged self-assembled （SA） films of cis-di（thiocyanato）-bis（2,2＇-bipyridyl-4,4＇-dicarboxylate） ruthenium were fabricated and characterized by contact angle, UV spectra, cyclic voltammetry and XPS. Their photoinduced electron transfer properties （PETP） were examined. Among the titled systems, the highest steady anodic photocurrent of 1773-1843 nA/cm^2 and the highest quantum yield of 3.2% were achieved. The effects of incident light intensity, bias voltage, and electron donor were also studied. The possible mechanism of electron transfer was proposed. The results reveal that different metal ion in SA films could affect significantly the photoinduced electron transfer property. Our experimental results clearly show that bridging metal ions can play both functional and structural roles in these self-assembled systems. This method of forming functional films can provide a new approach to regulate the property of similar systems.

Characterization and tribological investigation of self-assembled trimethoxysilyl-functionalized poly(phthalazinone ether ketone)thin films on glass substrates

Trimethoxysilyl-functionalized PPEK（PKGS） films had been designed to serve as wear resistant coatings for silicon surfaces. These surface films were formed by a dip-coating technique applied to self-assembled monolayers（SAMs）.The formation and wetting behavior of PKGS films were characterized by means of contact angle measurement.The friction coefficient of the film prepared is very low（about 0.1）,and the anti-wear behavior is good,with a lack of failure after sliding over 1800 s.

Characterization and tribological investigation of self-assembled MPTS-MPTES/RE composite films

γ-mercapto-propyl trimethoxysilane （MPTS） and γ-methacryloxy propyltrimethoxysilane （MPTES） were self-assembled on a hy- droxylated glass substrate to form a two-dimensional organic monolayer （MPTS-MPTES SAM）. The terminal thiol groups （-SH） in the MPTS-MPTES SAM were in-situ oxidized into sulfonic acid groups （-SO3H） to endow the film with good chemisorption ability. Then rare earth （RE） （lanthanum-based） composite thin films were prepared by self-assembly technique based on the as-prepared SAM, taking advantage of the chemisorption ability of the sulfonic acid groups. Automatic force microscope （AFM）, X-ray photoelectron spectrometry （XPS）, contact angle measurement and ellipsometer were used to characterize MPTS-MPTES/RE composite films. The macrofriction and wear behaviors of the films sliding against an AISI-52100 steel ball were examined on a unidirectional friction and wear tester, and the worn surface morphologies were observed on an AFM. The results showed that MPTS-MPTES/RE films had a low friction coefficient （0.09） and a long wear life （5980 sliding pass） at a light load （50 mN）. It indicated that the superior tribological properties of the MPTS-MPTES/RE composite films were attributed to the special characteristic of RE elements, the mobility of the films and good bonding strength.

Self-assembled activated carbon sandwiched graphene film for symmetrical supercapacitors

Activated carbon(AC)particles sandwiched reduced graphene oxide sheets(rGO)film has been successfully fabricated via a facile self-assemble approach.The as-formed AC/rGO film is self-standing,flexible and mechanically robust,allowing to be transferred to any substrate on demand without rupture.Since AC particles effectively suppressed the restacking of the rGO sheet,AC/rGO film exhibits loose layer-by-layer stacking structures with various gaps between AC particles and rGO sheets,which is different from compact structures of pure graphene films.The as-formed gaps provide fast diffusion channels for electrolyte ions and enhanced accessible surface area of rGO.Therefore,the AC/rGO electrode delivers improved electrochemical performance over the voltage range of 0.0−3.0 V.This work offers a promising strategy to design free-standing supercapacitor electrodes based on traditional nanocarbon materials.