Significance of Zn Complex Concentration on Microstructure Evolution and Corrosion Behavior of Al/WS2.

Corrosion is a harmful processes which by definition is a chemical or electrochemical reaction between a substance (usually a metal) and the environment which leads to a change in the properties of the substance and has destructive effects. In this study, new composites consisting of Al/WS2/ZnTerp-2TH with 5 and 10 wt.% ZnTerp-2TH were prepared and the results were fully compared. Al/WS2 played the role of matrix and ZnTerp-2TH played the role of reinforcement. In other words, as a novelty to prevent the corrosion of Al/WS2, ZnTerp-2TH is designed and synthesized and showed good results when the corrosion ratio was reduced by the existence of ZnTerp-2TH. Furthermore, the NMR and mass analysis of ZnTerp-2TH were carried out, and the thermal properties, X-ray diffraction, Fourier-transform infrared (FTIR) spectroscopy, morphology, energy-dispersive X-ray spectroscopy (EDX) analysis and corrosion behavior of the composites were also discussed in detail. The crystal size values of composites were calculated by the modified Scherrer method 34, 26 and 27 nm for Al/WS2, Al/WS2/5 wt.% ZnTerp-2TH and Al/WS2/10 wt.% ZnTerp-2TH, respectively. The microstructural examination of the specimens showed that the reinforcing phase (ZnTerp-2TH) has a favorable distribution on the surface of Al/WS2 when it covers the cracks and holes. In addition, the corrosion investigation results showed that the addition of ZnTerp-2TH to Al/WS2 can improve the corrosion resistance when the Ecorr and Icorr values of Al/WS2/10 wt.% ZnTerp-2TH were recorded in tandem -724 mV/decade and 5 uA cm-2.

The Formation of Volume Transmission Gratings in Acrylamide-Based Photopolymers Using Curcumin as a Long-Wavelength Photosensitizer.

Curcumin, a natural dye found in the Curcuma longa rhizome, commonly called turmeric, is used as a photosensitizer in acrylamide-based photopolymers for holographic data storage. We studied the absorbance of photopolymer films that show two absorption bands due to curcumin, acrylamide monomer (AA), and the crosslinking agent N,N'-methylenebisacrylamide (MBA). Analysis of the real-time diffraction efficiency of these films shows a maximum of 16% for the sample with the highest curcumin concentration. Moreover, increasing the curcumin load enhanced the refractive index contrast from 7.8 × 10-4 for the photopolymer with the lowest curcumin load to 1.1 × 10-3 for the photopolymer with the largest load. The sensitivity and diffraction efficiency of the recorded gratings also increased from 7.0 to 9.8 cm·J-1 and from 7.9 to 16% with the increase in curcumin load, respectively. Finally, the influence of NaOH on the photopolymerization of the AA-curcumin-based sample shows a diffraction efficiency increase with the NaOH content, revealing that the curcumin enol form is more efficient as a photosensitizer.

Surface Relief Grating on Chitosan-N,N-dimethyl-4-(2-pyridylazo)aniline Thin Film.

We deposited homogeneous, thin, yellow-colored films of chitosan (Chi)-N,N-dimethyl-4-(2-pyridylazo)aniline (PADA) dye from an acid Chi-PADA solution by spin-coating on glass substrates. We characterized Chi, PADA, and Chi-PADA films by ATR-FTIR spectroscopy, which revealed a slight shift of 3170 and 3268 cm-1 bands, indicating H-bonding between the chitosan hydroxyl (OH) group and the amine (N) of the PADA pyridine ring. Based on these analyses, it was possible to determine the efficiency of the hydrogen bonds to form a Surface Relief Grating (SRG) on azo-polymer thin film. Moreover, we performed UV-VIS spectroscopy analysis of this film, which showed a broad band extending from 400 to 700 nm, with the maximum occurring at 428 nm. Therefore, we selected, within the absorption band, the 532 nm green laser wavelength to irradiate the azo-polymer films at room temperature. For the first time, natural polymer derivative and dye sample Chi-PADA thin films showed unique photoresponsive behavior under irradiation with two interfering laser beams. This permitted us to generate surface inscription patterning known as an SRG, which we confirmed by atomic force microscopy (AFM) and for which we determined a grating depth up to 50 nm. The present study opens the new possibility of using natural polymer-dye thin films.

Insight into OTFT Sensors Using Confocal Fluorescence Microscopy.

Confocal fluorescence microscopy provides a means to map charge carrier density within the semiconductor layer in an active organic thin film transistor (OTFT). This method exploits the inverse relationship between charge carrier density and photoluminescence (PL) intensity in OTFTs, originating from exciton quenching following exciton-charge energy transfer. This work demonstrates that confocal microscopy can be a simple yet effective approach to gain insight into doping and de-doping processes in OTFT sensors. Specifically, the mechanisms of hydrogen peroxide sensitivity are studied in low-voltage hygroscopic insulator field effect transistors (HIFETs). While the sensitivity of HIFETs to hydrogen peroxide is well known, the underlying mechanisms remain poorly understood. Using confocal microscopy, new light is shed on these mechanisms. Two distinct doping processes are discerned: one that occurs throughout the semiconductor film, independent of applied voltages; and a stronger doping effect occurring near the source electrode, when acting as an anode with respect to a negatively polarized drain electrode. These insights offer important guidance to future studies and the optimization of HIFET-based sensors. More importantly, the methods reported here are broadly applicable to the study of a range of OTFT-based sensors. This work demonstrates that confocal microscopy can be an effective research tool in this field.

Paste Aging Spontaneously Tunes TiO2 Nanoparticles into Reproducible Electrosprayed Photoelectrodes.

In this study, the spontaneous microstructure tuning of TiO2 was observed by aging the ethanol/water TiO2 paste for up to 20 days at ambient conditions. A dynamic light scattering study reveals that it formed the outstanding reproducible TiO2 microstructure with a ∼200 nm average particle size and stabilizes in 6 to 20 days under an ambient atmosphere. Interestingly, the as-deposited day 15 sample spontaneously changed its crystallinity upon keeping the paste at ambient conditions; meanwhile the day 0 sample showed an amorphous structure. A dense, uniform, and stable TiO2 electrode was cast on a fluorine doped-tin oxide substrate using the electrospray technique. We exploit the spontaneous evolution of the TiO2 nanopowder to revisit the fabrication procedure of the TiO2 photoelectrode for dye-sensitized solar cells (DSSCs). The controlled microstructure TiO2 film was used in DSSCs, which, to the best of our knowledge, achieved the highest power conversion efficiency of 9.65% using N719 dye in sensitizing the TiO2 photoanode.

Single-Crystal Bismuth Thiophosphate, BiPS4, as a Nontoxic and Mechanically Robust X-ray Detector.

Bismuth thiophosphate, BiPS4, is a promising nontoxic, high-density ternary chalcogenide semiconductor. Polycrystalline BiPS4 was synthesized from the stoichiometric melt of Bi, P, and S. Phosphorus was purified via an in-situ sublimation method. Single crystals of BiPS4 were grown using a modified vertical Bridgman method with a thermal gradient of 18 °C/cm. The material exhibits an electrical resistivity of 2 × 109 Ω·cm. The Knoop hardness of the single crystals is 128 ± 0.8 kg mm-2. A blocking contact behavior was observed with asymmetric contacts of Ga/BiPS4/Ag. A clear photocurrent response was observed from a BiPS4 crystal under an electric field as low as 1.14 V mm-1. Using a tungsten X-ray source, an X-ray sensitivity of 52 µ Gy-1 cm-2 was measured under an electric field of 80 V mm-1. When a single-crystal BiPS4 radiation detector device was used in a pulse-height radiation detection system, a clear charge collection response was observed under a 241Am α-particle radiation source.

Spray Pyrolyzed TiO2 Embedded Multi-Layer Front Contact Design for High-Efficiency Perovskite Solar Cells.

The photovoltaic performance of perovskite solar cells (PSCs) can be improved by utilizing efficient front contact. However, it has always been a significant challenge for fabricating high-quality, scalable, controllable, and cost-effective front contact. This study proposes a realistic multi-layer front contact design to realize efficient single-junction PSCs and perovskite/perovskite tandem solar cells (TSCs). As a critical part of the front contact, we prepared a highly compact titanium oxide (TiO2) film by industrially viable Spray Pyrolysis Deposition (SPD), which acts as a potential electron transport layer (ETL) for the fabrication of PSCs. Optimization and reproducibility of the TiO2 ETL were discreetly investigated while fabricating a set of planar PSCs. As the front contact has a significant influence on the optoelectronic properties of PSCs, hence, we investigated the optics and electrical effects of PSCs by three-dimensional (3D) finite-difference time-domain (FDTD) and finite element method (FEM) rigorous simulations. The investigation allows us to compare experimental results with the outcome from simulations. Furthermore, an optimized single-junction PSC is designed to enhance the energy conversion efficiency (ECE) by > 30% compared to the planar reference PSC. Finally, the study has been progressed to the realization of all-perovskite TSC that can reach the ECE, exceeding 30%. Detailed guidance for the completion of high-performance PSCs is provided.

Ionic Liquid-Assisted MAPbI3 Nanoparticle-Seeded Growth for Efficient and Stable Perovskite Solar Cells.

With the rapid improvement of perovskite solar cells (PSCs), long-life operational stability has become a major requirement for their commercialization. In this work, we devised a pristine cesium-formamidinium-methylammonium (termed as CsFAMA) triple-cation-based perovskite precursor solution into the ionic liquid (IL)-assisted MAPbI3 nanoparticles (NPs) through a seeded growth approach in which the host IL-assisted MAPbI3 NPs remarkably promote high-quality perovskite films with large single-crystal domains, enhancing the device performance and stability. The power conversion efficiency (PCE) of the MAPbI3 NP-seeded growth of MAPbI3 NPs/CsFAMA-based PSCs is as high as 19.44%, which is superior to those of MAPbI3 NPs and pristine CsFAMA films as the photoactive layer (9.52 and 17.33%, respectively). The long-term light-soaking and moisture stability of IL-aided MAPbI3 NPs/CsFAMA-based devices (non-encapsulated) remain above 90 and 80%, respectively, of their initial output after 2 h of light illumination (1 sun) and 6000 h storage at ambient with a relative humidity range of 30-40%. The use of the IL-assisted MAPbI3 NP-seeded growth for PSCs is a significant step toward developing stable and reliable perovskite photovoltaic devices.

A common optical approach to thickness optimization in polymer and perovskite solar cells.

The structure of experimentally designed solar cells was optimized in terms of the photoactive layer thickness for both organic bulk heterojunction and hybrid perovskite solar cells. The photoactive layer thickness had a totally different behavior on the performance of the organic and hybrid solar cells. Analysis of the optical parameters using transfer matrix modeling within the Maxwell-Garnett effective refractive index model shows that light absorbance and exciton generation rate in the photoactive layer can be used to optimize the thickness range of the photoactive layer. Complete agreement between experimental and simulated data for solar cells with photoactive materials that have very different natures proves the validity of the proposed modeling method. The proposed simple method which is not time-consuming to implement permits to obtain a preliminary assessment of the reasonable range of layer thickness that will be needed for designing experimental samples.

Low-Temperature Processed TiOx Electron Transport Layer for Efficient Planar Perovskite Solar Cells.

The most frequently used n-type electron transport layer (ETL) in high-efficiency perovskite solar cells (PSCs) is based on titanium oxide (TiO2) films, involving a high-temperature sintering (>450 °C) process. In this work, a dense, uniform, and pinhole-free compact titanium dioxide (TiOx) film was prepared via a facile chemical bath deposition process at a low temperature (80 °C), and was applied as a high-quality ETL for efficient planar PSCs. We tested and compared as-deposited substrates sintered at low temperatures (< 150 °C) and high temperatures (> 450 °C), as well as their corresponding photovoltaic properties. PSCs with a high-temperature treated TiO2 compact layer (CL) exhibited power conversion efficiencies (PCEs) as high as 15.50%, which was close to those of PSCs with low-temperature treated TiOx (14.51%). This indicates that low-temperature treated TiOx can be a potential ETL candidate for planar PSCs. In summary, this work reports on the fabrication of low-temperature processed PSCs, and can be of interest for the design and fabrication of future low-cost and flexible solar modules.

Solution Processing and Self-Organization of PbS Quantum Dots Passivated with Formamidinium Lead Iodide (FAPbI3).

Solution-processed lead sulfide quantum dots (PbS QDs) are very attractive as NIR-active semiconductors for the fabrication of cost-efficient optoelectronic devices. To control the thin film carrier transport, as well as stability, surface passivation is of crucial importance. Here, we present the successful surface passivation of PbS QDs by the formamidinium lead iodide (FAPbI3) ligand. An effective procedure for the fabrication of FAPbI3-passivated PbS QDs through a binary-phase ligand exchange protocol in hexane and n-methylformamide is demonstrated. It is shown that this solution-processed ligand exchange drastically changes the photoluminescence intensity, exciton recombination dynamics, and carrier lifetime of the nanocrystals. The solution casting of the ligand-exchanged nanocrystals into thin films results in the periodic ordering of QDs in a square superlattice with close contacts. Planar graphene/QD photodetectors fabricated with PbS QDs passivated with FAPbI3 show substantially increased thermal stability as compared to similar devices using PbS QDs passivated with commonly used methylammonium lead iodide.

Benzo[b]selenophene/thieno[3,2-b]indole-Based N,S,Se-Heteroacenes for Hole-Transporting Layers.

Two series of new N,S,Se-heteroacenes, namely, 6H-benzo[4',5']selenopheno[2',3':4,5]thieno[3,2-b]indoles and 12H-benzo[4″,5″]selenopheno[2″,3″:4',5']thieno[2',3'4,5]thieno[3,2-b]indoles, were successfully obtained using an effective strategy based on Fiesselmann thiophene and Fischer indole synthesis. The new molecules exhibit a large optical band gap (2.82 eV < E g opt < 3.23 eV) and their highest occupied molecular orbital (HOMO) energy formed by the plane π-core ranges between -5.2 and -5.6 eV, with the narrower optical band gap and lower HOMO level corresponding to selenated heteroacenes. In thin solid films of the heteroacenes, hole mobility measured using the conventional CELIV technique ranges between 10-5 and 10-4 cm2·V-1·s-1. All these make the proposed condensed-ring compounds a promising platform for the development of hole-transporting materials applicable in organic electronics.

Metal Oxide Compact Electron Transport Layer Modification for Efficient and Stable Perovskite Solar Cells.

Perovskite solar cells (PSCs) have appeared as a promising design for next-generation thin-film photovoltaics because of their cost-efficient fabrication processes and excellent optoelectronic properties. However, PSCs containing a metal oxide compact layer (CL) suffer from poor long-term stability and performance. The quality of the underlying substrate strongly influences the growth of the perovskite layer. In turn, the perovskite film quality directly affects the efficiency and stability of the resultant PSCs. Thus, substrate modification with metal oxide CLs to produce highly efficient and stable PSCs has drawn attention. In this review, metal oxide-based electron transport layers (ETLs) used in PSCs and their systemic modification are reviewed. The roles of ETLs in the design and fabrication of efficient and stable PSCs are also discussed. This review will guide the further development of perovskite films with larger grains, higher crystallinity, and more homogeneous morphology, which correlate to higher stable PSC performance. The challenges and future research directions for PSCs containing compact ETLs are also described with the goal of improving their sustainability to reach new heights of clean energy production.

Dibenzo[f,h]furazano[3,4-b]quinoxalines: Synthesis by Intramolecular Cyclization through Direct Transition Metal-Free C-H Functionalization and Electrochemical, Photophysical, and Charge Mobility Characterization.

Herein, we describe the synthesis of unsymmetrically substituted dibenzo[f,h]furazano[3,4-b]quinoxalines by intramolecular cyclization through direct transition metal-free C-H functionalization. The electrochemical and photophysical properties for several polycycles have been measured. In thin films of the dibenzo[f,h]furazano[3,4-b]quinoxalines, hole mobility is in the order of 10-4 cm2 V-1 s-1. The results show that the HOMO and LUMO energy levels are appropriate for using the compounds as hole-transport materials in thin-film devices, in particular, organic and perovskite solar cells.

Capture and light-induced release of antibiotics by an azo dye polymer.

The isomerisation of azo dyes can induce conformational changes which have potential applications in medicine and environmental protection. We developed an agar diffusion assay to test the capture and release of biologically active molecules from an azo electro-optic polymer, Poly (Disperse Red 1 methacrylate) (DR1/PMMA). The assay monitors the growth of bacteria placed in soft agar under a glass coverslip. Antibiotics can then be applied on the coverslip resulting in the clearance of the area under the coverslip due to growth inhibition. This assay demonstrates that DR1/PMMA is able to capture either tetracycline or ampicillin and the relative amount of DR1/PMMA required for capture was determined. Finally, the active antibiotics can be released from DR1/PMMA by exposure to green laser light. Exposure to white light from a torch or to heat does not release the antibiotic.

Electronic Transport in the Biopigment Sepia Melanin.

Eumelanin is the most common form of the pigment melanin in the human body, with diverse functions including photoprotection, antioxidant behavior, metal chelation, and free radical scavenging. Melanin also plays a role in melanoma skin cancer and Parkinson's disease. Sepia melanin is a natural eumelanin extracted from the ink sac of cuttlefish. Eumelanin is an ideal candidate to eco-design technologies based on abundant, biosourced, and biodegradable organic electronic materials to alleviate the environmental footprint of the electronics sector. Herein, the focus is on the reversible electrical resistive switching in dry and wet Sepia eumelanin pellets, pointing to the possibility of predominant electronic transport satisfying conditio sine qua non to develop melanin-based electronic devices. These findings shed light on the possibility to describe the transport physics of dry eumelanin using the amorphous semiconductor model. Results are of tremendous importance for the development of sustainable organic electronics.

Photonic-crystal-based broadband graphene saturable absorber.

The enhanced saturable absorption (SA) of a one-dimensional (1D) photonic crystal (PC) made from polymers and graphene composites by spin coating is observed. It shows obvious bandgaps at two wavelengths in transmittance. Femtosecond Z-scan measurement at 515 nm and 1030 nm reveals a distinct enhancement in the effective nonlinear absorption coefficient ßeff for graphene nanoflakes embedded in the PC, when compared with the bulk graphene-polymer composite. The effect is studied in a wide range of laser intensities. Graphene inclusion into a 1D PC remarkably decreases the SA threshold and saturation intensity, providing a desired solution for an advanced all-optical laser mode-locking device.

Competition between stimulated Brillouin scattering and two-photon absorption in dispersed boron nitride.

The design of transparent optical materials with stimulated Brillouin scattering (SBS) suppression is a topic of current interest. We measured two-photon absorption (2PA) cross-section σ2PA and Brillouin gain factor gB of a suspension of hexagonal boron nitride (hBN) in N-methyl-2-pyrrolidone at the second harmonic of a Nd:YAG laser. SBS exhibits a significant quenching with hBN concentration, like previously observed in graphene suspension. The melting of hBN flakes due to a large 2PA and the related changes in the acoustic damping coefficient explain the quenching mechanism.

Revisiting the Optimal Nano-Morphology: Towards Amorphous Organic Photovoltaics.

Organic photovoltaic cells commonly use an active layer with a polycrystalline bulk heterojunction. However, for simplifying the fabrication process, it may be worthwhile to use an amorphous active layer to lessen the burden on processing to achieve optimal performance. While polymers can adopt amorphous phases, molecular glasses, small molecules that can readily form glassy phases and do not crystallize over time, offer an appealing alternative, being monodisperse species. Our group has developed a series of reactive molecular glasses that can be covalently bonded to chromophores to form glass-forming adducts, and this strategy has been used to synthesize glass-forming donor and acceptor materials. Herein, the results of devices incorporating these materials in either partially or fully amorphous active layers are summarized. Additionally, these molecular glasses can be used as ternary components in crystalline systems to enhance efficiency without perturbing the morphology.

Simple Unbiased Hot-Electron Polarization-Sensitive Near-Infrared Photodetector.

Plasmonic nanostructures can generate energetic "hot" electrons from light in a broad band fashion depending on their shape, size, and arrangement. Such structures have a promising use in photodetectors, allowing high speed, broad band, and multicolor photodetection. Because they function without a band gap absorption, photon detection at any energy would be possible through engineering of the plasmonic nanostructure. Herein, a compact hot-electron-based photodetector that combines polarization sensitivity and circularly polarized light detection in the near-infrared region was fabricated using an indium tin oxide (ITO)-Au hybrid layer. Furthermore, the sensitivity of the device was significantly increased by adding a poled Azo molecular glass film in a capacitor configuration. The resulting device is capable of detecting light below the ITO band gap at ambient temperature without any bias voltage. This photodetector, which is amenable to large-area fabrication, can be integrated with other nanophotonic and nanoplasmonic structures for operation at telecom wavelengths.