Single-component Films Research Articles

Vapor phase assembly of benzotriazole and octadecylamine complex films on aluminum alloy surface

The complex films of benzotriazole and octadecylamine have been prepared on the surface of aluminum alloy via vapor phase self-assembly method. Their anticorrosion and wettability are investigated by the electrochemical measurements and the contact angle tests. It shows that the complex films have a better protection effect on aluminum alloys compared with the single component films. The performance of the complex films is related to the sequence of vapor phase self-assembly. The formation mechanism of the different complex films is discussed based on the self-assembly sequence.

Atomic layer deposition of void-free ZnFe2O4 thin films and their magnetic properties

Atomic layer deposition (ALD) is an excellent method for depositing single-component thin films, but it is not a suitable technique for directly depositing multi-component films because different precursor sources usually require incompatible growing conditions. Therefore, an effective method to grow multi-component films by ALD is to prepare multi-layers films and then post-anneal them to form multi-component films. However, as has been reported so far, Kirkendall voids always inevitably form during post-annealing of ZnO/Fe3O4 thin films to form pure-phase zinc ferrite (ZnFe2O4) films, making it hard to obtain a compact zinc ferrite films without voids. Therefore, it is still challenging to prepare high-quality spinel films without voids by ALD. In this work, we used ALD to grow pure-phase and Kirkendall void-free ZnFe2O4 spinel thin films. The systematic transmission electron microscopy and selected area electron diffraction investigations prove that the as-grown ZnO and Fe3O4 thin films are composed of a number of nano-crystalline particles embedded in an amorphous matrix. This kind of unique microstructure is favorable for the thermal diffusion of elements during the solid-state reaction to form high-quality spinel films at a low temperature. The magnetic characterizations indicate that the obtained ZnFe2O4 thin films have a net magnetization, exhibiting ferrimagnetic behavior at room temperature and a very low blocking temperature TB=17K±2K.

Influence of Free Volume Determined by Positron Annihilation Lifetime Spectroscopy (PALS) on Gas Permeability of Cellulose Nanocrystal Films.

Cellulose nanocrystals (CNCs) are of increasing interest for packaging applications because of their biodegradability, low cost, high crystallinity, and high aspect ratio. The objective of this study was to use positron annihilation lifetime spectroscopy (PALS) to investigate the free volume of CNC films with different structural arrangements (chiral nematic vs shear-oriented CNC films) and relate this information to gas barrier performance. It was found that sheared CNC films with higher CNC alignment have lower free volume and hence have more tortuosity than chiral nematic self-assembled films, which lowers gas diffusion throughout the films. The overall barrier performance of the aligned CNC film obtained in this study has a higher barrier performance than high barrier polymer films like PVOH and EVOH. Furthermore, a modified model was developed for single-component CNC films to predict the gas permeability with variation of CNC alignment with validation by the data taken.

A single-component, cross-linked, and surface-grafted polyelectrolyte film fabricated by the layer-by-layer assembly method

In this work, we demonstrate a versatile approach for the fabrication of a single-component polyelectrolyte layer with tunable thickness and functionality. Poly(ethylene glycol) methyl ether methacrylate (PEGMEMA) was copolymerized with either aminoethyl methacrylate (AMA) or methacrylic acid (MAA) to prepare statistical PEGMEMA copolymers carrying positive or negative charges, respectively. These polyelectrolytes were used in a conventional layer-by-layer assembly process followed by cross-linking to form a surface-grafted stable poly(PEGMEMA) layer carrying both negative and positive charges. To transform this layer into a single-component polyelectrolyte layer carrying just one type of ionizable group, the amino groups were quenched, thus leaving a single-component anionic PEGMEMA-based polyelectrolyte layer. Last, we demonstrate that compared to a zwitterionic layer, the anionic polyelectrolyte layer exhibits an enhanced protein-repelling property against bovine serum albumin (BSA).

Fabrication of Anticorrosion Dual-Component Silane Film on AZ31 Mg Alloy Surface by Self-assembly Method

Dual-component silane film consisting of 3-aminopropyltriethoxysilane (APS) and bis[3-(triethoxysilyl)propyl]tetrasulfide (BTESPT) has been prepared on the surface of AZ31 Mg alloy and the effect of different molar ratios and hydrolysis times on the corrosion resistance studied systematically. The results show that, compared with single-component silane films, the dual-component silane film exhibited good and long-term corrosion resistance in 3.5 wt.% NaCl solution when the molar ratio of APS to BTESPT was 1:2 and the hydrolysis time was 1 h. This can be ascribed to a high density of Si-O-Mg bonds in the silane film, tightly connected to the Mg alloy surface. Simultaneously, the substantial siloxane network in the silane film increased the length of the penetration paths for corrosive media, thereby improving the corrosion resistance of the Mg alloy.

Design of Friction, Morphology, Wetting, and Protein Affinity by Cellulose Blend Thin Film Composition.

Cellulose derivate phase separation in thin films was applied to generate patterned films with distinct surface morphology. Patterned polymer thin films are utilized in electronics, optics, and biotechnology but films based on bio-polymers are scarce. Film formation, roughness, wetting, and patterning are often investigated when it comes to characterization of the films. Frictional properties, on the other hand, have not been studied extensively. We extend the fundamental understanding of spin coated complex cellulose blend films via revealing their surface friction using Friction Force Microscopy (FFM). Two cellulose derivatives were transformed into two-phase blend films with one phase comprising trimethyl silyl cellulose (TMSC) regenerated to cellulose with hydroxyl groups exposed to the film surface. Adjusting the volume fraction of the spin coating solution resulted in variation of the surface fraction with the other, hydroxypropylcellulose stearate (HPCE) phase. The film morphology confirmed lateral and vertical separation and was translated into effective surface fraction. Phase separation as well as regeneration contributed to the surface morphology resulting in roughness variation of the blend films from 1.1 to 19.8 nm depending on the film composition. Friction analysis was successfully established, and then revealed that the friction coefficient of the films could be tuned and the blend films exhibited lowered friction force coefficient compared to the single-component films. Protein affinity of the films was investigated with bovine serum albumin (BSA) and depended mainly on the surface free energy (SFE) while no direct correlation with roughness or friction was found. BSA adsorption on film formed with 1:1 spinning solution volume ratio was an outlier and exhibited unexpected minimum in adsorption.

Edge States at Nematic Domain Walls in FeSe Films.

Quantum spin Hall (QSH) effect is an intriguing phenomenon arising from the helical edge states in two-dimensional topological insulators. We use molecular beam epitaxy (MBE) to prepare FeSe films with atomically sharp nematic domain boundaries, where tensile strains, nematicity suppression, and topological band inversion are simultaneously achieved. Using scanning tunneling microscopy (STM), we observe edge states at the Fermi level that spatially distribute as two distinct strips in the vicinity of the domain boundaries. At the end point of the boundaries, a bound state at the Fermi level is further observed. The topological origin of the edge states is supported by density functional theory calculations. Our findings not only demonstrate a candidate for QSH states but also provide a new pathway to realize topological superconductivity in a single-component film.

Growth and ferroelectric properties of yttrium-doped hafnium oxide/indium-tin oxide polycrystalline heterostructures with sharp and uniform interfaces

We report on the growth of polycrystalline yttrium-5%-doped HfO2 (YHO) films with sharp and uniform interfaces over a large area on indium-tin oxide (ITO) layers and their ferroelectric properties. On substrates of thermally oxidized silicon, YHO/ITO bilayers were deposited in amorphous form by means of pulsed-laser deposition and were subsequently crystalized by two-step post-deposition annealing (PDA) at low and high temperatures. The crystallized YHO/ITO heterostructures had ultraflat surfaces: atomic-force-microscopy images exhibited a root-mean-square roughness of 0.15 nm over an area of 100 μm2. The roughness was much smaller than that of single-component polycrystalline films of ITO. X-ray diffraction and transmission electron microscopy (TEM) suggested the formation of YHO in higher symmetry phases including ferroelectric orthorhombic (o) YHO. TEM also confirmed crystallization of YHO layers in a pseudo-coherent manner from the YHO/ITO interfaces and resultant sharp and uniform YHO/ITO interfaces. These results are attributable to good lattice matching between the o-YHO layer and the ITO layer. It is suggested that this lattice matching was realized by the reduction of ITO during the crystallization in the two-step PDA process. The reduction might occur in the vicinity of the YHO/ITO interface via H2O incorporated in the amorphous bilayers. Pt/YHO/ITO junctions fabricated by using the two-step PDA method showed a polarization–electric field (P–E) hysteresis loop with remanent polarizations (Pr) of no less than 13 μC/cm2 at YHO thicknesses of 12 and 6 nm. These results indicate that the two-step PDA method can be used to fabricate high-quality YHO/ITO heterostructures in terms of surface and interface morphology, as well as ferroelectric properties.

Photochromism of Amphiphilic Dithienylethenes as Langmuir-Schaefer Films.

Surface pressure-area isotherms were recorded under different irradiation conditions for single-component Langmuir films of three photochromic amphiphilic dithienylethenes. Nonirradiated films of these photochromic amphiphiles were mechanically stable. In addition, a shift of the isotherms to larger mean molecular areas was observed for films prepared from UV-light-irradiated dithienylethenes. Unexpectedly, a significant expansion was observed for a film prepared from visible-light-irradiated dithienylethene incorporating large branched alkyl chains. Upon further study, atomic force microscopy and transmission electron microscopy images of Langmuir-Schaefer films revealed that this pronged dialkyl derivative undergoes a photoinduced change in morphology, as circular aggregates coalesce into larger continuous aggregated structures. Nevertheless, its photoisomerization was completely reversible as single-component multilayer thin films upon direct UV or visible light irradiation.

(Invited) Photocarrier Generation in Single-Absorber Organic Solar Cells

Power Conversion efficiency of organic photovoltaic devices has exceeded 10% by taking advantage of bulk heterojunction (BHJ) structure, where donor and acceptor molecules are microscopically mixed. A remained problem is photovoltage loss from absorbed photon energy. In the BHJ system, LUMO offset is required to promote photodissociation at the donor-acceptor interface, causing serious photovoltage loss. To solve this problem, we are approaching it from single absorber cells, where there is no donor-acceptor interface. Generally, photogeneration efficiency in organic film bulk is quite low because of large exciton binding energy of Frenkel exciton. On the other hand, photogeneration from CT excitons occurs almost spontaneously in the BHJ system. If we could generate charge-transfer (CT) excitons in the single-component film directly, photovoltage loss would be reduced. Recently, we found intramolecular charge-transfer molecules including donor and acceptor units within one molecule show considerable high performance in the single-absorber device. In particular, DTDCPB having triphenyl amine unit (donor) and benzothiadiazole unit (acceptor) was a promising material for the single-absorber system. In this presentation, photogeneration process in the single-component film of CT molecules was investigated from several viewpoints. Molecular design for intramolecular charge-transfer absorption is discussed from the viewpoint of quantum chemical calculation and organic synthesis. The photocarrier dynamics in the single-absorber solar cells is investigated by several techniques such as intensity-modulated photovoltage/photocurrent (IMVS/IMPS) and time delayed collection field (TDCF). Exciton binding energy, that is a key factor for photodissociation in the film bulk, was estimated by Onsager-Braun analysis by using a planar device. Figure 1

Heterogeneous oxidation of indoor surfaces by gas-phase hydroxyl radicals.

We investigate heterogeneous oxidation kinetics of monolayer-thick, surface-sorbed organics, namely di-n-octyl phthalate (DnOP) and palmitic acid (PA), with gas-phase OH. The pseudo-first order rate constants for organic loss at OH concentrations of 1.6×108 molecules/cm3 are: (2.3±0.1)×10-4 to (4.8±0.8)×10-4 s-1 , and (1.3±0.5)×10-4 s-1 for DnOP and PA, respectively. Films developed in indoor office environments over a few weeks are also oxidized using the same OH concentration. Heterogeneous decay rate constants of mass signals from these films, attributed to phthalates (MW=390.6) and to PA, are similar to those for the single-component films, ie, (1.9±0.4)×10-4 to (3.4±0.5)×10-4 s-1 , and (1.1±0.4)×10-4 s-1 , respectively. These results suggest that the lifetimes for OH heterogeneous oxidation of monolayer-thick indoor organic films will be on the timescale of weeks to months. To support this argument, we present the first analysis of the mass transfer processes that occur when short-lived gas-phase molecules, such as OH, are taken up by reactive indoor surfaces. Due to rapid chemical production, the diffusion limitation to mass transfer is less important for short-lived molecules than for molecules with little chemical production, such as ozone.

Identifying Molecular Orientation in a Bulk Heterojunction Film by Infrared Reflection Absorption Spectroscopy.

The molecular orientation of organic molecules of zinc phthalocyanine (ZnPc) in single-component films on copper iodide (CuI) substrates can be controlled to achieve a molecular orientation lying flat on the substrate (flat-on) owing to π–d orbital interactions between the ZnPc molecules and the CuI. A 3-fold enhancement in the performance of organic photovoltaic cells has been reported by introducing a CuI interlayer between a ZnPc:fullerene (C60) bulk heterojunction (BHJ) film and the substrate. However, the mechanism underpinning the resultant solar cell performance enhancement was unclear. Herein, we report on the results of using in situ reflection absorption spectroscopy measurements during the vacuum deposition of coevaporated ZnPc:C60 BHJ films on various substrates to investigate the ZnPc molecular orientation. Our results revealed that the flat-on molecular orientation of ZnPc molecules in ZnPc:C60 BHJ films on CuI interlayers and flat-on ZnPc substrates can be successfully identified via the strong π–π interactions between the BHJ film and the substrate. The π–π interactions between individual ZnPc molecules are stronger than the π–d interactions between ZnPc molecules and CuI in coevaporated ZnPc:C60 films, as is evident from the molecular orientation of ZnPc, as determined by in situ reflection absorption spectroscopy. Our findings demonstrate that precisely controlling the molecular orientations of the films could enhance organic photovoltaic (OPV) performance. The present work provides important insights that will enable the design of higher performance OPV cells.

Formation and Photodynamic Behavior of Transition Metal Dichalcogenide Nanosheet-Fullerene Inorganic/Organic Nanohybrids on Semiconducting Electrodes.

Composite films that consisted of C60 and well-exfoliated nanosheets of transition metal dichalcogenides (TMDs), such as MoS2 or WS2 , with a bulk heterojunction structure were easily fabricated onto a semiconducting SnO2 electrode via a two-step methodology: self-assembly into their composite aggregates by injection of a poor solvent into a good solvent with the dispersion, and subsequent electrophoretic deposition. Upon photoexcitation, the composites on SnO2 exhibited enhanced transient conductivity in comparison with single components of TMDs or C60 , which demonstrates that the bulk heterojunction nanostructure of TMD and C60 promoted the charge separation (CS). In addition, the decoration of the TMD nanosheets with C60 hindered the undesirable charge recombination (CR) between an electron in SnO2 and a hole in the TMD nanosheets. Owing to the accelerated CS and suppressed CR, photoelectrochemical devices based on the MoS2 -C60 and WS2 -C60 composites achieved remarkably improved incident photon-to-current efficiencies (IPCEs) as compared with the single-component films. Despite more suppressed CR in WS2 -C60 than MoS2 -C60 , the IPCE value of the device with WS2 -C60 was smaller than that with MoS2 -C60 owing to its inhomogeneous film structure.

Beyond Donor-Acceptor (D-A) Approach: Structure-Optoelectronic Properties-Organic Photovoltaic Performance Correlation in New D-A1 -D-A2 Low-Bandgap Conjugated Polymers.

Low-bandgap near-infrared polymers are usually synthesized using the common donor-acceptor (D-A) approach. However, recently polymer chemists are introducing more complex chemical concepts for better fine tuning of their optoelectronic properties. Usually these studies are limited to one or two polymer examples in each case study so far, though. In this study, the dependence of optoelectronic and macroscopic (device performance) properties in a series of six new D-A1 -D-A2 low bandgap semiconducting polymers is reported for the first time. Correlation between the chemical structure of single-component polymer films and their optoelectronic properties has been achieved in terms of absorption maxima, optical bandgap, ionization potential, and electron affinity. Preliminary organic photovoltaic results based on blends of the D-A1 -D-A2 polymers as the electron donor mixed with the fullerene derivative [6,6]-phenyl-C71 -butyric acid methyl ester demonstrate power conversion efficiencies close to 4% with short-circuit current densities (J sc ) of around 11 mA cm-2 , high fill factors up to 0.70, and high open-circuit voltages (V oc s) of 0.70 V. All the devices are fabricated in an inverted architecture with the photoactive layer processed in air with doctor blade technique, showing the compatibility with roll-to-roll large-scale manufacturing processes.

Using Diffusion To Characterize Interfacial Heterogeneity

We report on the use of molecular diffusional motion over a range of length scales to characterize compositional heterogeneity in monolayer structures. This work focuses on the diffusional motion of perylene in two types of films supported on functionalized silica surfaces: single-component (stearic acid) and two-component (hydrocarbon/fluorocarbon) films. Langmuir-Blodgett (LB) monolayers were deposited directly on silica or were bound to surface-modified silica by means of metal ion complexation. The LB films were characterized by their π-A isotherms and by Brewster angle microscopy (BAM) during formation and deposition. Chromophore mobility and monolayer structural heterogeneity were evaluated by comparing rotational diffusion data (fluorescence anisotropy decay imaging) and translational diffusion data (fluorescence recovery after photobleaching) on the same LB films. Our results indicate that the mobility of the chromophore depends sensitively on both metal ion identity and film composition.

First observation of 3D aggregates in a single-component Langmuir film below the equilibrium spreading pressure

Single component monolayers from Dipalamitoyl Phosphatidyl Ethanolamine head labelled with the fluorescent chromophore NitroBenzoxaDiazole (DP-NBD-PE) were investigated at the air-water interface as Langmuir films and deposited on silicon wafers or glass plates as Langmuir-Blodgett (LB) films. A step compression and monitoring of the pressure relaxation together with domain formation as observed with Brewster angle microscopy suggests that main transition from liquid expanded to liquid compressed state start at around 6.9 mN/m though on the isotherm it starts around 9 mN/m at 25° C. Brewster angle microscopy also reveals a nonuniform structure in the monolayer. 3D aggregates - cylinders with 50 – 150 nm diameter and bilayer height were observed with Atomic Force Microscopy when deposition was carried at 7 mN/m, above the main phase transition but considerably lower than the equilibrium spreading pressure of 19.6 mN/m for this molecule. When LB film deposition is carried just below the main phase transition a uniform height layer of film in a liquid phase is observed with AFM with no structures. Both compression and deposition were carried at very low speeds with large time to relax in ordered to avoid kinetic effects. These 3D aggregates are not due to the transfer process or interaction with the substrate. These aggregates provide a highly developed area combined with monolayer thick structure which can produce very fast and highly sensitive biosensors.

Zeolite-loaded poly(dimethylsiloxane) hybrid films for highly efficient thin-film microextraction of organic volatiles in water.

ZSM-5 zeolite-loaded poly(dimethylsiloxane) (PDMS) hybrid thin films were demonstrated for efficient thin-film microextraction (TFME) coupled with gas chromatography-mass spectrometry for analyzing organic volatiles in water. The extraction efficiency for a series of aliphatic alcohols and two aromatic compounds was significantly improved owing to the presence of ZSM-5 zeolites. The extraction efficiency of the hybrid films was increased in proportion to the content of ZSM-5 in the PDMS film, with 20wt% of ZSM-5 showing the best results. The 20wt% ZSM-5/PDMS hybrid film exhibited higher volatile organic content extraction compared with the single-component PDMS film or PDMS hybrid films containing other types of zeolite (e.g., SAPO-34). Limits of detection and limits of quantitation for individual analytes were in the range of 0.0034-0.049ppb and of 0.010-0.15 ppb, respectively. The effects of experimental parameters such as extraction time and temperature were optimized, and the molecular dispersion of the zeolites in/on the hybrid film matrix was confirmed with scanning electron microscopy and atomic force microscopy. Furthermore, the optimized hybrid film was preliminarily tested for the analysis of organic volatiles contained in commercially available soft drinks.

Three-dimensional ordered titanium dioxide-zirconium dioxide film-based microfluidic device for efficient on-chip phosphopeptide enrichment

HypothesisMicrofluidic technology plays a significant role in separating biomolecules, because of its miniaturization, integration, and automation. Introducing micro/nanostructured functional materials can improve the properties of microfluidic devices, and extend their application. Inverse opal has a three-dimensional ordered net-like structure. It possesses a large surface area and exhibits good mass transport, making it a good candidate for bio-separation. This study exploits inverse opal titanium dioxide-zirconium dioxide films for on-chip phosphopeptide enrichment. ExperimentsTitanium dioxide-zirconium dioxide inverse opal film-based microfluidic devices were constructed from templates of 270-, 340-, and 370-nm-diameter poly(methylmethacrylate) spheres. The phosphopeptide enrichments of these devices were determined by matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry. FindingsThe device constructed from the 270-nm-diameter sphere template exhibited good comprehensive phosphopeptide enrichment, and was the best among these three devices. Because the size of opal template used in construction was the smallest, the inverse opal film therefore had the smallest pore sizes and the largest surface area. Enrichment by this device was also better than those of similar devices based on nanoparticle films and single component films. The titanium dioxide-zirconium dioxide inverse opal film-based device provides a promising approach for the efficient separation of various biomolecules.

Mixed layered WO3/ZrO2 films (with and without rhodium) as active supports for PtRu nanoparticles: enhancement of oxidation of ethanol

Mixed-valent tungsten(VI,V) oxide and zirconium(IV) oxide have been sequentially deposited and integrated through voltammetric potential cycling to form robust sub-microstructured mixed metal oxide (WO3/ZrO2) films on glassy carbon electrode. Attractive interactions between anionic tungstate units (of the inner WO3 layer) and cationic oxo-zirconium surface species (existing in acid media on ZrO2 nanostructures in the outer layer) tend to stabilize the mixed oxide system. By dispersing bimetallic platinum-ruthenium (PtRu) nanoparticles over such active WO3/ZrO2 supports, the activity of PtRu toward the oxidation of ethanol has been enhanced in terms of both increasing the electrocatalytic currents and lowering the onset potential of this reaction. The catalytic effect is more pronounced relative to the performance of PtRu nanoparticles deposited at the same loading of 100μgcm−2 onto single-component metal oxide films, WO3 or ZrO2. Immobilization of rhodium nanoparticles onto WO3 inner layer (before over-coating with outer ZrO2 layer and deposition of PtRu) has led to further remarkable increases of electrocatalytic (voltammetric, chronoamperometric) currents recorded at the room temperature (22°C) in 0.5moldm−3H2SO4 containing 0.5moldm−3 ethanol. Among important issues is the initial activation of ethanol molecule (presumably by inducing the CC bond breaking) before catalytic electrooxidation at PtRu. Furthermore, the mixed WO3/ZrO2 film (support) is characterized by high acidity and fast charge (electron, proton) propagation during the system’s redox transitions. High population of OH reactive groups and good mobility of protons (particularly at zirconia sites) is expected to increase activity of PtRu sites toward the oxidative removal of poisoning (CO) intermediates.

Thermally Induced Charge Reversal of Layer-by-Layer Assembled Single-Component Polymer Films.

Temperature can be harnessed to engineer unique properties for materials useful in various contexts and has been shown to affect the layer-by-layer (LbL) assembly of polymer thin films and cause physical changes in preassembled polymer thin films. Herein we demonstrate that exposure to relatively low temperatures (≤ 100 °C) can induce physicochemical changes in cationic polymer thin films. The surface charge of polymer films containing primary and secondary amines reverses after heating (from positive to negative), and different characterization techniques are used to show that the change in surface charge is related to oxidation of the polymer that specifically occurs in the thin film state. This charge reversal allows for single-polymer LbL assembly to be performed with poly(allylamine) hydrochloride (PAH) through alternating heat/deposition steps. Furthermore, the negative charge induced by heating reduces the fouling and cell-association of PAH-coated planar and particulate substrates, respectively. This study highlights a unique property of thin films which is relevant to LbL assembly and biofouling and is of interest for the future development of thin polymer films for biomedical systems.