Preparation of Hybrid Films Based in Aluminum 8-Hydroxyquinoline as Organic Semiconductor for Photoconductor Applications.

In the present work, we have investigated an organic semiconductor based on tris(8-hydroxyquinoline) aluminum (AlQ3) doped with tetracyanoquinodimethane (TCNQ), which can be used as an organic photoconductor. DFT calculations were carried out to optimize the structure of semiconductor species and to obtain related constants in order to compare experimental and theoretical results. Subsequently, AlQ3-TCNQ films with polypyrrole (Ppy) matrix were fabricated, and they were morphologically and mechanically characterized by Scanning Electron Microscopy, X-ray diffraction and Atomic Force Microscopy techniques. The maximum stress for the film is 8.66 MPa, and the Knoop hardness is 0.0311. The optical behavior of the film was also analyzed, and the optical properties were found to exhibit two indirect transitions at 2.58 and 3.06 eV. Additionally, photoluminescence measurements were carried out and the film showed an intense visible emission in the visible region. Finally, a photoconductor was fabricated and electrically characterized. Applying a cubic spline approximation to fit cubic polynomials to the J-V curves, the ohmic to SCLC transition voltage VON and the trap-filled-limit voltage VTFL for the device were obtained. Then, the free carrier density and trap density for the device were approximated to n0=4.4586×10191m3 and Nt=3.1333×10311m3, respectively.

Pentacoordinated Organotin(IV) Complexes as an Alternative in the Design of Highly Efficient Optoelectronic and Photovoltaic Devices: Synthesis and Photophysical Characterization.

The synthesis of four pentacoordinated organotin(IV) complexes prepared in a one-pot reaction from 2-hydroxy-1-naphthaldehyde, 2-amino-3-hydroxypyridine and organotin oxides is reported. The complexes were characterized by UV-Vis, IR, MS, 1H, 13C and 119Sn NMR techniques. The compound based on 2,2-diphenyl-6-aza-1,3-dioxa-2-stannanaphtho[1,2-h]pyrido[3,2-d]cyclononene revealed the formation of a monomeric complex with a distorted five-coordinated molecular geometry intermediate between the trigonal bipyramidal and square pyramidal. In order to find possible applications in photovoltaic devices, hybrid films of organotin(IV) complexes embedded in poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) with graphene were deposited. The topographic and mechanical properties were examined. The film with the complex integrated into the cyclohexyl substituent has high plastic deformation, with a maximum stress of 1.69 × 107 Pa and a Knoop hardness of 0.061. The lowest values of 1.85 eV for the onset gap and 3.53 eV for the energy gap were obtained for the heterostructure having the complex with the phenyl substituent. Bulk heterojunction devices were fabricated; these devices showed ohmic behavior at low voltages and a space-charge-limited current (SCLC) conduction mechanism at higher voltages. A value of 0.02 A was found for the maximum carried current. The SCLC mechanism suggests hole mobility values of between 2.62 × 10-2 and 3.63 cm2/V.s and concentrations of thermally excited holes between 2.96 × 1018 and 4.38 × 1018 m-3.

Physico-Chemical Characterization and Antimicrobial Properties of Hybrid Film Based on Saponite and Phloxine B.

This research was aimed at the preparation of a hybrid film based on a layered silicate saponite (Sap) with the immobilized photosensitizer phloxine B (PhB). Sap was selected because of its high cation exchange capacity, ability to exfoliate into nanolayers, and to modify different surfaces. The X-ray diffraction of the films confirmed the intercalation of both the surfactant and PhB molecules in the Sap film. The photosensitizer retained its photoactivity in the hybrid films, as shown by fluorescence spectra measurements. The water contact angles and the measurement of surface free energy demonstrated the hydrophilic nature of the hybrid films. Antimicrobial effectiveness, assessed by the photodynamic inactivation on hybrid films, was tested against a standard strain and against methicillin-resistant bacteria of Staphylococcus aureus (MRSA). One group of samples was irradiated (green LED light; 2.5 h) and compared to nonirradiated ones. S. aureus strains manifested a reduction in growth from 1-log10 to over 3-log10 compared to the control samples with Sap only, and defects in S. aureus cells were proven by scanning electron microscopy. The results proved the optimal photo-physical properties and anti-MRSA potential of this newly designed hybrid system that reflects recent progress in the modification of surfaces for various medical applications.

Reversibility-Dependent Photovoltammetric Behavior of Electroactive Compounds on a CdS-Graphene Hybrid Film Electrode.

Photovoltammetric behaviors of irreversible, quasi-reversible and reversible electrochemical systems represented by 2,4-dichlorophenol (DCP), hydroquinone (HQ) and K3 [Fe(CN)6 ], respectively, were investigated on a CdS-graphene hybrid film electrode. The cyclic voltammetric (CV) curves of HQ and K3 [Fe(CN)6 ] showing a pair of redox peaks became sigmoidal in shape under visible light irradiation. In contrast, the CV curve shape of DCP showing an oxidation peak was not changed under photoirradiation, although the oxidation peak current was enhanced by the photoelectrocatalysis. Thus, the reversibility-dependent photovoltammetric behaviors were observed. Furthermore, it was demonstrated that the photovoltammetric curve shapes were not changed by pH and intensity of light source, but were tunable with scan rate and concentration of reactants depending on the reversibility of the electrochemical reactions.

High Performance Flexible Actuator of Urchin-Like ZnO Nanostructure/Polyvinylenefluoride Hybrid Thin Film with Graphene Electrodes for Acoustic Generator and Analyzer.

A bass frequency response enhanced flexible polyvinylidene fluoride (PVDF) based thin film acoustic actuator is successfully fabricated. High concentrations of various zinc oxide (ZnO) is embedded in PVDF matrix, enhancing the ß phase content and the dielectric property of the composite thin film. ZnO acts as a nucleation agent for the crystallization of PVDF. A chemical vapor deposition grown graphene is used as electrodes, enabling high electron mobility for the distortion free acoustic signals. The frequency response of the fabricated acoustic actuator is studied as a function of the film thickness and filler content. The optimized film has a thickness of 80 µm with 30 wt% filler content and shows 72% and 42% frequency response enhancement in bass and midrange compared to the commercial PVDF, respectively. Also, the total harmonic distortion decreases to 82% and 74% in the bass and midrange regions, respectively. Furthermore, the composite film shows a promising potential for microphone applications. Most of all, it is demonstrated that acoustic actuator performance is strongly influenced by degree of PVDF crystalline.

Lattice relaxation at the interface of two-dimensional crystals: graphene and hexagonal boron-nitride.

Heteroepitaxy of two-dimensional (2D) crystals, such as hexagonal boron nitride (BN) on graphene (G), can occur at the edge of an existing heterointerface. Understanding strain relaxation at such 2D laterally fused interface is useful in fabricating heterointerfaces with a high degree of atomic coherency and structural stability. We use in situ scanning tunneling microscopy to study the 2D heteroepitaxy of BN on graphene edges on a Ru(0001) surface with the aim of understanding the propagation of interfacial strain. We found that defect-free, pseudomorphic growth of BN on a graphene edge "substrate" occurs only for a short distance (<1.29 nm) perpendicular to the interface, beyond which misfit zero-dimensional dislocations occur to reduce the elastic strain energy. Boundary states originating from a coherent zigzag-linked G/BN boundary are observed to greatly enhance the local conductivity, thus affording a new avenue to construct one-dimensional transport channels in G/BN hybrid interface.

Advanced hydrostable, recyclable and degradable cellulose hybrid films as renewable alternatives to synthetic plastics.

Strong, tough and sustainable materials are in high demand in various engineering applications. We demonstrate a potential sustainable hybrid film made from natural cellulose and a biobased slurry. Through a simple and scalable approach, cellulose can be processed into an advanced material with over 2.8 and 9.2-fold increase in dry strength and toughness after curing and a 728-fold increase in wet strength, respectively. In addition, these hybrid composite films display an outstanding antioxidant activity surpassing 90 %, along with excellent ultraviolet radiation shielding and thermal insulation properties. Further, the hybrid films can be fabricated by integrating all-natural materials and still guarantee their unique functionality. We also demonstrate the feasibility of a circular bioeconomy by recycling the hybrid film using a green, deep eutectic solvent to fabricate a recycled hybrid film that displays excellent mechanical and optical properties. When recycling is unsuitable or economical, the hybrid film can naturally degrade in the soil under 6 months. These encouraging findings suggest the promise of cellulose hybrid films as a renewable, low-cost, tough, and strong material with the potential to replace nonrenewable synthetic plastics and products.

Photochromic Spiropyran-Based Dual-Emitting Luminescent Hybrid Films for Dynamic Information Anticounterfeiting.

Photoluminescent materials are widely used for information storage and anticounterfeiting, while most of them have the disadvantages of static information performance and weak processability, which is still a challenging task in developing dynamic anticounterfeiting materials with high security levels. Herein, we fabricated a novel photostimuli-responsive dual-emitting luminescent material UPTES-SPn-Tb-hfa, which was obtained by introducing the photochromic molecule spiropyran (SP) and lanthanide complex (Tb-hfa) into a siloxane-polyether matrix using the sol-gel process. Due to the conformation-dependent photochromic fluorescence resonance energy transfer between the Tb-hfa donor and SP acceptor, the ring-closing (SP)/ring-opening (MC) isomerization of the SP unit leads to a reversible luminescence switching in UPTES-SPn-Tb-hfa. This composite material has great potential for advanced anticounterfeiting because of the advantage of rapidly repeatable encryption/decryption for at least 8 times and dynamic luminescent colors within 15 s. In addition, due to its two luminescent centers (Tb3+ and MC), the luminescent color of this material can be regulated by 254 and 365 nm UV-light irradiation, which facilitates the design of multicolored anticounterfeiting labels. Our work presents a novel design methodology to fabricate dynamic anticounterfeiting materials, significantly enhancing the security of anticounterfeiting applications.

Synthesis of Hydrophilic Poly(vinylpyrrolidone)/CuS Free-Standing Thin Films Exhibiting Photothermal Conversion.

Free-standing films without the need for any support materials attract attention because of their excellent flexibility in use and ability to be transferred to various substrates. However, free-standing films containing large amounts of inorganic crystalline particles are hard to achieve due to their low strength. In this study, we found the possibility of preparing a free-standing composite film of CuS/polyvinylpyrrolidone (PVP) at a large loading of CuS (>50%) from a concentrated colloidal dispersion of CuS nanoparticles modified with PVP. Despite the large amount of inorganic crystals contained in the free-standing film, the film was strong enough to be handled without any support materials. As a proof-of-concept application of the free-standing film, a solar water evaporation experiment was performed. The CuS/PVP free-standing film exhibited photothermal conversion under light illumination to generate heat and accelerate water evaporation, achieving an evaporation rate of 4.35 kg·m-2 h-1 and an evaporation efficiency of 96.3% at a power density of 3 suns. In addition, thanks to the free-standing feature, one side of the CuS/PVP film could be hydrophobized with polydimethylsiloxane to form a Janus thin film, allowing for floating on the water surface. As a result, effective water evaporation was achieved because of the selective evaporation of water from the air/water interface.

Hybridization of Polymer-Encapsulated MoS2-ZnO Nanostructures as Organic-Inorganic Polymer Films for Sonocatalytic-Induced Dye Degradation.

The development of environmentally friendly technology is vital to effectively address the issues related to environmental deterioration. This work integrates ZnO-decorated MoS2 (MZ) to create a high-performing PVDF-based PVDF/MoS2-ZnO (PMZ) hybrid polymer composite film for sonocatalytic organic pollutant degradation. An efficient synergistic combination of MZ was identified by altering the ratio, and its influence on PVDF was assessed using diverse structural, morphological, and sonocatalytic performances. The PMZ film demonstrated very effective sonocatalytic characteristics by degrading rhodamine B (RhB) dye with a degradation efficiency of 97.23%, whereas PVDF only degraded 17.7%. Combining MoS2 and ZnO reduces electron-hole recombination and increases the sonocatalytic degradation performance. Moreover, an ideal piezoelectric PVDF polymer with MZ enhances polarization to improve redox processes and dye degradation, ultimately increasing the degradation efficiency. The degradation efficiency of RhB was seen to decrease while employing isopropanol (IPA) and p-benzoquinone (BQ) due to the presence of reactive oxygen species. This suggests that the active species •O2- and •OH are primarily responsible for the degradation of RhB utilizing PMZ2 film. The PMZ film exhibited improved reusability without substantially decreasing its catalytic activity. The superior embellishment of ZnO onto MoS2 and effective integration of MZ into the PVDF polymer film results in improved degrading performance.

Antibacterial Biomimetic Hybrid Films.

In this work, we present a novel method to prepare a hybrid coating based on dextran grafted to a substrate and embedded with silver nanoparticles (Ag NPs). First, the Ag NPs are synthesized in situ in the presence of oxidized dextran in solution. Second, the oxidized dextran is exposed to an amine functionalized surface resulting in the simultaneous grafting of dextran and the trapping of Ag NPs within the layer. The NP loading is controlled by the concentration of silver nitrate, which is 2 mM (DEX-Ag2) and 5 mM (DEX-Ag5). The dried film thickness increases with silver nitrate concentration from 2 nm for dextran to 7 nm and 12 nm for DEX-Ag2 and DEX-Ag5, respectively. The grafted dextran film displays features with a diameter and height of ~ 50 nm and 2 nm, respectively. For the DEX-Ag2 and DEX-Ag5, the dextran features as well as individual Ag NPs (~ 5 nm) and aggregates of Ag NPs are observed. Larger and more irregular aggregates are observed for DEX-Ag5. Overall, the Ag NPs are embedded in the dextran film as suggested by AFM and UVO studies. In terms of its antimicrobial activity, DEX-Ag2 resists bacterial adhesion to a greater extent than DEX-Ag5, which in turn is better than dextran and silicon. Because these antibacterial hybrid coatings can be grafted to a variety of surfaces, many biomedical applications can be envisioned, ranging from coating implants to catheters.

Influence of the Polymeric Matrix on the Optical and Electrical Properties of Copper Porphine-Based Semiconductor Hybrid Films.

In this study, we assessed the electrical and optical behavior of semiconductor hybrid films fabricated from octaethyl-21H,23H-porphine copper (CuP), embedded in polymethylmethacrylate (PMMA), and polystyrene (PS). The hybrid films were characterized structurally and morphologically using infrared spectroscopy (IR), atomic force microscopy (AFM), scanning electron microscopy (SEM), and X-ray diffraction (XRD). Subsequently, the PMMA:CuP and PS:CuP hybrid films were evaluated optically by UV-vis spectroscopy, as well as electrically, with the four-point collinear method. Hybrid films present a homogeneous and low roughness morphology. In addition, the PS matrix allows the crystallization of the porphin, while PMMA promotes the amorphous structure in CuP. The polymeric matrix also affects the optical behavior of the films, since the smallest optical gap (2.16 eV) and onset gap (1.89 eV), and the highest transparency are obtained in the film with a PMMA matrix. Finally, the electrical behavior in hybrid films is also affected by the matrix: the largest amount of current carried is approximately 0.01 A for the PS:CuP film, and 0.0015 A for the PMMA:CuP film. Thanks to the above properties, hybrid films are promising candidates for use in optoelectronic devices.

Salt-Assisted Fabrication of a Water-Based Covalent Organic Framework Ink and Its Hybrid Films for Photothermal Actuators.

The exceptional properties of two-dimensional covalent organic framework materials (2D-COFs), including their large π-conjugated structure at the molecular level and π-π multilayer stacking, have attracted interest for soft photothermal actuator applications. However, the conventional synthesis of COFs as microcrystalline powders limits their processing in water due to their limited dispersibility. Herein, we present a simple and environmentally friendly method to fabricate water-suspended COF inks by adjusting the surface potential of COF powders through adsorption of ionic species such as Na+ and Cl-. This technique effectively prevents the accumulation and aggregation of COF powder, resulting in an aqueous COF ink that can be easily cast into homogeneous hybrid COF films by Mayer-rod coating. In addition, the resulting photothermal actuator exhibited a fast response time within 3 s at a curvature of 2.35 cm-1 in the near-infrared light. This facile and practical approach to fabricating water-based COFs ink represents a promising strategy for the development of practical applications of COFs in photothermal actuators.

Fabrication and Characterization of Hybrid Films Based on NiFe2O4 Nanoparticles in a Polymeric Matrix for Applications in Organic Electronics.

Hybrid films for applications in organic electronics from NiFe2O4 nanoparticles (NPs) in poly(3,4 ethylene dioxythiophene), poly(4-styrenesulfonate) (PEDOT:PSS), and poly(methyl methacrylate) (PMMA) were fabricated by the spin-coating technique. The films were characterized by infrared spectroscopy, atomic force microscopy, scanning electron microscopy, and energy-dispersive spectroscopy to subsequently determine their optical parameters. The electronic transport of the hybrid films was determined in bulk heterojunction devices. The presence of NiFe2O4 NPs reinforces mechanical properties and increases transmittance in the hybrid films; the PEDOT:PSS-NiFe2O4 NPs film is the one that has a maximum stress of 28 MPa and a Knoop hardness of 0.103, while the PMMA-NiFe2O4 NPs film has the highest transmittance of (87%). The Tauc band gap is in the range of 3.78-3.9 eV, and the Urbach energy is in the range of 0.24-0.33 eV. Regarding electrical behavior, the main effect is exerted by the matrix, although the current carried is of the same order of magnitude for the two devices: glass/ITO/polymer-NiFe2O4 NPs/Ag. NiFe2O4 NPs enhance the mechanical, optical, and electrical behavior of the hybrid films and can be used as semi-transparent anodes and as active layers.

Atomic/Molecular Layer-Deposited Laminated Li2O-Lithicone Interfaces Enabling High-Performance Silicon Anodes.

Silicon-based materials are of long-standing interest as the anodes for next-generation lithium-ion batteries, yet their low initial Coulombic efficiency and poor interfacial stability are lethal limitations. In this work, we used atomic layer deposition (ALD) and molecular layer deposition (MLD) techniques to fabricate a lithium-containing laminated Li2O-lithicone hybrid film (∼5 nm) on a silicon electrode. The laminated film provides an additional surface Li source around silicon cores, which can partially reimburse the Li loss during battery cycling. Characterization of interfacial components shows that such a laminated Li2O-lithicone interface undergoes gentle element changes and participates in a hybrid solid electrolyte interphase with Li2CO3, Li2O, LixPOFy, and LiF species. Finite element model analysis and morphology characterization demonstrate that the laminated structure design can help relieve the interfacial stress and thus retain the integrity and reactivity of the silicon composite anode during cycling. Moreover, the lithium-based laminated film leads to a fast Li+ migration kinetics on the surface of the electrode as revealed by the galvanostatic intermittent titration technique and density functional theory calculation. Benefiting from the above merits, a silicon anode with a 91.2% initial Coulombic efficiency, a rate performance of 1460 mA h g-1 at 2 A g-1, and a reversible capacity over 646 mA h g-1 after 850 cycles was achieved. This work exemplifies the advantages of lithium-based hybrid films precisely engineered by ALD/MLD techniques for improving performances of advanced silicon anode batteries and deepens understandings on the mechanism of interfacial stability and reaction kinetics.

One-Step In Situ Patternable Reduction of a Ag-rGO Hybrid Using Temporally Shaped Femtosecond Pulses.

In recent years, metallic nanoparticle (NP)-two-dimensional material hybrids have been widely used for photocatalysis and photoreduction. Here, we introduce a femtosecond laser reduction approach that relies on the repetitive ablation of recast layers by usi-ng temporally shaped pulses to achieve the fast fabrication of metallic NP-two-dimensional material hybrids. We selectively deposited silver-reduced graphene oxide (Ag-rGO) hybrids on different substrates under various fabrication conditions. The deposition of the hybrids was attributed to the redistribution of the cooling ejected plume after multiple radiation pulses and the exchange of carriers with ejected plume ions containing activated species such as small carbon clusters and H2O. The proposed one-step in situ fabrication method is a competitive fabrication process that eliminates the additive separation process and exhibits morphological controllability. The Ag-rGO hybrids demonstrate considerable potential for chemomolecular and biomolecular detection because the surface-enhanced Raman scattering signal of the enhancement factor reached 4.04 × 108.

Highly Luminescent and Stable Organic-Inorganic Hybrid Films for Transparent Luminescent Solar Concentrators.

Here, a highly luminescent, stable, and visible-transparent organic-inorganic hybrid film was in situ synthesized in a siloxane-polyether (di-ureasil) sol-gel process by dissolving a 4-hydroxy-2-methyl-1,5-naphthyridine-3-carbonitrile (2mCND) ligand and a europium(III) ion. Doping a europium(III) complex into di-ureasil achieves an boost in photoluminescence quantum efficiency (PLQY) from 23.25 to 68.9%. In particular, the excellent photostability of the hybrid film was demonstrated after a 15 h aging experiment in strong UV-LED irradiation (∼468 mW/cm2). Compared to the polymethyl methacrylate (PMMA) matrix, di-ureasil containing a europium(III) complex shows an improved UV resistance, making it a promising candidate for various photonic applications. By integrating the hybrid film onto an acrylic substrate, a transparent luminescent solar concentrator (LSC) was fabricated, which reveals an optical conversion efficiency of ∼0.51% with a G factor of 3.1 at an optical transmission level of ∼90%. Such an LSC could be of particular interest in future transparent photovoltaic windows.

Electrospun Hybrid Films for Fast and Convenient Delivery of Active Herb Extracts.

Herb medicines are popular for safe application due to being a source of natural herbs. However, how to deliver them in an efficacious and convenient manner poses a big challenge to researchers. In this study, a new concept is demonstrated that the electrospun polymer-based hybrid films can be a platform for promoting the delivery of a mixture of active herb extract, i.e., Lianhua Qingwen Keli (LQK), also a commercial traditional Chinese patent medicine. The LQK can be co-dissolved with the filament-forming polymeric polyvinylpyrrolidone K60 and a sweeter sucralose to prepare an electrospinnable solution. A handheld electrospinning apparatus was explored to transfer the solution into solid nanofibers, i.e., the LQK-loaded medicated films. These films were demonstrated to be composed of linear nanofibers. A puncher was utilized to transfer the mat into circular membrane a diameter of 15 mm. Two self-created methods were developed for disclosing the dissolution performances of the electrospun mats. Both the water droplet experiments and the wet paper (mimic tongue) experiments verified that the hybrid films can rapidly disintegrate when they encounter water and release the loaded LQK in an immediate manner. Based on the reasonable selections of polymeric excipients, the present protocols pave a way for delivering many types of active herb extracts in an effective and convenient manner.

Smart DNA-gold nanoparticle hybrid hydrogel film based portable, cost-effective and storable biosensing system for the colorimetric detection of lead (II) and uranyl ions.

A portable, cost-effective and storable DNA-gold nanoparticle (AuNP) hybrid hydrogel film based biosensing system was developed, with AuNPs serving as both the crosslinking units of the film and the signaling units. Using a layer-by-layer assembly method, hydrogel film composed of three-dimensional hydrophilic network of densely packed AuNPs interconnected by responsive DNA structures was constructed onto a glass slide. By programming the sequence of DNA structures, target-responsive hybrid films were constructed. As a proof of concept, the sequence of a substrate DNA which can be identified and cleaved by Pb2+-dependent DNAzyme was encoded to construct Pb2+-responsive DNA-AuNP hybrid hydrogel film. The high-density packing of AuNPs as signal substances significantly improved the sensitivity of the ultrathin film biosensing system while reduced the cost of expensive DNA materials. A hydrogel film composed of 10 layers of assembled DNA-AuNP structures generated sufficient visual colorimetric signals for Pb2+ detection, with a detection limit of 2.6 nM. By introducing UO22+-dependent DNAzyme, the system could be further applied in the sensitive and selective detection of UO22+, with a detection limit of 10.3 nM. Compared with bulk-sized DNA hydrogel biosensing systems, the DNA-AuNP hydrogel film biosensing system exhibited faster response thanks to the sub-micrometer ultrathin film structures. Moreover, the protection of fragile non-covalently crosslinked DNA films with solid slides also facilitated the portable application and long-term storage of the resulting biosensing system, with 95% of the response signal retained after three months of storage. The DNA-AuNPs hydrogel film biosensing system is highly promising for future rapid on-site detection applications.

Recent Progress on Optical Tomographic Technology for Measurements and Inspections of Film Structures.

In this review, we present the recent progress on film metrology focused on the advanced and novel technologies during the last two decades. This review consists of various technologies and their measurement schemes to provide the inspiration for understanding each of the measurement principles and applications. In the technology and analysis section, several optical techniques used in film metrology are introduced and described with their benefits and limitations. The temporal, spatial and snapshot measurement schemes of optical film metrology are introduced in the measurement scheme section, and finally, the prospect on optical film metrology will be provided and discussed with the technology trend.