Self-assembled Films Research Articles

Radical Anions and Dianions of Naphthalenediimides Generated within Layer-by-Layer Zirconium Phosphonate Thin Films.

Chemical reduction of N,N'-bis(2-phosphonoethyl)-1,4,5,8-naphthalenediimide (PNDI) with the reducing agent sodium dithionite gave stable colored reduced species, both in homogeneous solutions and in self-assembled thin films. When colorless PNDI aqueous solutions were titrated with the reducing agent, stepwise reduction was observed, giving first the radical anion (PNDI-•) and then the dianion (PNDI2-) species, which were detected by UV-visible-NIR spectroscopy, allowing the unambiguous determination of absorption maxima and molar absorptivities for each species. The radical anion PNDI-• was found to form π-dimers in water, but monomeric PNDI-• was formed in the presence of the cationic surfactant cetyltrimethylammonium bromide, indicating association with the micelles. Thin films of PNDI with 25 layers were grown by the zirconium phosphonate method on quartz substrates. Reduction of the films with sodium dithionite also produced radical anions and dianions of PNDI. However, reduction in the films was much slower than in solution, evidencing the compactness of the films. Moreover, reduction in the films did not proceed to completion, even with excess of the reducing agent, which can be attributed to the repulsion of negative charges within the film.

Rational design of a self-assembled surfactant film in nanopipettes: combined fluorescence and electrochemical sensing.

Herein, a generalizable method based on the formation of a self-assembled surfactant film was reported to build a nanopipette system. Using this nanopipette, it was found that arginine metabolism shows an age-related difference in Alzheimer's disease.

Self-Assembled Porous Polymer Films for Improved Oxygen Sensing

Self-Assembled Porous Polymer Films for Improved Oxygen Sensing

Self-assembled cellulose nanofiber-carbon nanotube nanocomposite films with anisotropic conductivity.

In this study, a nanocellulose-based material showing anisotopic conductivity is introduced. The material has up to 1000 times higher conductivity along the dry-line boundary direction than along the radial direction. In addition to the material itself, the method to produce the material is novel and is based on the alignment of cationic cellulose nanofibers (c-CNFs) along the dry-line boundary of an evaporating droplet composed of c-CNFs in two forms and conductive multi-walled carbon nanotubes (MWCNTs). On the one hand, c-CNFs are used as a dispersant of MWCNTs, and on the other hand they are used as an additional suspension element to create the desired anisotropy. When the suspended c-CNF is left out, and the nanocomposite film is manufactured using the high energy sonicated c-CNF/MWCNT dispersion only, conductive anisotropy is not present but evenly conducting nanocomposite films are obtained. Therefore, we suggest that suspending additional c-CNFs in the c-CNF/MWCNT dispersion results in nanocomposite films with anisotropic conductivity. This is a new way to obtain nanocomposite films with substantial anisotropic conductivity.

Layer by Layer Self-Assembled Hybrid Thin Films of Porphyrin/Polyoxometalates@Pt Nanoparticles for Photo & Electrochemical Application

Layer by Layer Self-Assembled Hybrid Thin Films of Porphyrin/Polyoxometalates@Pt Nanoparticles for Photo & Electrochemical Application

Multi-component self-assembled molecular-electronic films: towards new high-performance thermoelectric systems.

The thermoelectric properties of parallel arrays of organic molecules on a surface offer the potential for large-area, flexible, solution processed, energy harvesting thin-films, whose room-temperature transport properties are controlled by quantum interference (QI). Recently, it has been demonstrated that constructive QI (CQI) can be translated from single molecules to self-assembled monolayers (SAMs), boosting both electrical conductivities and Seebeck coefficients. However, these CQI-enhanced systems are limited by rigid coupling of the component molecules to metallic electrodes, preventing the introduction of additional layers which would be advantageous for their further development. These rigid couplings also limit our ability to suppress the transport of phonons through these systems, which could act to boost their thermoelectric output, without comprising on their impressive electronic features. Here, through a combined experimental and theoretical study, we show that cross-plane thermoelectricity in SAMs can be enhanced by incorporating extra molecular layers. We utilize a bottom-up approach to assemble multi-component thin-films that combine a rigid, highly conductive ‘sticky’-linker, formed from alkynyl-functionalised anthracenes, and a ‘slippery’-linker consisting of a functionalized metalloporphyrin. Starting from an anthracene-based SAM, we demonstrate that subsequent addition of either a porphyrin layer or a graphene layer increases the Seebeck coefficient, and addition of both porphyrin and graphene leads to a further boost in their Seebeck coefficients. This demonstration of Seebeck-enhanced multi-component SAMs is the first of its kind and presents a new strategy towards the design of thin-film thermoelectric materials.

Bio-inspired non-iridescent structural coloration enabled by self-assembled cellulose nanocrystal composite films with balanced ordered/disordered arrays

Cellulose nanocrystal (CNC) is an interesting polysaccharide nanomaterial that can self-assemble into a chiral nematic liquid crystalline structure in aqueous solution, producing brightly structural color upon selectively reflection of visible light. However, till now, only iridescent structural colors can be created by such colloidal array, making it impossible to be used as colorimetric sensors. Here, inspired by longhorn beetle having short-range ordered but long-range disordered microstructures, it is demonstrated to develop low-/non-angle-dependent structural-color CNC composite films through interference against the long-range orders as a result of introducing positively charged poly (dimethyl diallyl ammonium chloride) (PDDA). By exploring balanced ordered/disordered structures, vivid angle-independent structural colors are realized, enabling accurate cognition for environmental signals, which is crucial to promising applications in sensing, anti-counterfeit, and decoration technology. • Low-/non-angle-dependent structural-color CNC composite films are fabricated. • Balanced ordered/disordered arrays are manipulated by co-assembly with PDDA. • The composite films can be used as colorimetric sensor.

UV-response behavior and chiral structure determination of Langmuir-Blodgett films consisting of polypeptide and dye molecules

Molecular self-assembly is a technology in which different structural components spontaneously form assemblies with special functions through weak, reversible non-covalent interactions on the basis of molecular recognition. The amphiphilic and biocompatibility of polypeptides make it has natural advantage in self-assembly at the air-water interface. In this work, the self-assembled films of palmitoyl pentapeptide-4 (PP4) and dye molecules were prepared by Langmuir-Blodgett (LB) technology. It was found that the PP4/dye composite film had good acid-alkali gas response. In addition, the LB film prepared by PP4 and methyl orange (MO) showed chiral signal, which was reflected in the circular dichroism spectrum. The current research work provides new clues for the preparation of functional self-assembled films and their applications as gas sensors and chemical switches.

Synergistic effect of 4-dimethylaminopyridine with sodium dodecyl sulfonate and potassium bromide on the corrosion inhibition of mild steel in HCl medium: a collective experimental and computational investigation

In this work, the synergistic inhibition performance of three readily available compounds that 4-dimethylaminopyridine (DMAP), potassium bromide (KBr), and sodium dodecyl sulfonate (SDS), which for the corrosion of mild steel in 1 M HCl solution was investigated by weight loss measurements, electrochemical measurements, surface analysis methods, and molecular simulation technique. The weight loss measurement shows that the ternary corrosion inhibitor still has excellent corrosion inhibition performance at high temperature, and the corrosion inhibition efficiency can be as high as 93%. Potentiodynamic polarization (PDP) results suggested that the mixture belongs to the mixed-type inhibitor which mainly inhibits the anodic reaction. Electrochemical impedance spectroscopy (EIS) measurements demonstrated that a self-assembled barrier film can be formed on the steel surface, which increased the polarization resistance and effectively hindered the corrosion. The efficiency of the mixture corrosion inhibitor reaches 83.6%, which is significantly higher than that of a single corrosion inhibitor. Surface analysis showed that the roughness of the substrate surface decreased due to the adsorption of DMAP-SDS-KBr mixture. The combined Monte Carlo (MC) and molecular dynamics (MD) simulations revealed the synergistic adsorption mechanism, which confirmed the experimental findings.

Electronically integrated microcatheters based on self-assembling polymer films.

Existing electronically integrated catheters rely on the manual assembly of separate components to integrate sensing and actuation capabilities. This strongly impedes their miniaturization and further integration. Here, we report an electronically integrated self-assembled microcatheter. Electronic components for sensing and actuation are embedded into the catheter wall through the self-assembly of photolithographically processed polymer thin films. With a diameter of only about 0.1 mm, the catheter integrates actuated digits for manipulation and a magnetic sensor for navigation and is capable of targeted delivery of liquids. Fundamental functionalities are demonstrated and evaluated with artificial model environments and ex vivo tissue. Using the integrated magnetic sensor, we develop a strategy for the magnetic tracking of medical tools that facilitates basic navigation with a high resolution below 0.1 mm. These highly flexible and microsized integrated catheters might expand the boundary of minimally invasive surgery and lead to new biomedical applications.

Self-assembling nano films on metal surface as corrosion inhibitors

Self-assembling molecules form protective layers on metal surfaces Self assembled nanofilms of adipic acid, N-cetyl-N,N,N-trimethyl ammonium bromide, Tween- 60, Sodium dodecyl sulphate and an aqueous extract of banana peel have been formed on the surface of carbon steel by the immersion method. The formation of the nanofilms has been confirmed by Fourier Transform Infrared spectral study and Atomic Force Microscopy Study. The corrosion inhibitive nature of the protective film has been estimated by the classical weight loss method and electrochemical study such as polarization study. The hydrophobic nature of the protective film has been investigated by measurement of contact angles of the protective films. The hydrophobic surfaces may find application in various exciting fields such as corrosion protection, raincoats, water proof surfaces and biomaterials. Copyright © 2017 VBRI Press.

Dry-Etchable Molecular Layer-Deposited Inhibitor Using Annealed Indicone Film for Nanoscale Area-Selective Deposition.

In semiconductor production, the technology node of a device is becoming extremely small below 5 nm. Area selective deposition (ASD) is a promising technique for creating improved overlay or self-alignment, remedying a conventional top-down method. However, the conventional materials and process (self-assembled monolayer, polymer and carbon film fabricated by chemical vapor deposition, and spin coating) for ASD are not suitable for highly conformal deposition. Thus, we investigated a new strategy to deposit conformal films in ASD by molecular layer deposition (MLD). The MLD processes were conducted for an indicone film deposited by INCA-1 (bis(trimethysily)amidodiethyl indium) and hydroquinone (HQ), as well as an alucone film deposited by TMA (trimethylaluminum) and HQ. After thermal heat treatment of the MLD films, variations in thickness, refractive index, and constituent elements of the annealed MLD films were investigated. The indicone film was used as an inhibiting layer for ASD and was etchable with a dry-etching process. The reactive ion etching process on annealed indicone film was optimized according to plasma power, gas concentration, and working pressure. Ruthenium (Ru) ALD was then performed on the annealed MLD films to investigate nucleation delaying cycles and inhibiting properties. A patterned substrate with an MLD/Si line was created via the RIE process, which was allowed to observe the selectivity of the annealed MLD films. In addition, a patterned substrate of SiO2/annealed indicone/Mo was used to investigate the Ru-selective ALD at the nanoscale. The Ru thin film was selectively deposited on the Mo side-wall surface of a 3D trench structure. The growth of the Ru film was inhibited selectively on an annealed indicone surface of approximately 5 nm.

Fabrication and characterization of mussel-inspired layer-by-layer assembled CL-20-based energetic films via micro-jet printing

Three-dimensional (3D) micro-jet printing is a droplet deposition technique based on liquid-phase materials. To improve the deposition density and performance of energetic films with micro/nanoscale on an energetic chip, polydopamine (PDA) was utilized as a linker bridge to induce the in-situ self-assembly of CL-20-based energetic film via 3D micro-jet printing. The self-assembly was extensively characterized by confocal laser scanning microscopy (CLSM), SEM, power-XRD, XPS, and DSC. The performance of the self-assembled film was verified by the mechanical properties and detonation properties, and a possible self-assembly mechanism in the layer-by-layer micro-jet printing process was proposed. The results indicated PDA-induced self-assembly enhanced the physical entanglement between the binders and energetic crystal, reduced the porosity from 15.87% to 11.28%, and improved the elastic modulus and the detonation performance of the CL-20-based energetic film. This work proposes a novel and promising energetic film design and fabrication strategy to enhance the interaction between the energetic composite layers in the micro-jet printing process.

Exploring the Spatial Control of Topotactic Phase Transitions Using Vertically Oriented Epitaxial Interfaces

HighlightsAn epitaxial nanocomposite approach is developed for exploring spatial control of oxygen vacancy-driven topotactic phase transition of La0.7Sr0.3MnO3-x (LSMO).The ultrahigh density of epitaxial interfaces created in the self-assembled LSMO-NiO nanocomposite films strongly influence the oxygen vacancy formation and topotactic phase distribution in LSMO.The distinct intermediate topotactic nanostructures controlled by the NiO fraction broadens the tuning range of correlated magnetic and transport properties of LSMO.

The effect of anion architecture on the lubrication chemistry of phosphonium orthoborate ionic liquids

Phosphonium ionic liquids with orthoborate anions have been studied in terms of their interfacial film formation, both physisorbed and sacrificial from chemical breakdown, in sheared contacts of varying harshness. The halogen-free anion architecture was varied through (i) the heteronuclear ring size, (ii) the hybridisation of the constituent atoms, and (iii) the addition of aryl functionalities. Time of Flight-Secondary Ion Mass Spectrometry analysis revealed the extent of sacrificial tribofilm formation allowing the relative stability of the ionic liquids under tribological conditions to be determined and their breakdown mechanisms to be compared to simple thermal decomposition. Overall, ionic liquids outperformed reference oils as lubricants; in some cases, sacrificial films were formed (with anion breakdown a necessary precursor to phosphonium cation decomposition) while in other cases, a protective, self-assembly lubricant layer or hybrid film was formed. The salicylate-based anion was the most chemically stable and decomposed only slightly even under the harshest conditions. It was further found that surface topography influenced the degree of breakdown through enhanced material transport and replenishment. This work thus unveils the relationship between ionic liquid composition and structure, and the ensuing inter- and intra-molecular interactions and chemical stability, and demonstrates the intrinsic tuneability of an ionic liquid lubrication technology.

Layer-by-Layer Self-Assembled Thin Films for Triboelectric Energy Harvesting under Harsh Conditions

With the rapid growth in triboelectric nanogenerator (TENG) technology, selecting appropriate tribomaterial (TM) with high electrical output performance and a cheap fabrication technique is vital for sustainable nanogenerator operations. Thus, we prepared an electrostatic bonded thin poly(diallyldimethylammonium chloride) and poly(4-styrene-sulfonic acid) multilayered-based film as a potential positive TM via facile and cheap layer-by-layer (LbL) self-assembly fabrication technique. The high electrical output performance of the LbL-TENGs depends on the number of BL films was optimized by changing the number of bilayers (BLs) from 10 to 50. The 30 BL TENG shows a significant voltage of 189 V and a current density of 17 mA m–2 under the harsh environment of 65% RH, indicating the sustainability of the LbL-TENG device. Furthermore, the single-electrode mode of the optimized TENG exhibited an impressive TENG performance of 215 V and 79 mA m–2 and lit up 39 green light-emitting diodes just by tapping the TENG by hand.

High Loading Capacity and Wear Resistance of Graphene Oxide/Organic Molecule Assembled Multilayer Film.

Taking advantage of the strong charge interactions between negatively charged graphene oxide (GO) sheets and positively charged poly(diallyldimethylammonium chloride) (PDDA), self-assembled multilayer films of (GO/PDDA)n were created on hydroxylated silicon substrates by alternating electrostatic adsorption of GO and PDDA. The formation and structure of the films were analyzed by means of water contact angle measurement, thickness measurement, atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). Meanwhile, tribological behaviors in micro- and macro- scale were investigated by AFM and a ball-on-plate tribometer, respectively. The results showed that (GO/PDDA)n multilayer films exhibited excellent friction-reducing and anti-wear abilities in both micro- and macro-scale, which was ascribed to the special structure in (GO/PDDA)n multilayer films, namely, a well-stacked GO–GO layered structure and an elastic 3D crystal stack in whole. Such a film structure is suitable for design molecular lubricants for MEMS and other microdevices.

Ultrahigh In-Plane Thermoelectric Performance in Self-Assembled PbSe:Au Films With Vertically Aligned Nanopillar

Self-assembled nanocomposites with tunable physical properties have potential applications in advanced devices. In this work, self-assembled PbSe:Au films with vertically aligned nanopillars (VAN) were fabricated by pulsed laser deposition. Detailed heterostructures with atomic-resolution have been investigated by cross-sectional scanning tunnelling microscopy. The results show that self-assembled Au nanopillars in a PbSe matrix is realized. Compared with PbSe matrix, PbSe:Au vertical interface can facilitate energy filter effect and lower the in-plane thermal conductivity. The maximum ZT values for n-type self-assembled VAN film is ~2.6 at 523 K, which is ~400% higher than that of pure PbSe film (ZT=0.5). This study suggests that the vertical interface in the unique VAN provide a viable route to manipulate the thermoelectric properties for the thermoelectric materials.

Self-assembled donor-acceptor hole contacts for inverted perovskite solar cells with an efficiency approaching 22%: The impact of anchoring groups

Self-assembled molecules (SAMs) have shown great potential in replacing bulk charge selective contact layers in high-performance perovskite solar cells (PSCs) due to their low material consumption and simple processing. Herein, we design and synthesize a series of donor-acceptor (D-A) type SAMs (MPA-BT-CA, MPA-BT-BA, and MPA-BT-RA, where MPA is 4-methoxy-N-(4-methoxyphenyl)-N-phenylaniline; BT is benzo[c][1,2,5]-thiadiazole; CA is 2-cyanoacrylic acid, BA is benzoic acid, RA is rhodanine-3-propionic acid) with distinct anchoring groups, which show dramatically different properties. MPA-BT-CA with CA anchoring groups exhibited stronger dipole moments and formed a homogeneous monolayer on the indium tin oxide (ITO) surface by adopting an upstanding self-assembling mode. However, the MPA-BT-RA molecules tend to aggregate severely in solid state due to the sp3 hybridization of the carbon atom on the RA group, which is not favorable for achieving a long-range ordered self-assembled layer. Consequently, benefiting from high dipole moment, as well as dense and uniform self-assembled film, the device based on MPA-BT-CA yielded a remarkable power conversion efficiency (PCE) of 21.81%. Encouragingly, an impressive PCE approaching 20% can still be obtained for the MPA-BT-CA-based PSCs as the device area is increased to 0.80 cm2. Our work sheds light on the design principles for developing hole selecting SAMs, which will pave a way for realizing highly efficient, flexible, and large-area PSCs.

Sensing enhancement ammonia gas sensor based on a hybrid film fiber

A sensing enhancement sensor based on hybrid film fiber has been proposed to detect ammonia. The hybrid film coated on the MMF-SMF-MMF (Multimode Fiber–Single-mode Fiber–Multimode Fiber) structure is composed of single-walled carbon nanotubes with carboxylic acid groups (SWCNTs-COOH) self-assembled film and the silver film that was used to excite surface plasmon polariton (SPP) which contribute to enhancing the sensitive for refractive index (RI). The presence of free carboxylic acid functional groups and large surface area on the SWCNTs-COOH leads to high adsorption and selectivity toward amine compounds. The sensor works under a wavelength modulation scheme. And the resonance wavelength showed a red shift with an increase of the effective RI of the SWCNTs-COOH self-assembled film affected by ammonia concentration. The experimental results show that the sensor coated with hybrid film has high sensitivity and selectivity to ammonia gas. The proposed sensor is linearly responsive to ammonia concentration in the range 0 - 30 ppm, with a maximum sensitivity of 0.8 nm/ppm, the resolution 0.375 ppm, and the measured response 30 s, respectively. Finally, the sensor also has the advantages of simple structure and compact size, excellent stability, and low cost.