Optical Materials Research Articles

Review of Polarized Light‐Spin/Dipole Interactions: Fundamental Physics and Application in Circularly Polarized Detecting

AbstractCircularly polarized light (CPL) has attracted great attention due to its unique electromagnetic vector, which possesses potential practical applications in optical imaging, biometrics, and other interdisciplinary areas. At present, many materials with spontaneous CPL emitting have been extensively studied and reviewed for the generation of CPL. For the detection of CPL, mainly concentrate on the technical problems, that is, how to combine circularly polarized optical active materials with device structures to meet detection needs. Essentially, the resolution of CPL depends on the interaction between CPL and matter, Herein, the interactive modes including polarized light‐spin and light‐dipole (or charge) interactions in devices are summarized. Also, direct and indirect interactions of polarized light‐spin are presented. Meanwhile, the progress of light‐spin/dipole interaction dependence of CPL detectors is analyzed based on artificial structures of photoconductors, photodiodes, and photo field effect transistors. It is hoped that the review can broaden the bridge between the fundamental photon‐spin‐dipole interaction and CPL detectors with high performance, and then deepen the understanding of CPL detection and promote the development of CPL detectors.

The electronic structure and optical properties of BaBiBO4, a promising compound with high birefringence

Birefringence is a crucial parameter for various advanced optical devices like birefringent crystals, and nonlinear optical materials. In this paper, the electronic structures and optical properties of centrosymmetric BaBiBO4 are investigated using the first-principles method. The results show that BaBiBO4 could be a good birefringent compound whose birefringence is 0.195 @ 1064 nm and 0.266 @ 532 nm. The spin–orbit-coupling effect plays an important role in electronic structures, leading to downshift and band splitting of the conduction band, resulting in a reduced bandgap of 3.32 eV and enhanced birefringence. The projected density of states and real-space atom-cutting results reveal that BiO5 groups with asymmetric distribution of stereochemical active lone pairs and the staggered parallel arrangement of the BO3 groups give the main contribution to birefringence.

Photoconvertible and Photoactivatable Perylene BisImide Based on Photocyclization

AbstractPhotomodulable fluorophores constitute advanced materials as they possess the ability to modify their photophysical properties upon photoirradiation. A new mechanism of photoconversion is recently established, called Directed Photooxidation Induced Conversion based on the coupling of fluorophores with Aromatic Singlet oxygen Reactive Moieties (ASORMs). In this work, The Directed Photooxidation Induced Conversion (DPIC) mechanism is intended to be applied to Perylene BisImide (PBI) due to its appealing photophysical properties. The experimental results showed that coupling two ASORMs to the PBI core, here furan and pyrrole, led to impressive photomodulable fluorophores. While PBI‐F exhibited a photoconversion of 100 nm shift, PBI‐P displayed an 80‐fold fluorescence intensity enhancement upon photoactivation. Analysis of the photoproducts showed that the conversion do not involve an addition of singlet oxygen on the ASORM. Instead, photoconversion occurred through efficient successive photocyclizations. Finally, intracellular vesicles are successfully photoconverted by means of endocytosed PLGA‐polymer nanoparticles loaded with PBI‐F. This study highlights the unique capability of furan‐ and pyrrole‐conjugated fluorophores to enable advanced optical materials with phototransformation properties.

K0.9Rb2.1B8PO16: Design and Synthesis of a Deep-Ultraviolet Nonlinear Optical Crystal with Balanced Performance Derived from π-Conjugated and Non-π-Conjugated Groups.

A new deep-ultraviolet (DUV) nonlinear optical (NLO) material K0.9Rb2.1B8PO16 (KRBPO) has been designed and synthesized by adjusting the B/P molar ratio to 8:1. The KRBPO crystals were synthesized by a flux method and crystallized in noncentrosymmetric (NCS) and polar space group Cc. This compound exhibits a double-layer structure in which the A layer is composed of [B2O5] and [BO4] units and the B layer is formed by interconnected [B3O7] and [BO3] groups, and the two layers are connected by [PO4] tetrahedron. The theoretical calculations and experiments show that the synergistic interaction of π-conjugated and non-π-conjugated units leads to relatively well-balanced NLO properties of the title compound, including moderated SHG (0.7 × KDP), short UV cutoff edge (λcutoff < 190 nm), and a large band gap of 6.16 eV. Specifically, the coplanar arrangement of B-O groups in double-layer makes the KRBPO display a large birefringence (0.075@532 nm) and enables the shortest phase-matched wavelength to reach an important laser output wavelength of 266 nm.

Integrating simulated and experimental studies on novel single crystal bis(guanidininium) n-carboxylatephenylalanine towards enhanced antitumor effect

A novel organic crystal bis(guanidininium) n-carboxylatephenylalanine (GUPA) was synthesized and X-ray diffraction outcomes exposed P21, triclinic space group with cell dimensions a = 6.6492(3) Å, b = 16.2440(7) Å, c = 7.8985(3) Å, β = 0.127(2) °, V = 853.11(6) Å3, Z = 2 and possess good agreement with experimental data. Intermolecular interactions were revealed through hirshfeld and major contribution from O-H interaction confirms the presence of intermolecular hydrogen bonds. Through B3LYP algorithm with set 6–311++ G (d, p), chemical reactivity forms and molecular structure of GUPA was investigated, confirming a good stability and hard electrophilic nature. While first order hyperpolarizability value (35.37 × 10−31 esu) was indicative of good nonlinear optical material and hyperconjugate interactions and charge delocalization was further confirmed by natural bond orbitals. To further investigate the electronic properties theoretical (TD-DFT) and experimental absorption wavelengths were compared and excitation energies, oscillator strength and type of electronic transition with contributions have also been studied. The topological properties were evaluated using ELF/LOL maps and RDG with NCI were used to establish the type of interaction present in the GUPA molecular system. The anti-breast cancer effect of GUPA was computationally studied through molecular docking against p53 gene and was further investigated through in vitro MDA-MB-231 cell line studies and GUPA showed better inhibition of cancer cells and their expression.

Accelerated Computer-Aided Screening of Optical Materials: Investigating the Potential of Δ-SCF Methods to Predict Emission Maxima of Large Dye Molecules.

Accurate simulation of electronic excited states of large chromophores is often difficult due to the computationally expensive nature of existing methods. Common approximations such as fragmentation methods that are routinely applied to ground-state calculations of large molecules are not easily applicable to excited states due to the delocalized nature of electronic excitations in most practical chromophores. Thus, special techniques specific to excited states are needed. Δ-SCF methods are one such approximation that treats excited states in a manner analogous to that for ground-state calculations, accelerating the simulation of excited states. In this work, we employed the popular initial maximum overlap method (IMOM) to avoid the variational collapse of the electronic excited state orbitals to the ground state. We demonstrate that it is possible to obtain emission energies from the first singlet (S1) excited state of many thousands of dye molecules without any external intervention. Spin correction was found to be necessary to obtain accurate excitation and emission energies. Using thousands of dye-like chromophores and various solvents (12,318 combinations), we show that the spin-corrected initial maximum overlap method accurately predicts emission maxima with a mean absolute error of only 0.27 eV. We further improved the predictive accuracy using linear fit-based corrections from individual dye classes to achieve an impressive performance of 0.17 eV. Additionally, we demonstrate that IMOM spin density can be used to identify the dye class of chromophores, enabling improved prediction accuracy for complex dye molecules, such as dyads (chromophores containing moieties from two different dye classes). Finally, the convergence behavior of IMOM excited state SCF calculations is analyzed briefly to identify the chemical space, where IMOM is more likely to fail.

Near-Infrared-II Photoactivated Iron(III) Complexes for Highly Efficient RNS and ROS Synergistic Therapy.

Reactive nitrogen species (RNS) are more lethal than reactive oxygen species (ROS), which gives them a very promising future in the field of cancer treatment. However, there are still a few drugs available for RNS generation. In this work, two 5th-order nonlinear optical materials, FB-Fe(III)/SNP@PEG and FB-Fe(II)-FB/SNP@PEG, are synthesized. The outstanding nonlinear optical properties of FB-Fe(III)/SNP@PEG help to achieve generation of bounteous superoxide anions (O2•-) in deep tissues, while sodium nitroprusside (SNP) provides NO in the body, both of which are prerequisites for RNS generation. Meanwhile, type I and type II ROS were also generated under irradiation of a 1600 nm laser. Based on the synergistic effect of ROS and RNS, FB-Fe(III)/SNP@PEG induced mitochondrial damage and DNA fragmentation and inhibited tumor cells through apoptosis, possessing better therapeutic effects than FB-Fe(II)-FB/SNP@PEG. This work put forward an innovative strategy to achieve the cooperative release of RNS and ROS in deep tissues, which provides insights and ideas for applying nonlinear optical materials to RNS therapy.

Preparation and optical properties of Bi3+-doped K4SrGe3O9 as a UVA phosphor

Optical materials with UV emission have diverse applications, for example, in phototherapy, anti-counterfeiting, disinfection, and photocopying. Yet, these materials are mainly activated by rare earth ions with narrow and inflexible emission characteristics. Here, we report on UVA emission from a Bi3+-doped K4SrGe3O9 phosphor synthesized by conventional high-temperature solid state reaction at ambient atmosphere. The structure, morphology and luminescent properties of the material were characterized using X-ray diffraction, scanning electron microscopy (SEM) and photoluminescence spectroscopy, demonstrating broadband emission of ultraviolet-A (UVA) light peaking at 353 nm (FWHM ∼ 46 nm) when stimulated by ultraviolet radiation at a wavelength of 304 nm. The maximum emission intensity was found for K4SrGe3O9:0.001Bi3+, with a quantum yield of 46% and a lifetime of 477 ns.

Stimulated Emission and Lasing from Bulk CdSe Nanocrystals.

Nanocrystals with a size in the regime of vanishing quantum confinement, or bulk nanocrystals (BNCs), have emerged recently as viable solution processable optical gain materials in the green part of the spectrum. Here, we show that these properties can be extended to the crucial red region using CdSe BNCs. Through quantitative time-resolved spectroscopy, we can model these nanocrystals as bulk semiconductors, thereby revealing that the gain originates from an unbound electron-hole plasma state. The gain is broadband in nature and is not capped by Auger processes, but by a slower second-order recombination resulting in nanosecond gain lifetimes. Finally, optically pumped lasers under femtosecond pulsed and quasi-continuous wave operation are demonstrated using a photonic crystal surface emitting laser cavity, thereby stretching from 635 to 720 nm. Our results indicate that compositional variation can indeed provide spectral versatility to the BNC concept, while preserving the excellent gain metrics associated with it.

Synthesis, Structure, and Light Absorption of Octanoyl Amino Acids

Amino acid lanthanide complexes are a promising class of environmentally friendly and non-toxic optical organic materials that find extensive applications in biomedicine, molecular probes, and optical devices. In this study, three amino acid lanthanide complexes, octanoyl glycine gadolinium (Gd(oct-ala)3×H2O), octanoyl serine gadolinium (Gd(oct-ser)3×H2O), and octanoyl phenylalanine gadolinium (Gd(oct-phe)3×H2O), were synthesized by reacting octanoyl amino acid ligands with gadolinium chloride. The coordination structure of the gadolinium complexes was determined by elemental analysis and infrared spectroscopy. XRD and polarized light microscopy confirmed the amorphous structure of the complexes. DSC and TG-DTA were used to investigate the thermodynamic stability of the gadolinium complexes, and their solubility and UV-visible light absorption properties were also evaluated. Our results demonstrate that all three gadolinium complexes exhibit excellent UV-visible light absorption performance, with the Gd(oct-phe)3×H2O containing a phenyl ring showing the highest light absorption efficiency.

Experimental, quantum chemical spectroscopic investigation, topological, molecular docking/dynamics and biological assessment studies of 2,6-Dihydroxy-4-methyl quinoline

The present work is a comprehensive investigation of the spectral, electronic structure, bonding, and reactivity of the 2,6-dihydroxy-4-methylquinoline (26DH4MQ) molecule through a wide range of experimental and quantum chemical spectroscopic calculations techniques, along with its applications as nonlinear optical materials and biological assessments. The study utilized density functional theory (DFT) and time-dependent density functional theory (TD-DFT) with the B3LYP method and the 6-311G++(d,p) basis set to analyze the structural and molecular properties of 26DH4MQ. The findings from UV–Vis, FT-IR, and FT-NMR spectroscopy show a strong agreement between the experimentally obtained vibrational frequencies and chemical shifts and those predicted by computational methods. Local reactivity descriptors, such as the dual descriptor, Fukui functions, and the molecular electrostatic potential (MEP) map, were used to identify the reactive regions of the molecule. Additionally, natural bond orbital (NBO) analysis provided insights into the charge transfer characteristics of 26DH4MQ, which helps to stabilize the molecular system. The study also revealed notable nonlinear optical (NLO) properties, with polarizability (18.52 × 10–24e.s.u.) and first-order hyperpolarizability (2.26 × 10–30e.s.u.) values that surpass those of standard organic compounds, suggesting significant potential for optoelectronic applications. The biological evaluation of 26DH4MQ assessed its drug-likeness, toxicity, enzyme inhibition, and ADME (Absorption, Distribution, Metabolism, and Excretion) parameters, highlighting its pharmaceutical potential. Furthermore, molecular docking and dynamics studies illustrated the compound's interaction with proteins, indicating its potential role as an insulin inhibitor.

Atomic-engineered gradient tunable solid-state metamaterials

Metamaterial has been captivated a popular notion, offering photonic functionalities beyond the capabilities of natural materials. Its desirable functionality primarily relies on well-controlled conditions such as structural resonance, dispersion, geometry, filling fraction, external actuation, etc. However, its fundamental building blocks-meta-atoms-still rely on naturally occurring substances. Here, we propose and validate the concept of gradient and reversible atomic-engineered metamaterials (GRAM), which represents a platform for continuously tunable solid metaphotonics by atomic manipulation. GRAM consists of an atomic heterogenous interface of amorphous host and noble metals at the bottom, and the top interface was designed to facilitate the reversible movement of foreign atoms. Continuous and reversible changes in GRAM's refractive index and atomic structures are observed in the presence of a thermal field. We achieve multiple optical states of GRAM at varying temperature and time and demonstrate GRAM-based tunable nanophotonic devices in the visible spectrum. Further, high-efficiency and programmable laser raster-scanning patterns can be locally controlled by adjusting power and speed, without any mask-assisted or complex nanofabrication. Our approach casts a distinct, multilevel, and reversible postfabrication recipe to modify a solid material's properties at the atomic scale, opening avenues for optical materials engineering, information storage, display, and encryption, as well as advanced thermal optics and photonics.

Synthesis and fluorescence properties of europium complex functionalized fiberglass paper.

The development of novel rare earth fluorescent materials and the exploration of their applications have consistently been focal points of research in the fields of materials science and chemistry. In this work, a novel rare earth composite material with good photo-fluorescence properties and self-supporting has been prepared via a simple ultrasonic solvent reaction method. Initially, the Phen moieties is immobilized onto the surface of a self-supporting fiberglass paper using ICPTES, followed by the coordination of Eu(TTA)3 moieties with Phen moieties through a convenient ultrasonic solvent reaction. The resulting GF-Phen-Eu(TTA)3 has been characterized using FTIR, UV-Vis DRS, fluorescence measurements, and so on. The results indicate that the composite material exhibits strong fluorescent emission and presents a vivid red color under ultraviolet light. Further research has shown that the fluorescence of GF-Phen-Eu(TTA)3 strips demonstrated a pronounced quenching effect in response to some transition metal ions (1 mM). Hence, the rare earth composite materials presented here can be utilized not only for the production of optical materials, but also for the development of fluorescence sensing strips.

Terpyridine-Based Metal-Organic Cage with Enhanced Emission via Coordination-Induced Rigidity.

Realizing the regulation of photophysical properties by precisely controlling the molecular composition and configuration, thereby obtaining high-performance optical materials, remains of great significance. Due to the directionality and reversibility of the coordination bond, coordination-driven self-assembly endows the molecule with customized thermodynamically stable structures and desired properties. In this paper, a luminous metal-organic cage [Zn12L6] (S) was elaborately designed and quantitatively synthesized by self-assembly of tetrapodal TQPP chromophore-containing terpyridine ligand L with Zn2+. Complex S possessed a rigid cage-like structure, which endows a higher fluorescence quantum efficiency both in solution (∼88%) and neat solid (16%) than the corresponding ligand L. Further, using complex S as the photoactive component, two light-emitting diodes (LEDs) were successfully fabricated and the emission of pure white light (CIE coordinates: 0.3341, 0.3300) was achieved. These results afford a method to obtain enhanced luminescence performance via the formation of rigid coordination-driven supramolecular architectures.

Non-Foster approach to broadband optical metamaterials based on Lorentzian gain materials

All passive metamaterials are inherently narrowband due to fundamental dispersion-energy constraints, and their dispersive properties are usually approximated by a Lorentz model. However, there are broadband active metamaterials in the radio frequency (RF) regime based on negative capacitors with non-Foster dispersion properties. Non-Foster dispersion is usually considered as an “electronic-engineering trick” that cannot be applied at optical frequencies. Here, we demonstrate that the dispersion relation of a RF non-Foster capacitor is similar to that of an optical gain material described by a Lorentz model. This insight paves the way to realize non-Foster optical metamaterial structures. As the simplest example, we develop a broadband non-Foster optical epsilon-near-zero slab with a 1:10 bandwidth.

Exploring the impact of heterocyclic bridges for tuning the amplitudes of Nonlinear optical properties under Gas, IEFPCM and COSMO solvent models

Nonlinear optical (NLO) materials are a distinctive class of materials due to their NLO response and wide range of applications. We present a systematic quantum chemical study for designing triphenylamine based derivatives (1Ph to 3PhDTDZ) by modifying central bridge with various size and types of heterocyclic rings. Density functional theory (DFT) method is used to calculate the NLO properties including linear and third-order NLO polarizabilities (α and γ) by using M06-2X functional coupled with the 6-311G** basis set. The calculation results predict that among the designed compounds, 1PhDTDZ has the highest third-order NLO polarizability of 2347.7 x 10−36 esu and lowest transition energy of 1.828 eV. On the other hand, 3PhDTDZ has a greater amplitude (108.5 x 10−24 esu) of static linear polarizability (αiso). We also computed frequency-dependent third-order NLO polarizability values at various laser wavelengths (1500 nm to 1970 nm). This provides valuable information about the complex interaction between light and matter. Dynamic second hyperpolarizability of electro-optic Pockels effect (EOPE effect, (γ (−ω; ω,0,0)) is calculated at 1500 nm laser wavelength with a larger γ-amplitude of 36708.4 x 10−36 esu. The effect of solvent on α and γ has also been the primary focus of this research. An extensive solvation impact has been studied using integral equation formalism Polarizable Continuum Model (IEFPCM) and Conductor-like Screening Model (COSMO). Magnitudes of αiso and 〈γ〉 have shown variation from gas to solvent methods. While among solvents, amplitudes are seen 3.87 % to 11.29 % greater under the effect of COSMO-methanol than PCM-methanol. The Frontier molecular orbital (FMO) studies found a significant decrease in energy band gaps from 5.75 eV to 2.98 eV. Since our systems exhibit remarkable photovoltaic properties, they can be used as dye-sensitized solar cells (DSSCs). Their open circuit voltage (VOC) ranging from 1 eV to 4 eV. Thus, our designed triphenylamine based derivatives with distinct central heterocyclic bridges showcase remarkable efficiency as NLO materials, with additional benefits of exhibiting good photovoltaic properties.

Smart sensing property of Eu3+-induced polyelectrolyte nanoaggregates on nitrofuran antibiotics in aqueous environments

Pollution of water with antibiotics is a very serious global issue. So, simple, fast, and ecofriendly detection of such pollutants in aqueous environments has aroused great attention. Several intriguing properties such as narrow emission band, large stokes shift, long luminescence decay time and resistance to photobleaching distinguishes europium-based materials from commonly used fluorophores in biology as a superior optical smart material for applications in diverse fields. Herein, strongly luminescent Eu3+-induced polyelectrolyte nanoaggregates (EINAP) were synthesized and successfully characterized. The biocompatible polysaccharides hyaluronic acid and chitosan are used to disperse organic europium complexes resulting in formation of hybrid nanoaggregates. As synthesized EINAP demonstrated excellent quantum yield (89.29 %) and luminescence lifetime (656 µs). The EINAP also have high sensitivity and low limit of detection with good analytical precision for nitrofuran antibiotics in aqueous environments. The luminescent nano sensor developed in this work could be a novel tool for assessment of antibiotic pollution in the environment. The overall sensing mechanisms for detection of nitrofurans in aqueous environments were found to be the combination of inner filter effect and photoinduced electron transfer respectively.

Enabling Lignocellulose-Sourced Feedstocks to Fabricate Optical Filters with Desired Blocking Wavelength.

Near-infrared (NIR) filters have broad applications in fields such as information safety and privacy protection and environmental monitoring. Traditional NIR filters primarily rely on complex optical designs and environmentally unfriendly substrates, while lignocellulose-sourced NIR filters do not achieve the desired blocking wavelength and therefore face challenges in various application conditions. In this study, we propose a thickness adjustment strategy to precisely control the blocking wavelength of the NIR optical filters. The obtained optical filters with tailored thickness exhibited selective blocking wavelength in visible region (400-650 nm) as well as a high NIR transmittance (over 90%) and ultralow haze at 1400 nm. Given their selective wavelength blocking and high NIR transmittance, these bioselectors demonstrate potential applications in NIR optical fields, such as data security and privacy protection, presenting a promising advancement in next-generation sustainable NIR optical materials fabricated from all-lignocellulose feedstocks.

Mn2+ doped Zn2SiO4 phosphors: A threefold-mode sensing approach for optical thermometry in the visible region at 525 nm

Optical functional materials such as nanostructured silicates have been studied for photonics applications involving energy conversion. In this scenario, we studied Zn2SiO4:Mn2+ nanostructured powders prepared by combustion synthesis for optical thermometry based on photon downshifting. The structural analysis showed that Zn2SiO4 particles were found embedded in clustered silica nanoparticles. The photoluminescence analysis showed that the samples exhibit intense green emission (centered around 525 nm), corresponding to the electronic transition 4T1 → 6A1 of Mn2+, when exposed to a low power ultraviolet lamp (centered around 255 nm). The temperature sensing performance of this material was evaluated using three different methodologies, i.e. the luminescence decay time constant, the spectral full width at half maximum, and the luminescence peak intensity from the 4T1 → 6A1 radiative transition. The thermometric analysis based on luminescence peak intensity provided a maximum relative sensitivity of ∼4.9x10−3 K−1 at 498 K, while the decay lifetime and the spectral width at half maximum provided maximum relative temperature sensitivities of ∼2.9x10−3 K−1 at 523 K and ∼1.7x10−3 K−1 at 298 K, respectively.

Effect of morphology on the optical limiting of BiVO4 films

Precise control over the morphology and crystal structure of semiconductor-based optical materials is essential for optimizing their nonlinear optical properties. Morphological factors significantly affect the material’s interaction with light, influencing nonlinear absorption, harmonic generation, and optical confinement. In this study, the nonlinear optical (NLO) properties and optical limiting (OL) performance of bismuth vanadate (BiVO4) films depending on precursor solution pH condition, powder morphology and weight percentage of the BiVO4 powders in PMMA (10–30 wt.%) were investigated. The BiVO4 powders were synthesized via the hydrothermal method and the effect of precursor solution pH (pH of 1, 7.5 and 12) was investigated on the size and morphology of the BiVO4 powders. BiVO4 films were prepared using the spin coating method utilizing the BiVO4 powders and PMMA. The bandgap values of films were found to change from 3.39 to 3.56 eV depending on the BiVO4 growth solution pH. The nonlinear absorption coefficients (βeff), saturation intensity thresholds (ISAT) and optical limiting (OL) threshold were obtained using the open aperture (OA) Z-scan experiment. It has been observed that the nonlinear absorption and optical limitation performance of the BiVO4 films can be altered by changing the powder morphology and BiVO4 weight concentration. BiVO4 thin films fabricated using a precursor solution pH 12 and weight concentration of 30 wt.% showed the best performance among all fabricated films with the highest nonlinear absorption coefficient (βeff), saturation density threshold (ISAT) and lowest OL threshold value.