Tunable Optical Properties Research Articles

Mass Transport and Energy Conversion of Magnetic Nanofluids from Nanoparticles’ Movement and Liquid Manipulation

Magnetic nanofluids, also referred to as ferromagnetic particle levitation systems, are materials with highly responsive magnetic properties. Due to their magnetic responsiveness, excellent controllability, favorable thermal characteristics, and versatility, magnetic nanofluids have sparked considerable interest in both industrial manufacturing and scientific research. Magnetic nanofluids have been used and developed in diverse areas such as materials science, physics, chemistry and engineering due to their remarkable characteristics such as rapid magnetic reaction, elastic flow capacities, and tunable thermal and optical properties. This paper provides a full and in-depth introduction to the diverse uses of ferrofluids including material fabrication, fluid droplet manipulation, and biomedicine for the power and machinery sectors. As a result, magnetic nanofluids have shown promising applications and have provided innovative ideas for multidisciplinary research in biology, chemistry, physics and materials science. This paper also presents an overview of the device construction and the latest developments in magnetic-nanofluid-related equipment, as well as possible challenging issues and promising future scenarios.

Hot-Injection Synthesis of Cesium Lead Halide Perovskite Nanowires with Tunable Optical Properties.

Metal halide perovskite semiconductors have emerged as promising materials for various optoelectronic applications due to their unique crystal structure and outstanding properties. Among different forms, perovskite nanowires (NWs) offer distinct advantages, including a high aspect ratio, superior crystallinity, excellent light absorption, and carrier transport properties, as well as unique anisotropic luminescence properties. Understanding the formation mechanism and structure-property relationship of perovskite NWs is crucial for exploring their potential in optoelectronic devices. In this study, we successfully synthesized all-inorganic halide perovskite NWs with high aspect ratios and an orthorhombic crystal phase using the hot-injection method with controlled reaction conditions and surface ligands. These NWs exhibit excellent optical and electrical properties. Moreover, precise control over the halogen composition through a simple anion exchange process enables the tuning of the bandgap, leading to fluorescence emission, covering a wide range of colors across the visible spectrum. Consequently, these perovskite NWs hold great potential for efficient energy conversion and catalytic applications in photoelectrocatalysis.

Highly controlled synthesis of symmetrically branched tripod and pentapod nanocrystals with enhanced photocatalytic performance

Anisotropic nanostructures with tunable optical properties induced by controllable size and symmetry have attracted much attention in many applications. Herein, we report a controlled synthesis of symmetrically branched AuCu alloyed nanocrystals. By varying Au:Cu atom ratio in precursor, Y-shaped tripods with three-fold symmetry and star-shaped pentapods with five-fold symmetry are synthesized, respectively. The growth mechanism of AuCu tripods from icosahedral seeds and AuCu pentapods from decahedral seeds is revealed. Aiming to excellent photocatalytic performance, CdS nanocrystals are controlled grown onto the sharp tips of AuCu tripods and pentapods. In addition, a carrier-selective blocking layer of Ag2S is introduced between AuCu and CdS, for achieving effective charge separation in AuCu-Ag2S-CdS nanohybrids. Through evaluating the photocatalytic performance by hydrogen generation experiments, the AuCu-Ag2S-CdS tripod nanocrystals exhibit an optimized hydrogen evolution rate of 2182 μmol·g−1·h−1. These findings will contribute greatly to the understanding of complex nanoparticle growth mechanism and provide a strategy for the design of anisotropic nanoalloys for widely photocatalytic applications.

A holistic understanding of optical properties in amorphous H-terminated Si-nanostructures: Combining TD-DFT with AIMD

Silicon, traditionally known as an indirect band gap semiconductor, unveils intriguing properties at the nanoscale, stemming from deviations from k-conservation rules within nanostructures. In our study, we scrutinized four hydrogenated Si 0D-nanostructures—Si10H16, Si14H20, Si18H24, and Si22H28—to unravel their dynamic stability under thermal fluctuations and optical characteristics. We initiated our exploration by employing the TD-DFT framework to generate and analyze the optical properties of these geometrically optimized nanostructures. Simultaneously, we conducted ab initio molecular dynamics simulations to examine the structural robustness and thermal stability of the four structures. Leveraging the Car-Parrinello molecular dynamics approach within the Quantum ESPRESSO open software suite, we observed temperature evolution and stability differences among the nanostructures at targeted temperatures 40 and 300 K. Our subsequent investigation delved into the Turbo-Lanczos time-dependent DFT method, unraveling the optical properties and excited-state dynamics of hydrogenated Si nanostructures. The results unveiled shifts towards higher energy absorption edges E0, accompanied by alterations in the permittivity tensor, complex refractive index, oscillator strength, and reflectivity. Notably, the analysis revealed an enlarged HOMO-LUMO gap, distinctive from bulk Si. Furthermore, our models predicted the elimination of phase-dependent E1/E2 optical transition peaks in the imaginary part of the dielectric function, and a gradual decrease in the low-frequency dielectric response with increased hydrogenation of the amorphous structures. These findings underscore the promising applications of hydrogenating Si nanostructures in diverse technological domains such as optoelectronics, memristors, sensors, and quantum computing. Their tunable optical properties, size-dependent behaviors, and compatibility with existing silicon-based devices make them particularly appealing for next-generation technologies.

Unique Synthetic Strategy for Probing in Situ Lysosomal NO for Screening Neuroinflammatory Phenotypes against SARS-CoV-2 RNA in Phagocytotic Microglia.

In the pathogenesis of microglia, brain immune cells promote nitrergic stress by overproducing nitric oxide (NO), leading to neuroinflammation. Furthermore, NO has been linked to COVID-19 progression, which has caused significant morbidity and mortality. SARS-CoV-2 infection activates inflammation by releasing excess NO and causing cell death in human microglial clone 3 (HMC3). In addition, NO regulates lysosomal functions and complex machinery to neutralize pathogens through phagocytosis. Therefore, developing lysosome-specific NO probes to monitor phagocytosis in microglia during the COVID-19 infection would be a significant study. Herein, a unique synthetic strategy was adopted to develop a NO selective fluorescent probe, PDM-NO, which can discriminate activated microglia from their resting state. The nonfluorescent PDM-NO exhibits a turn-on response toward NO only at lysosomal pH (4.5-5.5). Quantum chemical calculations (DFT/TD-DFT/PCM) and photophysical study revealed that the photoinduced electron transfer (PET) process is pivotal in tuning optical properties. PDM-NO demonstrated good biocompatibility and lysosomal specificity in activated HMC3 cells. Moreover, it can effectively map the dynamics of lysosomal NO against SARS-CoV-2 RNA-induced neuroinflammation in HMC3. Thus, PDM-NO is a potential fluorescent marker for detecting RNA virus infection and monitoring phagocytosis in HMC3.

A Ligand-Directed Spatial Regulation to Structural and Functional Tunability in Aggregation-Induced Emission Luminogen-Functionalized Organic-Inorganic Nanoassemblies.

Aggregation-induced emission luminogen (AIEgen)-functionalized organic-inorganic hybrid nanoparticles (OINPs) are an emerging category of multifunctional nanomaterials with vast potential applications. The spatial arrangement and positioning of AIEgens and inorganic compounds in AIEgen-functionalized OINPs determine the structures, properties, and functionalities of the self-assembled nanomaterials. In this work, a facile and general emulsion self-assembly tactic for synthesizing well-defined AIEgen-functionalized OINPs is proposed by coassembling alkane chain-functionalized inorganic nanoparticles with hydrophobic organic AIEgens. As a proof of concept, the self-assembly and structural evolution of plasmonic-fluorescent hybrid nanoparticles (PFNPs) from concentric circle to core shell and then to Janus structures is demonstrated by using alkane chain-modified AuNPs and AIEgens as building blocks. The spatial position of AuNPs in the signal nanocomposite is controlled by varying the alkane ligand length and density on the AuNP surface. The mechanism behind the formation of various PFNP nanostructures is also elucidated through experiments and theoretical simulation. The obtained PFNPs with diverse structures exhibit spatially tunable optical and photothermal properties for advanced applications in multicolor and multimode immunolabeling and photothermal sterilization. This work presents an innovative synthetic approach of constructing AIEgen-functionalized OINPs with diverse structures, compositions, and functionalities, thereby championing the progressive development of these OINPs.

Synthesis and Characterization of PVA-Encapsulated Fe2O3-ZnO as New Composites with Tunable Optical Properties

Synthesis and Characterization of PVA-Encapsulated Fe2O3-ZnO as New Composites with Tunable Optical Properties

Zirconium Oxynitride Thin Films for Photoelectrochemical Water Splitting.

Transition metal oxynitrides are a promising class of functional materials for photoelectrochemical (PEC) applications. Although these compounds are most commonly synthesized via ammonolysis of oxide precursors, such synthetic routes often lead to poorly controlled oxygen-to-nitrogen anion ratios, and the harsh nitridation conditions are incompatible with many substrates, including transparent conductive oxides. Here, we report direct reactive sputter deposition of a family of zirconium oxynitride thin films and the comprehensive characterization of their tunable structural, optical, and functional PEC properties. Systematic increases of the oxygen content in the reactive sputter gas mixture enable access to different crystalline structures within the zirconium oxynitride family. Increasing oxygen contents lead to a transition from metallic to semiconducting to insulating phases. In particular, crystalline Zr2ON2-like films have band gaps in the UV-visible range and are n-type semiconductors. These properties, together with a valence band maximum position located favorably relative to the water oxidation potential, make them viable photoanode candidates. Using chopped linear sweep voltammetry, we indeed confirm that our Zr2ON2 films are PEC-active for the oxygen evolution reaction in alkaline electrolytes. We further show that high-vacuum annealing boosts their PEC performance characteristics. Although the observed photocurrents are low compared to state-of-the-art photoanodes, these dense and planar thin films can offer a valuable platform for studying oxynitride photoelectrodes, as well as for future nanostructuring, band gap engineering, and defect engineering efforts.

Influence of polymer matrices on the structural, morphological, thermal, and optical properties of PbS nanoparticles embedded in electrospun nanofibers

The development of electrospun nanomaterials with tunable optical and structural properties has significant implications for various applications. Herein, we develop a controllable and efficient strategy for in situ-grown Lead sulfide (PbS) nanoparticles (NPs) in the electrospun PVA-PVP blend nanofibers. The fibrous mats have been synthesized for different concentrations of PbS NPs grown in the PVA-PVP blend along with its parent polymers, PVA and PVP. The study uniquely enables the in-situ growth of PbS NPs within these matrices, resulting in nanofibers with tunable optical and structural properties. The synthesized PbS/Polymer nanofibers exhibit significant variation in bandgap values, ranging from 2.7 to 1.16 eV for PbS concentrations between 0.05 M and 0.2 M across all polymer matrices. Furthermore, our findings suggest that the interaction between the PbS NPs and polymer matrix does not solely result in simple additive effects. The observed results have been comprehensively analyzed, considering the intricate effects of quantum confinement.

Confining carbon dots in extra-large pore zeolite SYSU-3 assembled in a mixed-template system

The 24-membered ring -SYT type extra-large pore zeolite, denoted as DESO-SYSU-3, has been synthesized by employing N,N′-diethylsophoridine and trimethylsulfanium in a mixed-template system, where the N,N′-diethylsophoridine and trimethylsulfanium played different roles in the crystallization process. A single usage of N,N′-diethylsophoridine led to the formation of an unknown phase (donated as SYSU-5). These results reveal that the utilization of alkaloid-derived organic structure-directing agents (OSDAs) is an efficient synthetic strategy to produce specific extra-large pore zeolites and related structures. Compared to the prototype SYSU-3, the addition of TMSF into the system not only improved the silicon content in the framework of DESO-SYSU-3 but also facilitated the generation of carbon dots (CDs) confined in extra-large pore structure. The structure and the proposed formation mechanism of CDs were investigated based on HRTEM, XPS, FI-IR, UV–Vis, Raman and photoluminescence spectrum. The CDs@zeolite composite exhibited intriguing optical properties of both fluorescence and room temperature phosphorescence, respectively. This work extends extra-large pore zeolite as the matrix for the development of CDs@zeolite composites with tunable optical properties.

Aerosol assisted-chemical vapour deposition of tetrahedrite copper antimony sulphide thin films: the effect of zinc(II) impurities on optical properties

Non-stoichiometric semiconducting copper antimony sulphide (CAS) thin films, both undoped and with Zn2+ ions incorporated, were deposited at 500, 550 and 600 °C onto glass substrates by aerosol-assisted chemical vapour deposition (AACVD) using metal diethyldithiocarbamate precursors. Data from powder X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy, and scanning electron microscopy – energy dispersive X-ray spectroscopy suggest a correlation of composition of the non-stoichiometric sulphur-deficient tetrahedrite phase (cubic structure) microcrystalline CAS (Cu12Sb4S13) thin films with particle sizes ranging from 0.1 to 4 µm. For undoped thin films, visible optical absorption with a bandgap of ∼2.1 eV is likely associated with compositional variations involving intrinsic lattice defects, including shallow electronic states such as copper interstitials and vacancies of sulphur as deep-lying donors, and copper-antimony anti-sites and antimony vacancies as deep-lying acceptors. Additionally, tetrahedrite phase CAS (tCAS) thin films with Zn2+ ions incorporated (Znx-tCAS) exhibit tunable composition-driven electronic structure for small Zn2+ content influencing narrower bandgaps between 1.7 and 1.9 eV. The Raman data suggest that the phase purity is affected by small fractions of the famatinite (tetragonal) phase. Overall, the thin films display broad emission of fast dual radiative recombination, and an additional recombination pathway exhibited for Znx-tCAS associated with zinc-related point defects. Though further studies are required to explore in more detail the defect chemistry, these results show the utility of AACVD in tuning compositional and optical properties of undoped tCAS and Znx-tCAS thin films.

A pressure tunable optical and thermoelectric properties of Rb2CuSbX6 (X = cl, Br, and I) by FPLAPW+lo method

The pressure dependencies of the structural, electrical, elastic, optical, and thermoelectric characteristics of the Halide double perovskites (HDPs) Rb2CuSbX6 (X = Cl, Br, and I) compounds were computed using the FP-LAPW method within the density functional theory framework, under high pressure conditions. HDPs received a lot of attention due to their potential application in optoelectronic and thermoelectric devices. The Perdew-Burke-Ernzerhof (PBEsol-GGA) is used to investigate the structural properties of selected compounds, while the modified Becke-Johnson (mBJ) functional is used to obtain a better agreement between the calculated optoelectronic and electronic properties and experimental observations. The Born criteria and formation energy are explored for the stability of all selected HDPs. The elastic constants of cubic symmetry are investigated to determine the difference between ductile and brittle nature, anisotropy, and bulk modulus. The bandgaps for Rb2CuSbCl6, Rb2CuSbBr6, and Rb2CuSbI6 are 1.08 eV, 0.72 eV, and 0.33 eV, respectively. Decrease band gap with increase in pressure. The density of states plots under zero pressure exhibit a combination of ionic and covalent bonding, whereas an increase in pressure results in a reinforcement of covalent bonding. The absorption spectra are observed in the infrared region. All HDPs were further analyzed with respect to optical absorption, refractive index, and dielectric constants for the energy range 0–10 eV. Additionally, Boltzmann classical theory explains the lower lattice temperature, greater Seebeck coefficient, thermal conductivity, and electrical conductivity of HDPs, making them for thermoelectric applications.

Near‐unity quantum efficiency wavelength‐tunable NIR phosphors (Sr2−yCay)Sc1−xSbO6: xFe3+ with excellent thermal stability

AbstractFe3+ ions as near‐infrared (NIR) activators are emerging as an alternative to Cr3+.1–5 However, it is a challenge to develop Fe3+‐activated NIR phosphors featuring tunable optical properties, high efficiency, and thermal stability. Herein, we present a series of near‐unity internal quantum efficiency (IQE), wavelength‐tunable and thermal stability NIR‐emitting phosphors Sr2−yCaySc1−xSbO6:xFe3+ (S2−yCyS1−xS:xFe3+). Sr2ScSbO6:1%Fe3+ (SSS:1%Fe3+) phosphor shows broadband NIR emission at 904 nm and near‐unity IQE under excitation at 300 nm. Experimental and theoretical calculation results demonstrate that introduced Ca ions could increase the bandgap value and Debye temperature (ΘD) of host from Eg = 3.702 eV, ΘD = 609 K of y = 0 to Eg = 3.801 eV, ΘD = 692 K of y = 2. Significantly, the resultant S2−yCyS1−xS:1%Fe3+ NIR phosphors show wavelength‐tunable emission from 904 to 952 nm and high IQE of 84.6%–97.5% as well as enhanced thermal stability (I423K/I298K = 76.9%) of Ca2ScSbO6:1%Fe3+ (CSS:1%Fe3+) in comparison with that (I423K/I298K = 70.6%) of pristine sample. We fabricated an NIR light‐emitting diodes (LED) device by using CSS:1%Fe3+ NIR phosphors with ultraviolet LED chip and demonstrated its potential applications in anticounterfeiting, information encryption, and night vision.

Graphene-Tuned, Tightly Coupled Hybrid Plasmonic Meta-Atoms.

Tightly coupled meta-atoms (TCMAs) are densely packed metamaterials with unnatural refractive indexes. Actively modulated TCMAs with tunable optical properties have found many applications in beam shaping, holography, and enhanced light-matter interactions. Typically, TCMAs are studied in the classic Bloch theory. Here, tightly coupled H-shaped meta-atoms are proposed with an ultra-high permittivity of ~6000, and their active modulation with graphene is designed by using the tightly coupled dipole array (TCDA) theory. The H-shaped meta-atoms are used as dipole arms, and the graphene strips function as the dipole loads. By tuning the chemical potential of graphene, the resonant amplitude, frequency, and permittivity are dynamically modulated. The simulations indicate that the real and imaginary parts of permittivity change from 6854 to 1522 and from 7356 to 2870, respectively. The experimental validation demonstrates a modulation depth of 11.6% in the resonant frequency, i.e., from 219.4 to 195 GHz, and a substantial 52.5% modulation depth in transmittance under a bias voltage of less than 1.5 V.

Tunable Electronic and Optical Properties of MoGe2N4/AlN and MoSiGeN4/AlN van der Waals Heterostructures toward Optoelectronic and Photocatalytic Applications

Tunable Electronic and Optical Properties of MoGe2N4/AlN and MoSiGeN4/AlN van der Waals Heterostructures toward Optoelectronic and Photocatalytic Applications

Strain tunable optical and transport properties of intrinsic ferromagnetic semiconductor CrOCl monolayer

Based on density functional theory, the electronic structure, transport, and optical properties of monolayer CrOCl are studied theoretically. The electronic structure analysis shows that monolayer CrOCl is a ferromagnetic semiconductor with an indirect band gap of 2.45 eV, and the electronic properties of monolayer CrOCl can be changed significantly by applying external strain. When 12 % uniaxial tensile strain is applied along the a-axis, the band gap of monolayer CrOCl decreases to 1.94 eV, the hole mobility can reach 1520.11 cm2 V−1·s−1, and the mobility difference between holes and electrons increase to 1471.53 cm2 V−1·s−1. Furthermore, the applied strain, regardless of tensile or compressive, can cause the redshift of the optical absorption peak of monolayer CrOCl, thereby improving the absorption performance in the visible light region. In addition, it was found that the in-plane absorption of bilayer CrOCl increased to nearly twice as compared with the monolayer one. These results indicate that single and few layers of CrOCl have the potential application prospect in the field of optoelectronic devices.

Photocatalytic Hydrogen Peroxide Production through Functionalized Semiconductive Metal-Organic Frameworks.

Hydrogen peroxide (H2O2) holds significance as a vital chemical with the potential to serve as an energy carrier. Compared with the conventional anthraquinone process, photocatalytic H2O2 production has emerged as an appealing alternative because of its energy efficiency and environmental sustainability. However, the existing photocatalysts suffer from low catalytic efficiency, limited tunability of optical properties, and reliance on sacrificial agents due to high energy loss caused by inefficient charge separation. Therefore, developing catalysts with tunable optical properties and efficient charge separation is desirable. In this work, we introduce postsynthetic functionalization into an electrically conductive metal-organic framework, namely, DPT-MOF. Leveraging DPT (3,6-di(4-pyridyl)-1,2,4,5-tetrazine) as a pillar ligand, we exploited click-type chemistry to manipulate band position and charge separation efficiency, allowing for photocatalytic nonsacrificial H2O2 production. Notably, the fluorine-functionalized MOF exhibited the highest H2O2 production rate of 1676 μmol g-1 h-1 under visible light in O2-saturated water among our other samples. This high production rate is attributed to the tuned electronic structure and prolonged charge lifetime facilitated by the fluorine groups. This work highlights the effectiveness of postsynthetic methodology in tuning optical properties, opening a promising avenue for advancing the field of semiconductive MOF-based photocatalysis.

Two-dimensional lead halide perovskite lateral homojunctions enabled by phase pinning

Two-dimensional organic-inorganic hybrid halide perovskites possess diverse structural polymorphs with versatile physical properties, which can be controlled by order-disorder transition of the spacer cation, making them attractive for constructing semiconductor homojunctions. Here, we demonstrate a space-cation-dopant-induced phase stabilization approach to creating a lateral homojunction composed of ordered and disordered phases within a two-dimensional perovskite. By doping a small quantity of pentylammonium into (butylammonium)2PbI4 or vice versa, we effectively suppress the ordering transition of the spacer cation and the associated out-of-plane octahedral tilting in the inorganic framework, resulting in phase pining of the disordered phase when decreasing temperature or increasing pressure. This enables epitaxial growth of a two-dimensional perovskite homojunction with tunable optical properties under temperature and pressure stimuli, as well as directional exciton diffusion across the interface. Our results demonstrate a previously unexplored strategy for constructing two-dimensional perovskite heterostructures by thermodynamic tuning and spacer cation doping.

Tracing the entry process of submicrometre plastics in soybean sprouts by leaf-derived fluorescent carbon dots

As a global emerging contaminant, microplastics (MPs) in water or soil can accumulate in vegetables, making them easily ingested through the diet. With excellent and tunable optical properties, carbon dots (CDs) are highly advantageous for tracing the entry process of MPs. Originally, long-wavelength CDs were synthesized from leaf-derived extracts, and fluorescent submicrometer plastics (CDs-MPs) with clean surfaces and concentrated particle sizes were obtained by soap-free microemulsion polymerization. The concentration of CDs-MPs exhibits a significant linear relationship with long-wavelength fluorescence intensity (λEx/λEm: 415/676 nm). Soybean sprouts (SBS), as an important type of food, are susceptible to contamination of MPs due to their soft epidermis and rapidly growing biomass. The results showed that CDs-MPs could be embedded into the cortex of SBS and enter the plant with cell division and elongation, leading to an increase in pore size on the cell wall surface. After entering the root system, CDs-MPs will pass through the Casparian strip and migrate in the vessels. Then, CDs-MPs enter the leaves through vascular bundles, and the distribution and size of epicuticular wax on leaves have changed. Furthermore, SBS showed resistant growth and increased levels of oxidative response when exposed to MPs/CDs-MPs. It is the first study to demonstrate the application of leaf-derived CDs in the prevention of MPs pollution by revealing the migration behavior of submicrometre plastics in SBS.

Tunable electronic structure and optical properties of GaN monolayer via substituted doping and strain

In this study, the stability, optical properties and electronic structure of transition metal (TM) (Cr, Mn, Fe) doped GaN monolayers is investigated within the first-principles calculation methods. Additionally, the influence of biaxial strain on the aforementioned system is explored. The results demonstrate that substitutional doping effectively adjusts the electronic structure of GaN monolayer, enhancing its performance. The TM-doped GaN monolayer structures exhibit strong dynamic stability: doping with Cr and Fe bring magnetic properties, while Mn doping results in a half-metallicity property. In terms of optical absorption, the GaN:Mn system exhibits significant absorption in the infrared region, while GaN:Cr and GaN:Fe systems show stronger absorption in the visible light and ultraviolet regions compared to the pristine GaN monolayer. Under the biaxial strain from −3% to +12%, with increments of 3%, the band gap types of GaN:Cr, GaN:Fe, and GaN:Mn systems undergo minimal changes, with gradual reduction in gap values. Meanwhile, the optical absorption of doped systems exhibits systematic growth and redshift, particularly evident in the infrared-visible-ultraviolet spectral regions for the GaN:Mn system. These results indicate the controllability and variability of two-dimensional GaN materials, providing new avenues for the potential use of GaN as a material for optoelectronic devices.