Enhanced performance of a solar cell based on a layer-by-layer self-assembled luminescence down-shifting layer of core–shell quantum dots

In this paper, core–shell quantum dots（QDs） with two polar surface functional groups（ZnSe/ZnS–COOH QDs and ZnSe/ZnS–NH;QDs） are synthesized in an aqueous phase. Photoluminescence（PL） and absorption spectra clearly indicate luminescence down-shifting（LDS） properties. On the basis of QDs, surface functional group multilayer LDS films（MLDSs） are fabricated through an electrostatic layer-by-layer（LBL） self-assembly method. The PL intensity increases linearly with the number of bilayers, showing a regular and uniform film growth. When the M-LDS is placed on the surface of a Si-based solar cell as an optical conversion layer for the first time, the external quantum efficiency（EQE） and shortcircuit current density（Jsc） notably increases for the LDS process. The EQE response improves in a wavelength region extending from the UV region to the blue region, and its maximum increase reaches more than 15% between 350 nm and 460 nm.

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.

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.

Solid Additive-Assisted Layer-by-Layer Processing for 19%Efficiency Binary Organic Solar Cells

Morphology is of great significance to the performance of organic solar cells(OSCs),since appropriate morphology could not only promote the exciton dissociation,but also reduce the charge recombination.In this work,we have developed a solid additive-assisted layer-by-layer(SAA-LBL)processing to fabricate high-efficiency OSCs.By adding the solid additive of fatty acid(FA)into polymer donor PM6 solution,controllable pre-phase separation forms between PM6 and FA.This intermixed morphology facilitates the diffusion of acceptor Y6 into the donor PM6 during the LBL processing,due to the good miscibility and fast-solvation of the FA with chloroform solution dripping.Interestingly,this results in the desired morphology with refined phase-separated domain and vertical phase-separation structure to better balance the charge transport/collection and exciton dissociation.Consequently,the binary single junction OSCs based on PM6:Y6 blend reach champion power conversion efficiency(PCE)of 18.16%with SAA-LBL processing,which can be generally applicable to diverse systems,e.g.,the PM6:L8-BO-based devices and thick-film devices.The efficacy of SAA-LBL is confirmed in binary OSCs based on PM6:L8-BO,where record PCEs of 19.02%and 16.44%are realized for devices with 100 and 250 nm active layers,respectively.The work provides a simple but effective way to control the morphology for high-efficiency OSCs and demonstrates the SAA-LBL processing a promising methodology for boosting the industrial manufacturing of OSCs.

Active straining engineering on self-assembled stacked Ni-based hybrid electrode for ultra-low overpotential

Generating sufficient strains on metal surfaces are highly challenging owing to that most metals can deform plastically to relax the strains on the surfaces.In this work,we developed a facile but highly efficient stacked deposition strategy to in situ activation and reconstruction of NiO/NiOOH on Ni matrix,following with the migration of Fe ions to NiOOH.The Fe sites on the Ni/NiO/NiOOH facilitate the formation of the stable*OH oxygenated intermediates,and the Ni matrix in the catalyst provides the catalyst excellent stability.The oxygen evolution reaction(OER)performance of the stacked NiFe-5 with compressive strain displays the strengthened binding to oxygenated intermediates and superior OER activity,the ultralow overpotentials of 162 versus reversible hydrogen electrode at 10 mA cm^(-2).On the other hand,the Ni-5 without the incorporation of Fe has shown an outstanding hydrogen evolution reaction(HER)activity,affording an overpotential of 47 mV at 10 mA cm^(-2).The NiFe-5‖Ni-5 enables the overall water splitting at a voltage of 1.508 V to achieve 20 mA cm^(-2) with remarkable durability.The stacked deposition strategy improves binding strength of Ni-based catalysts to oxygenated intermediates via generating compressive strain,causing high catalytic activities on OER and HER.

Au@Ag Core-shell Nanorods Self-assembled on Polyelectrolyte Multilayers for Ultra-High Sensitivity SERS Fiber Probes

We demonstrated a chemical process in the fabrication of a SERS fiber probe with an ultrahigh sensitivity.The synthesis was carried out by preparing Au@Ag core-shell nanorods (Au@Ag-NRs) selfassembled on polyelectrolyte (PE) multilayers,for which Au@Ag-NRs were controlled by adjusting the silver layer thickness.The effect of silver layer thickness of Au@Ag-NRs on the SERS performance of the fiber probe was investigated.The SERS fiber probe shows the best performance when the silver layer thickness is controlled at 8.57 nm.Under the condition of optimizing silver layer thickness,the fiber probe exhibits ultra-high sensitivity (i e,10^(-10) M crystalline violet,CV),good reproducibility (i e,RSD of 3.5%) and stability.Besides,electromagnetic field distribution of the SERS fiber probe was also investigated.The strongest enhancement is found within the core of fiber,whereas a weakened electromagnetic field exists in the fiber cladding layer.The SERS fiber probe can be a good candidate in ultra-trace detection for biomedical and environmental areas.

Self-assembly of perovskite nanocrystals:From driving forces to applications

Self-assembly of metal halide perovskite nanocrystals(NCs)into superlattices can exhibit unique collective properties,which have significant application values in the display,detector,and solar cell field.This review discusses the driving forces behind the self-assembly process of perovskite NCs,and the commonly used self-assembly methods and different self-assembly structures are detailed.Subsequently,we summarize the collective optoelectronic properties and application areas of perovskite superlattice structures.Finally,we conclude with an outlook on the potential issues and future challenges in developing perovskite NCs.

Alcohol solvent effect on the self-assembly behaviors of lignin oligomers

The interactions between lignin oligomers and solvents determine the behaviors of lignin oligomers self-assembling into uniform lignin nanoparticles(LNPs).Herein,several alcohol solvents,which readily interact with the lignin oligomers,were adopted to study their effects during solvent shifting process for LNPs’production.The lignin oligomers with widely distributed molecular weight and abundant guaiacyl units were extracted from wood waste(mainly consists of pine wood),exerting outstanding self-assembly capability.Uniform and spherical LNPs were generated in H_(2)O-n-propanol cosolvent,whereas irregular LNPs were obtained in H_(2)O-methanol cosolvent.The unsatisfactory self-assembly performance of the lignin oligomers in H_(2)O-methanol cosolvent could be attributed to two aspects.On one hand,for the initial dissolution state,the distinguishing Hansen solubility parameter and polarity between methanol solvent and lignin oligomers resulted in the poor dispersion of the lignin oligomers.On the other hand,strong hydrogen bonds between methanol solvent and lignin oligomers during solvent shifting process,hindered the interactions among the lignin oligomers for self-assembly.

Layer by Layer Self-assembly Fiber-based Flexible Electrochemical Transistor

Poly(3,4-ethylenedioxyethiophene)-polystyrene sulfonic acid(PEDOT:PSS)/polyallyl dimethyl ammonium chloride modified reduced graphene oxide(PDDA-rGO)was layer by layer self-assembled on the cotton fiber.The surface morphology and electric property was investigated.The results confirmed the dense membrane of PEDOT:PSS and the lamellar structure of PDDA-rGO on the fibers.It has excellent electrical conductivity and mechanical properties.The fiber based electrochemical transistor(FECTs)prepared by the composite conductive fiber has a maximum output current of 8.7 mA,a transconductance peak of 10 mS,an on time of 1.37 s,an off time of 1.6 s and excellent switching stability.Most importantly,the devices by layer by layer self-assembly technology opens a path for the true integration of organic electronics with traditional textile technologies and materials,laying the foundation for their later widespread application.

Biomimetic“Nacre-like”Films Prepared via Layer-by-Layer Self-assembly of Mica,Polyvinyl Alcohol and Polymethyl Methacrylate

A film with“brick-and-mortar”structure was prepared by layer-by-layer(LBL)technique using polyvinyl alcohol(PVA)and polymethyl methacrylate(PMMA)as the flexible material or“mortar”and mica as the rigid material or“brick”.The film deposited on a glass slide after self-assembly cycles had a thickness of 3μm thick and an uneven,wavy surface.The film exhibits enhanced mechanical properties,i e,the hardness and indentation modulus values could reach 6.14 and 68.41 GPa,respectively.The hardness and elastic toughness were found to be depended on three factors,i e,the ratio of PVA to mica,the number of self-assembly cycles,and the pretreatment method of the mica suspension.The self-assembly process was driven by formation of the hydrogen bonds between the silanol groups of mica and the hydroxyl groups of PVA and carbonyl groups of PMMA.

Layer-by-layer electrostatic selfassembly of anionic and cationic carbon nanotubes

The layer-by-layer(LBL) self assembly of anionic and cationic multi-walled carbon nanotubes(MWNTs) through electrostatic interaction has been carried out to fabricate all-MWNT multilayer films.The alternate uniform assembly of anionic and cationic MWNTs was investigated by UV-vis spectroscopy.Scanning electron microscopy(SEM) images displayed the growth of the MWNT films.

In vitro corrosion resistance,antibacterial activity and cytocompatibility of a layer-by-layer assembled DNA coating on magnesium alloy

A chitosan/deoxyribonucleic acid(CHI/DNA)_(5)coating was constructed by layer-by-layer(LbL)assembly dip coating method with Mg(OH)_(2)coating as an inner protective layer on AZ31 alloy.X-ray diffractometry,X-ray photoelectron spectrometry,Fourier transform infrared spectroscopy and field-emission scanning electron microscopy were utilized to represent the chemical compositions and surface morphologies of the coatings.Electrochemical tests and hydrogen evolution measurements were implemented to confirm the good corrosion resistance of the composite coating in artificial body fluid.Antimicrobial activity of the composite coatings was tested via the plate-counting method,and the cytotoxicity of the samples was appraised by MTT assay and Live/dead staining.A double action was put into effect for the composite coating,which the inner Mg(OH)2 coating plays the part of physical barrier,and the outer(CHI/DNA)5 coating is employed as an inducer to fabricate a biocompatible Ca-P corrosion product coating during immersion,making up for its thin thickness.Otherwise,the composite coating is also beneficial for the growth of bone,resulting from the biomineralization effect of the outer polyelectrolyte multilayer.The good antibacterial property of the(CHI/DNA)5/Mg(OH)2 coating is ascribed to the contact-killing strength of CHI.Thus,the obtained(CHI/DNA)5/Mg(OH)2 coating has a wide application prospect in the field of Mg-based bone implantation.

Gradient nanoporous phenolics as substrates for high-flux nanofiltration membranes by layer-by-layer assembly of polyelectrolytes

Thin film composite(TFC) membranes represent a highly promising platform for efficient nanofiltration(NF)processes. However, the improvement in permeance is impeded by the substrates with low permeances. Herein,highly permeable gradient phenolic membranes with tight selectivity are used as substrates to prepare TFC membranes with high permeances by the layer-by-layer assembly method. The negatively charged phenolic substrates are alternately assembled with polycation polyethylenimine(PEI) and polyanion poly(acrylic acid)(PAA)as a result of electrostatic interactions, forming thin and compact PEI/PAA layers tightly attached to the substrate surface. Benefiting from the high permeances and tight surface pores of the gradient nanoporous structures of the substrates, the produced PEI/PAA membranes exhibit a permeance up to 506 L? m-2?h-1?MPa-1, which is ~2–10 times higher than that of other membranes with similar rejections. The PEI/PAA membranes are capable of retaining N 96.1% of negatively charged dyes following the mechanism of electrostatic repulsion. We demonstrate that the membranes can also separate positively and neutrally charged dyes from water via other mechanisms.This work opens a new avenue for the design and preparation of high-flux NF membranes, which is also applicable to enhance the permeance of other TFC membranes.

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).

Attachment of tyrosinase on mixed self-assembled monolayers for the construction of electrochemical biosensor

A mixed self-assembled monolayers （SAMs） of thioctic acid （T-COOH） and thioctic acid amide （T-NH2） were used to immobilize tyrosinase for fabricating biosensor. The results showed that the mixed SAMs prepared from solution at the ratio of 1：4 provided an excellent microenvironment for enzymatic reaction between tyrosinase and substrate. The biosensor exhibited a fast response and high sensitivity for sensing substrate.

Application of Layer-by-Layer Solidification Principle to Optimization of Large Chain Wheel Foundry Technology

In order to get a sound casting of the alloy with a solidification range, the principle of directional solidification (DS) and the layer-by-layer solidification(LBLS) should be followed, especially in designing foundry process of steel casting. Using the principles, the reasons for the forming of the defects on the surface of the chain wheels teeth and groove and the forming of MT (magnetic particle testing) thin lines were analyzed. The results of the metallographic observation and the numerical simulation show that the low temperature gradient results in a wider mushy zone at the S/L interface that causes the defects and MT thin lines on the surface of the chain wheel casting. Based on the analysis, a new casting technology of the chain wheel was designed and used in the casting production successfully.

Layer-by-layer growth of ZIF-8 on electrospun carbon nanofiber membranes for high-performance supercapacistor electrode

In the past few decades, supercapacitor(SC) has attracted great attention due to its significant advantages over traditional rechargeable battery systems, such as high power density, fast charge-discharge rate, long cycle life and environmental friendliness [1]. Up to now, supercapacitors have been widely used in backup power, electric vehicles, mobile power and so on [2,3].

Preparation and characterization of 3-mercaptopropyl trimethoxysilane self-assembled monolayers

Silane coupling regent （3-mercaptopropyl trimethoxysilane （MPTS）） was prepared on the single-crystal silicon substrate to form 2-dimensional self-assembled monolayers （SAMs）. The growth behavior of SAMs formed from 3-MPTS was investigated using atomic force microscopy （AFM）, contact angle measurements, ellipsometry, and X-ray photoelectron spectroscopy （XPS）. The formation behavior of MPTS SAMs was investigated by a series of AFM images and the roughness of MPTS SAMs on silicon substrates with the assembling time from 1 min to 24 h. The water contact angle measurements indicated the growth behavior of MPTS that correlated with the AFM measurements at different immersion times, too. The chemical states of the typical elements in the MPTS SAMs were analyzed using X-ray photoelectron spectroscopy. The results show that MPTS is self-assembled on the substrate.

Targeted transfer of self-assembled CdSe nanoplatelet film onto WS_(2) flakes to construct hybrid heterostructures

Colloidal CdSe nanoplatelets are thin semiconductor materials with atomic flatness surfaces and one-dimensional strong quantum confinement,and hence they own very narrow and anisotropic emission.Here,we present a polydimethylsiloxane(PDMS)assisted transferring method that can pick up single layer CdSe nanoplatelet films self-assembled on a liquid surface and then precisely transfer to a target.By layer-by-layer picking up and transferring,multiple layers of CdSe films can be built up to form CdSe stacks with each single layer having dominant in-plane transition dipole distribution,which both material and energic structures are analogous to traditional multiple quantum wells grown by molecular-beam epitaxy.Additionally,with the great flexibility of colloidal nanoplatelets and this transferring method,CdSe nanoplatelets films can be combined with other materials to form hybrid heterostructures.We transferred a single-layer CdSe film onto WS_(2) flakes,and precisely studied the fast energy transfer rate with controlled CdSe nanoplatelet orientation and by using a streak camera with a ps time resolution.