Progress on lanthanide-based organic–inorganic hybrid phosphors

Research on organic–inorganic hybrid materials containing trivalent lanthanide ions (Ln3+) is a very active field that has rapidly shifted in the last couple of years to the development of eco-friendly, versatile and multifunctional systems, stimulated by the challenging requirements of technological applications spanning domains as diverse as optics, environment, energy, and biomedicine. This tutorial review offers a general overview of the myriad of advanced Ln3+-based organic–inorganic hybrid materials recently synthesised, which may be viewed as a major innovation in areas of phosphors, lighting, integrated optics and optical telecommunications, solar cells, and biomedicin

Smart optical sensors for internet of things: integration of temperature monitoring and customized security physical unclonable functions

Nowadays, the Internet of Things (IoT) has an astonishingly societal impact in which healthcare services stand out. Amplified by the COVID-19 pandemic scenario, challenges include the development of authenticatable smart IoT devices with the ability to simultaneously track people and sense in realtime human body temperature aiming to infer a health condition in a contactless and remote way through user-friendly equipment such as a smartphone. Univocal smart labels based on quick response (QR) codes were designed and printed on medical substrates (protective masks and adhesive) using flexible organicinorganic luminescent inks. Luminescence thermometry and physical unclonable functions (PUFs) are simultaneously combined allowing non-contact temperature detection, identification, and connection with the IoT environment through a smartphone. This is an intriguing example where luminescent inks based on organic-inorganic hybrids modified by lanthanide ions are used to fabricate a smart label that can sense temperature with remarkable figures of merit, including maximum thermal sensitivity of Sr = 1.46 %K−1 and temperature uncertainty of δT = 0.2 K, and an authentication methodology accuracy, precision, and recall of 96.2%, 98.9%, and 85.7%, respectively. The methodology proposed is feasibly applied for the univocal identification and mobile optical temperature monitoring of individuals, allowing the control of the access to restricted areas and the information transfer to medical entities for post medical evaluation towards a new generation of mobile-assisted eHealth (mHealth).publishe

Upconverting nanoparticles as primary thermometers and power sensors

Luminescence thermometry is a spectroscopic technique for remote temperature detection based on the thermal dependence of the luminescence of phosphors, presenting numerous applications ranging from biosciences to engineering. In this work, we use the Er3+ emission of the NaGdF4/NaGdF4:Yb3+,Er3+/NaGdF4 upconverting nanoparticles upon 980 nm laser excitation to determine simultaneously the absolute temperature and the excitation power density. The Er3+ 2H11/2→4 I15/2 and 4 S3/2→4 I15/2 emission bands, which are commonly used for thermometric purposes, overlap with the 2 H9/2 →4 I13/2 emission band, which can lead to erroneous temperature readout. Applying the concept of luminescent primary thermometry to resolve the overlapping Er3+ transitions, a dual nanosensor synchronously measuring the temperature and the delivered laser pump power is successfully realized holding promising applications in laser-supported thermal therapies.publishe

Functional nanostructured chitosan–siloxane hybrids

New organic–inorganic hybrids were prepared by a sol–gel method from the biopolymer chitosan and a silane coupling agent, 3-isocyanatopropyltriethoxysilane (ICPTES), in which covalent bridges, essentially composed of urea, bond the chitosan to the poly(siloxane) network. The structural characterization of the advanced chitosan–siloxane hybrids was performed by Fourier transform infrared spectroscopy, X-ray diffraction and 29Si and 13C nuclear magnetic resonance. The presence of siloxane nanodomains was detected by small angle X-ray diffraction. The chitosan–siloxane hybrids are bifunctional materials with interesting photoluminescent features and bioactive behaviour. The photoluminescence spectra display an additional high-energy band with longer lifetime, relatively to the characteristic emission of pure chitosan. This band is associated with electron–hole recombinations arising from silicon-related defects at the surface of the siliceous nanodomains. The bioactive behaviour of these materials was also evaluated; the apatite formation was shown to depend on the amount and arrangement of silanol groups

Designing Ln3+-doped BiF3 particles for luminescent primary thermometry and molecular logic

The design of molecular materials suitable for disparate fields could lead to new advances in engineering applications. In this work, a series of Ln3+-doped BiF3 sub-microparticles were synthesized through microwave-assisted synthesis. The effects of doping are evaluated from the structural and morphological viewpoint. In general, increasing the Ln3+ concentration the octahedral habitus is distorted to a spheric one, and some aggregates are visible without any differences in the crystalline phase. The optical response of the samples confirms that the BiF3 materials are suitable hosts for the luminescence of the tested trivalent lanthanide (Ln3+) ions (Ln = Eu, Tb, Tm, Ho, Er, Yb). A Yb3+/ Er3+ co-doped sample is presented as an illustrative example of all-photonic molecular logic operations and primary luminescent thermometry.publishe

Functional mobile-based two-factor authentication by photonic physical unclonable functions

Given the rapid expansion of the Internet of Things and because of the concerns around counterfeited goods, secure and resilient cryptographic systems are in high demand. Due to the development of digital ecosystems, mobile applications for transactions require fast and reliable methods to generate secure cryptographic keys, such as Physical Unclonable Functions (PUFs). We demonstrate a compact and reliable photonic PUF device able to be applied in mobile-based authentication. A miniaturized, energy-efficient, and low-cost token was forged of flexible luminescent organic–inorganic hybrid materials doped with lanthanides, displaying unique challenge–response pairs (CRPs) for two-factor authentication. Under laser irradiation in the red spectral region, a speckle pattern is attained and accessed through conventional charge-coupled cameras, and under ultraviolet light-emitting diodes, it displays a luminescent pattern accessed through hyperspectral imaging and converted to a random intensity-based pattern, ensuring the two-factor authentication. This methodology features the use of a discrete cosine transform to enable a low-cost and semi-compact encryption system suited for speckle and luminescence-based CRPs. The PUF evaluation and the authentication protocol required the analysis of multiple CRPs from different tokens, establishing an optimal cryptographic key size (128 bits) and an optimal decision threshold level that minimizes the error probability.publishe

Optical strain sensor based on FPI micro-cavities produced by the fiber fuse effect

In this work we present a cost effective strain sensor based on micro-cavities produced through the re-use of optical fibers destroyed by the catastrophic fuse effect. The strain sensor estimated sensitivity is 2.22 +/- 0.08 pm/mu epsilon. After the fuse effect, the damaged fiber becomes useless and, consequently, it is an economical solution for sensing proposes, when compared with the cavities produced using other complex methods. Also, the low thermal sensitivity is of great interest in several practical applications, allowing eluding cross-sensitivity with less instrumentation, and consequently less cost

Crystal structure, topology, tiling and photoluminescence properties of 4d-4f hetero-metal organic frameworks based on 3,5-pyrazoledicaboxylate

Reaction of lanthanide oxides, cadmium acetate and 3,5-pyrazoledicarboxylic acid under hydrothermal conditions afforded five new isostructural 4d-4f hetero-metal organic frameworks, [Cd(3)Ln(pdc)(3)(H2O)] {H(3)pdc = 3,5-pyrazoledicarboxylic acid, Ln = La (1), Pr (2), Nd (3), Sm (4) and Eu (5)}. All compounds were characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis, X-ray diffraction, scanning electron microscopy and energy dispersive X-ray spectroscopy. The compounds feature a very interesting 3D structure built up from a secondary building unit, [Cd(12)Ln(8)(pdc)(6)], and possess a new topology type and complicated unique tiling. The solid state photoluminescence properties of compounds 3-5 were investigated at room temperature

Customized luminescent multiplexed quick‐response codes as reliable temperature mobile optical sensors for eHealth and Internet of Things

The need to sense and track in real time through sustainable and multifunctional labels is exacerbated by the COVID-19 pandemic, where the simultaneous measurement of body temperature and the fast tracking of people is required. One of the big challenges is to develop effective low-cost systems that can promote healthcare provision everywhere and for that, smarter and personalized Internet of things (IoT) devices are a pathway in large exploration, toward cost reduction and sustainability. Using the concept of color-multiplexed quick response (QR) codes, customized smart labels formed by two independent layers and smart location patterns provide simultaneous tracking and multiple synchronous temperature reading with maximum sensitivity values of 8.5% K−1 in the physiological temperature range, overwhelming the state-of-the-art optical sensor for healthcare services provided electronically via the internet (eHealth) and mobile sensors (mHealth).publishe

Multi-objective genetic algorithm applied to spectroscopic ellipsometry of organic-inorganic hybrid planar waveguides

The applicably of multi-objective optimization to ellipsometric data analysis is presented and a method to handle complex ellipsometric problems such as multi sample or multi angle analysis using multi-objective optimization is described. The performance of a multi-objective genetic algorithm (MOGA) is tested against a single objective common genetic algorithm (CGA). The procedure is applied to the characterization (refractive index and thickness) of planar waveguides intended for the production of optical components prepared sol-gel derived organic-inorganic hybrids, so-called di-ureasils, modified with zirconium tetrapropoxide, Zr(OPr(n))(4) deposited on silica on silicon substrates. The results show that for the same initial conditions, MOGA performs better than the CGA, showing a higher success rate in the task of finding the best final solution. (C) 2010 Optical Society of AmericaFCTFEDERPTDC/CTM/72093/2006SFRH/BD/41943/2007MP070