Dye-Based Photonic Sensing Systems

[EN] We report on dye-based photonic sensing systems which are fabricated and packaged at wafer scale. For the first time luminescent organic nanocomposite thin-films deposited by plasma technology are integrated in photonic sensing systems as active sensing elements. The realized dye-based photonic sensors include an environmental NO2 sensor and a sunlight ultraviolet light (UV) A + B sensor. The luminescent signal from the nanocomposite thin-films responds to changes in the environment and is selectively filtered by a photonic structure consisting of a Fabry Perot cavity. The sensors are fabricated and packaged at wafer-scale, which makes the technology viable for volume manufacturing. Prototype photonic sensor systems have been tested in real-world scenarios.The authors thank the EU (Phodye Strep Project 033793 and ERC Starting Grant M&M's 277879), and the Spanish Ministry of Economy and Competitiveness (MAT-2010-21228) and Junta de Andalucia (P09-TEP-5283) for financial support.Aparicio, F.; Alcaire, M.; González-Elipe, A.; Barranco, A.; Holgado, M.; Casquel, R.; Sanza, F.... (2016). Dye-Based Photonic Sensing Systems. Sensors and Actuators B Chemical. 228:649-657. https://doi.org/10.1016/j.snb.2016.01.092S64965722

Highly Porous ZnO Thin Films and 1D Nanostructures by Remote Plasma Processing of Zn-Phthalocyanine

In this paper the fabrication of highly porous 1D nanostructures by a vacuum and plasma etching combined protocol is presented. Zn-phthalocyanine (ZnPc) is utilized as a solid precursor to form the ZnO. First the ZnPc is sublimated in low argon pressure. Depending on the substrate temperature and microstructure, polycrystalline films or single crystal ZnPc nanowires are grown. These starting materials are then subjected to a remote plasma oxidizing treatment. Experimental parameters such as substrate position, plasma power, treatment duration, and substrate temperature determine the microstructure and properties of the final ZnO nanostructures. The article gathers an in depth study of the obtained porous nanostructured films following scanning and transmission electron microscopy (SEM and TEM), X-ray photoelectron spectroscopy (XPS), X-ray Diffraction (XRD), UV-Vis transmittance, and fluorescence spectroscopiesPeer Reviewe

Luminescent 3-hydroxyflavone nanocomposites with a tuneable refractive index for photonics and UV detection by plasma assisted vacuum deposition

Luminescent organic-thin-films transparent in the visible region have been synthesized by a plasma assisted vacuum deposition method. The films have been developed for their implementation in photonic devices and for UV detection. They consist of a plasma polymeric matrix that incorporates 3-hydroxyflavone molecules characterized by absorption of UV radiation and emission of green light. The present work studies in detail the properties and synthesis of this kind of transparent and luminescent material. The samples were characterized by X-ray photoemission (XPS), infrared (FT-IR) and secondary ion mass (ToF-SIMS) spectroscopies; and their optical properties were analysed by UV-Vis absorption, fluorescence and ellipsometry (VASE) spectroscopies. The key factors controlling the optical and luminescent properties of the films are also discussed. Indeed, our experimental results show how the optical properties of the films can be adjusted for their integration in photonic devices. Moreover, time resolved and steady state fluorescence analyses, including quantum yield determination, indicate that the fluorescence efficiency is a function of the deposition parameters. An outstanding property of these materials is that, even for high UV absorption values (i.e. large layer thickness and/or dye concentration), the emitted light is not reabsorbed by the film. Such highly UV absorbent and green emitting films can be used as UV photodetectors with a detection threshold smaller than 10 μW cm-2, a value similar to the limit of some commercial UV photodetectors. Based on these properties, the use of the films as visual tags for the detection of solar UV irradiation is proposed. This journal is © the Partner Organisations 2014.Peer Reviewe

Supported Porous Nanostructures Developed by Plasma Processing of Metal Phthalocyanines and Porphyrins

The large area scalable fabrication of supported porous metal and metal oxide nanomaterials is acknowledged as one of the greatest challenges for their eventual implementation in on-device applications. In this work, we will present a comprehensive revision and the latest results regarding the pioneering use of commercially available metal phthalocyanines and porphyrins as solid precursors for the plasma-assisted deposition of porous metal and metal oxide films and three-dimensional nanostructures (hierarchical nanowires and nanotubes). The most advanced features of this method relay on its ample general character from the point of view of the porous material composition andmicrostructure,mild deposition and processing temperature and energy constrictions and, finally, its straightforward compatibility with the direct deposition of the porous nanomaterials on processable substrates and device-architectures. Thus, taking advantage of the variety in the composition of commercially available metal porphyrins and phthalocyanines, we present the development of metal and metal oxides layers including Pt, CuO, Fe2O3, TiO2, and ZnO with morphologies ranging from nanoparticles to nanocolumnar films. In addition, we combine this method with the fabrication by low-pressure vapor transport of single-crystalline organic nanowires for the formation of hierarchical hybrid organic@metal/metal-oxide and @metal/metal-oxide nanotubes. We carry out a thorough characterization of the films and nanowires using SEM, TEM, FIB 3D, and electron tomography. The latest two techniques are revealed as critical for the elucidation of the inner porosity of the layers.Peer reviewe

Oxygen Optical Sensing in Gas and Liquids with Nanostructured ZnO Thin Films Based on Exciton Emission Detection

Transparent nanocolumnar porous ZnO thin films have been prepared by plasma-enhanced chemical vapor deposition. By controlling the H2/O2 ratio in the plasma gas, the deposition conditions were optimized to obtain an intense exciton emission at around 381 nm and virtually no luminescence in the visible region associated with electronic states in the gap. The intensity of the exciton band varied significantly and reversibly with the partial pressure of oxygen in the environment. This behavior and its variations with temperature and water vapor sustain the use of these thin films as photonic sensors of oxygen. Further experiments in liquid water show that fluorescence intensity also varies with the amount of dissolved oxygen even for concentrations lower than 0.02 mg/L where commercial oxygen galvanic sensors show limited sensitivity. These results and the use of ZnO as photonic sensor of oxygen are discussed by assuming a classical mechanism involving the photoactivated adsorption of oxygen when this oxide is irradiated with UV light during its fluorescence interrogation.Peer reviewe

Plasma deposition of perylene-adamantane nanocomposite thin films for NO 2 room-temperature optical sensing

This work reports the preparation, by a new remote assisted plasma deposition process, of luminescent nanocomposite thin films consisting of an insoluble organic matrix where photonically active perylene molecules are embedded. The films are obtained by the remote plasma deposition of adamantane and perylene precursor molecules. The results show that the adamantane precursor is very effective to improve the perylene-adamantane nanocomposite transparency in comparison with plasma deposited perylene films. The plasma deposited adamantane films have been characterized by secondary-ion mass spectrometry and FT-IR spectroscopy. These techniques and atomic force microscopy (AFM) have been also used for the characterization of the nanocomposite films. Their optical properties (UV-vis absorption, fluorescence, and refractive index) have been also determined and their sensing properties toward NO 2 studied. It is found that samples with the perylene molecules embedded within the transparent plasma deposited matrix are highly sensitive toward this gas and that the sensitivity of the films can be adjusted by modifying the aggregation state of the perylene molecules, as determined by the analysis of their fluorescence spectra. By monitoring the fluorescence emission of these films, it has been possible to detect a NO 2 concentration as low as 0.5 ppm in air at room temperature. Because of their chemical stability and transparency in the UV region, the remote plasma deposited adamantane thin films have revealed as an optimum host matrix for the development of photonically active composites for sensing applications. © 2012 American Chemical Society

Enhancing Moisture and Water Resistance in Perovskite Solar Cells by Encapsulation with Ultrathin Plasma Polymers

A compromise between high power conversion efficiency and long-term stability of hybrid organic–inorganic metal halide perovskite solar cells is necessary for their outdoor photovoltaic application and commercialization. Herein, a method to improve the stability of perovskite solar cells under water and moisture exposure consisting of the encapsulation of the cell with an ultrathin plasma polymer is reported. The deposition of the polymer is carried out at room temperature by the remote plasma vacuum deposition of adamantane powder. This encapsulation method does not affect the photovoltaic performance of the tested devices and is virtually compatible with any device configuration independent of the chemical composition. After 30 days under ambient conditions with a relative humidity (RH) in the range of 35–60%, the absorbance of encapsulated perovskite films remains practically unaltered. The deterioration in the photovoltaic performance of the corresponding encapsulated devices also becomes significantly delayed with respect to devices without encapsulation when vented continuously with very humid air (RH > 85%). More impressively, when encapsulated solar devices were immersed in liquid water, the photovoltaic performance was not affected at least within the first 60 s. In fact, it has been possible to measure the power conversion efficiency of encapsulated devices under operation in water. The proposed method opens up a new promising strategy to develop stable photovoltaic and photocatalytic perovskite devicesPeer reviewe

Plasma Enabled Conformal and Damage Free Encapsulation of Fragile Molecular Matter: from Surface-Supported to On-Device Nanostructures

Damage-free encapsulation of molecular structures with functional nanolayers is crucial to protect nanodevices from environmental exposure. With nanoscale electronic, optoelectronic, photonic, sensing, and other nanodevices based on atomically thin and fragile organic matter shrinking in size, it becomes increasingly challenging to develop nanoencapsulation that is simultaneously conformal at atomic scale and does not damage fragile molecular networks, while delivering added device functionality. This work presents an effective, plasma-enabled, potentially universal approach to produce highly conformal multifunctional organic films to encapsulate atomically thin graphene layers and metalorganic nanowires, without affecting their molecular structure and atomic bonding. Deposition of adamantane precursor and gentle remote plasma chemical vapor deposition are synergized to assemble molecular fragments and cage-like building blocks and completely encapsulate not only the molecular structures, but also the growth substrates and device elements upon nanowire integration. The films are insulating, transparent, and conformal at sub-nanometer scale even on near-tip high-curvature areas of high-aspect-ratio nanowires. The encapsulated structures are multifunctional and provide effective electric isolation, chemical and environmental protection, and transparency in the near-UV–visible–near-infrared range. This single-step, solvent-free remote-plasma approach preserves and guides molecular building blocks thus opening new avenues for precise, atomically conformal nanofabrication of fragile nanoscale matter with multiple functionalities

Bending induced self-organized switchable gratings on polymeric substrates

We present a straightforward procedure of self-surface patterning with potential applications as large area gratings, invisible labeling, optomechanical transducers, or smart windows. The methodology is based in the formation of parallel micrometric crack patterns when polydimethylsiloxane foils coated with tilted nanocolumnar SiO2 thin films are manually bent. The SiO2 thin films are grown by glancing angle deposition at room temperature. The results indicate that crack spacing is controlled by the film nanostructure independently of the film thickness and bending curvature. They also show that the in-plane microstructural anisotropy of the SiO2 films due to column association perpendicular to the growth direction determines the anisotropic formation of parallel cracks along two main axes. These self-organized patterned foils are completely transparent and work as customized reversible diffraction gratings under mechanical activation. © 2014 American Chemical Society.Peer Reviewe

Plasma enabled conformal and damage free encapsulation of fragile molecular matter:From surface-supported to on-device nanostructures

Damage-free encapsulation of molecular structures with functional nanolayers is crucial to protect nanodevices from environmental exposure. With nanoscale electronic, optoelectronic, photonic, sensing, and other nanodevices based on atomically thin and fragile organic matter shrinking in size, it becomes increasingly challenging to develop nanoencapsulation that is simultaneously conformal at atomic scale and does not damage fragile molecular networks, while delivering added device functionality. This work presents an effective, plasma-enabled, potentially universal approach to produce highly conformal multifunctional organic films to encapsulate atomically thin graphene layers and metalorganic nanowires, without affecting their molecular structure and atomic bonding. Deposition of adamantane precursor and gentle remote plasma chemical vapor deposition are synergized to assemble molecular fragments and cage-like building blocks and completely encapsulate not only the molecular structures, but also the growth substrates and device elements upon nanowire integration. The films are insulating, transparent, and conformal at sub-nanometer scale even on near-tip high-curvature areas of high-aspect-ratio nanowires. The encapsulated structures are multifunctional and provide effective electric isolation, chemical and environmental protection, and transparency in the near-UV–visible–near-infrared range. This single-step, solvent-free remote-plasma approach preserves and guides molecular building blocks thus opening new avenues for precise, atomically conformal nanofabrication of fragile nanoscale matter with multiple functionalities.</p