Near-infrared Research Articles

Optimized synthesis and characterization of La(OH)3 and LaB6 nanostructures for enhanced NIR optical filters

The present study describes a method for synthesizing nanostructured La(OH)3 and LaB6 materials with efficient field emission properties using the spin coating technique. The study was motivated by the significant demand for the optical properties of LaB6 with efficient field emission properties using the spin coating technique in the near-infrared (NIR) region. The optimization of the LaB6 synthesis process for economic and reproducible results is highlighted, showcasing a systematic approach starting from La(OH)3 formation through chemical mixing and high-temperature heating, followed by boron incorporation. The systematic methodology includes forming La(OH)3 through chemical mixing and high-temperature heating, followed by combining it with boron to achieve the LaB6 structure. Characterization methods such as XRD, FTIR, SEM, AFM, and SIMS validated the successful synthesis and uniformity of the materials. Optical analyses showed increased visible transmittance and reduced infrared transmittance for the LaB6 thin film. Optical analyses showed increased visible transmittance and decreased infrared transmittance in the 110 nm thick LaB6 film, with an absorption valley at 1000 nm. SEM images revealed microstructural features and AFM analysis indicated a homogeneous distribution of La and B atoms with an RMS value of 0.87 nm. SIMS analysis confirmed uniform atomic distribution throughout the film thickness. The optimized recipes contribute to the efficiency and controllability of the synthesis process. The presented results provide valuable insights into material synthesis methodologies and serve as a crucial reference for utilizing LaB6 materials in infrared devices.

Highly efficient Y3-xBaxAl5-xSixO12:Cr3+ near-infrared phosphor for plant growth

Near-infrared (NIR) phosphors enhance the growth of plants due to their superior penetration. However, relatively high thermal quenching and low quantum efficiency restrict the development of NIR phosphors. In this study, Y3-xBaxAl5-xSixO12:Cr3+ phosphors (YBAS:Cr3+) with varying concentrations of Ba2+-Si4+ and Cr3+ were studied. The results demonstrate high-purity phases are obtained with doping Ba2+-Si4+ and Cr3+. The Ba2+-Si4+ doping enhances crystallinity and near-spherical particles are synthesized. The theoretical calculations indicate a significant reduction in bandgap with doping Ba2+-Si4+, resulting in impurity levels appearing in the valence band region. The state density calculation shows that the band formation is contributed by all elements. The optimal Ba2+-Si4+ doping concentration is 0.05 mol and the Cr3+ doping content is 0.09 mol. The critical distance (R c ) is 16.62 Å. Dipole–dipole interactions and radiation reabsorptions are main concentration quenching mechanisms. Lattice distortions occur with the introduction of Ba2+-Si4+ and the value (D r ) is 0.052. The YBAS:0.09Cr3+ phosphor shows a crystal field strength with a Dq/B value of 2.76. The phosphor exhibits a high quantum efficiency (73.42%), superior thermal quenching resistance (∼70% initial intensity at 150°C), and a suitable fluorescence lifetime (130.04 µs). A near-infrared pc-LED with YBAS:0.09Cr3+ phosphor displays a high output power of 167.12 mW and a moderate conversion efficiency of 3.82%.

NIR stimulated epigallocatechin gallate loaded polydopamine with enhanced antibacterial and ROS scavenging abilities for improved infectious wound healing

Infectious wound healing is complicated with and limited by infection and oxidative stress at the wound site. In recent years, various evidences suggest that nanozymes with multiple enzymatic activities have enabled the development of novel strategies for infectious wound healing. In this study, epigallocatechin gallate loaded polydopamine (P@E) was developed to act as a potent reactive oxygen species (ROS) scavenger for scavenging ROS, alleviating inflammatory responses, and promoting infectious wound healing. Combining with near infrared (NIR) irradiation, P@E presented excellent antibacterial ability of Escherichia coli (E. coli, 93.6%) and methicillin-resistant Staphylococcus aureus (MRSA, 87.6%). Specifically, P@E+NIR exhibited the most potent antioxidant, anti-inflammatory and cell proliferation behaviors through down-regulating intracellular ROS levels (81.9% and 94.3% for NIH3T3 and RAW264.7 respectively) and inducible nitric oxide synthase (iNOS) expression level (55.7%), and up-regulating the expression levels of arginase-1 (Arg-1, 71.4%), heat shock protein 70 (HSP70, 48.6%) and platelet endothelial cell adhesion molecule (CD31, 35.3%) compared to control group. Meanwhile, it also efficiently induced M2 directional polarization of lipopolysaccharide induced murine macrophages to achieve anti-inflammation, indicated by the down-regulation of CD86 (86.2%), and up-regulation of CD206 (85.6%). Significantly, it was also observed that P@E+NIR presented the excellent behaviors of inhibiting wound infection, alleviating wound inflammation, as well as promoting skin tissue repairing. Altogether, it has developed the strategy of using P@E combining with NIR irradiation for the synergistic enhanced healing of infectious skin wound, which can serve as a promising therapeutic strategy for its clinical treatment.

Intelligent Monitoring of Post-Processing Characteristics in 3D-Printed Food Products: A Focus on Fermentation Process of Starch-gluten Mixture Using NIR and Multivariate Analysis

The production of three-dimensional (3D)-printed food products requires not only optimal 3D-printing adaptability but also appropriate post-processing characteristics. This study aimed to use near infrared (NIR) spectroscopy to predict the rheological properties of 3D-printed dough, enabling intelligent monitoring of the dough’s fermentation process. Utilizing support vector machine (SVM) classification model, the fermentation stages can be classified as under-fermentation, complete fermentation, and over-fermentation. Employing preprocessing methods with Synergy Interval Partial Least Square-Competitive Adaptive Reweighted Sampling (SIPLS-CARS) algorithm, 27, 39, 23, and 27 key wavelengths were filtered from the raw NIR spectral data, corresponding to the prediction of storage modulus (G'), loss modulus (G''), complex viscosity (η*), and loss factor (tan δ), respectively. Quantitatively, SVM (Support Vector Machine) regression outperformed Partial Least Squares (PLS) with Rc2 values (0.95, 0.94, 0.94) and Rp2 values (0.93, 0.93, 0.94) for G', G'', and η*. NIR spectra-based predictive models demonstrated superior performance compared to rheo-fermentation properties models. In summary, these findings show the potential of NIR spectroscopy as a rapid tool for predicting the fermentation progress of 3D-printed doughs.

Near-infrared luminescence in Ca3ZnMGe3O12:Cr3+ (M = Zr, Hf, Sn, Ti) garnet family for light-emitting diode applications

Near-infrared (NIR) phosphors as crucial components of NIR light sources have multifunctional and smart spectroscopy applications, prompting an increasing research interest in developing efficient and stable NIR materials. Focusing on this issue, the present study explored the luminescent properties of Cr3+-doped Ca3ZnMGe3O12 (M = Zr, Hf, Sn and Ti) garnet family. These materials exhibit an emission peak falls within the range of 785–805 nm with a full width at half maximum (FWHM) varying from 114 to 123 nm. Among them, the Ca3ZnZrGe3O12:Cr3+ phosphor shows the highest photoluminescence quantum yield (PLQY = 60.3 %) and an excellent thermal stability (I423K/I298K = 77.51 %). Moreover, the performance of a prototype Ca3ZnZrGe3O12:Cr3+-containing NIR pc-LED device was estimated, which achieves an NIR output of 23.46 mW and a photonic efficiency of 14.09 % under 100 mA driving current. Non-destructive examination can be realized using this light source, demonstrating the good potential of the material in NIR spectroscopy applications.

Extragalactic globular cluster near-infrared spectroscopy

Context. One way to constrain the evolutionary histories of galaxies is to analyse their stellar populations. In the local Universe, our understanding of the stellar population properties of galaxies has traditionally relied on the study of optical absorption and emission-line features. Aims. In order to overcome limitations intrinsic to this wavelength range, such as the age-metallicity degeneracy and the high sensitivity to dust reddening, we must use wavelength ranges beyond the optical. The near-infrared (NIR) offers a possibility to extract information on spectral signatures that are not as obvious in traditional optical bands. Moreover, with the current and forthcoming generation of instrumentation focusing on the NIR, it is mandatory to explore possibilities within this wavelength range for nearby-Universe galaxies. However, although the NIR shows great potential, we are only beginning to understand it. Widely used techniques such as a full spectral fitting and line strength indices need to be tested on systems that are as close to simple stellar populations as possible, and the result from the techniques need to be compared to the yields from a traditional optical analysis. Methods. We present a NIR spectral survey of extragalactic globular clusters (GCs). The set was composed of 21 GCs from the Centaurus A galaxy that were obtained with SOAR/TripleSpec4, which covered the ∼1.0–2.4 μm range with a spectral resolution (R = λ/Δλ) of 3500. These spectra cover Hβ equivalent widths between 0.98 Å and 4.32 Å, and [MgFe]′ between 0.24 Å and 3.76 Å. Results. This set was ideal for performing absorption band measurements and a full spectral fitting, and it can be used for kinematic studies and age and abundance measurements. With this library, we expect to be able to probe the capabilities of NIR models, as well as to further improve stellar population estimates for the GCs around the Centaurus A galaxy.

A near-infrared triggered multi-functional indocyanine green nanocomposite with NO gas release function inducing improved photothermal therapy

The integration of photothermal and near-infrared (NIR) imaging capabilities of indocyanine green (ICG) small molecules has attracted considerable attention in tumor diagnosis and treatment. However, the abnormal upregulation of cellular heat shock proteins (HSPs) induced by photothermal therapy (PTT) enhances cellular heat resistance, thereby severely affecting the efficacy of PTT. In this study, to address the impact of HSPs on the efficacy of PTT while obtaining high-quality NIR fluorescence imaging in the NIR region, we designed a targeted peptide@ICG nanofluorescent probe encapsulated in liposomes. The introduced cRGD targeting peptide not only possesses tumor-targeting capabilities but also features LA as the last amino acid in the targeting peptide, which can generate nitric oxide (NO) under reactive oxygen species (ROS) triggering. It can happen under 808 nm single-light source NIR light, and the guanidine group in the peptide decomposes and combines with singlet oxygen molecules to generate NO gas molecules, thereby exerting an elevated photothermal effect by inhibiting the expression of HSP70. In addition, the nanoprobes enable deep imaging and treatment of glioma in situ and can be combined with a laser speckle contrast imaging (LSCI) system for multimodal imaging. This composite probe demonstrates synergistic tumor therapeutic effects of photodynamic therapy (PDT), PTT, and gas therapy, offering a promising strategy for cancer treatment.

Broadband NIR‐II Emission Generated by Tetrahedral Cr3+/Cr4+ in SrLaGa3O7

AbstractBroadband near‐infrared (NIR) phosphors have garnered significant attention due to their potential applications in phosphor‐concerted NIR light‐emitting diodes (pc‐NIR‐LEDs). Cr3+‐doped NIR phosphors are particularly intriguing because of their broad NIR emission and high efficiency. However, reports on Cr3+‐doped NIR‐II (900–1700 nm) phosphors are scarce. In this study, a novel Cr3+‐doped SrLaGa3O7 NIR‐II phosphor is presented, where the Cr3+ ions are located at tetrahedral sites. The full width at half maximum (FWHM), peak wavelength, internal quantum efficiency (IQE), and thermal activation energy (ΔE) for the synthesized SrLaGa3O7:0.9%Cr3+ phosphor are 194 nm, 1167 nm, 76.12%, and 0.269 eV, respectively. The substitution of Sc3+ for Ga3+ enhances the luminescence performance, and the 0.9%Cr3+/3%Sc3+ co‐doped SrLaGa3O7 phosphor exhibits a peak wavelength of 1208 nm, an IQE of 92.78%, and a ΔE of 0.285 eV. Furthermore, the sintering process in the air induces a transition from Cr3+ to Cr4+, resulting in the formation of SrLaGa3O7:0.9%Cr4+ phosphor, which has a peak wavelength of 1270 nm and an FWHM of 305 nm. The potential application of the 0.9%Cr3+/3%Sc3+ co‐doped SrLaGa3O7 phosphor in pc‐NIR‐LEDs is also evaluated.

Growth of dendritic CuS nanostructures for photoacoustic image guided Chemo-Photothermal therapy

Herein, we report a unique method for design and development of carboxyl enriched dendritic CuS nanostructures (CuS NSs) for photoacoustic image guided chemo-photothermal therapy. The dendritic network was grown on the surface of CuS nanoparticles via layer-by-layer assembly of amino acid. XRD and TEM studies established the formation of crystalline well-spherical nanosized hexagonal covellite (CuS) phase. The successful growth of dendritic structure was apparent from the rise in surface charge, hydrodynamic diameter and characteristic vibrational band intensity of peptide bonds. The developed different generations of dendritic CuS NSs (D0-CuS NSs, D1-CuS NSs, D2-CuS NSs and D3-CuS NSs) displayed wide-ranging absorption band in near infrared (NIR) zone and exhibited good photothermal heating efficacy upon irradiation of 980 nm laser light. From in to vitro cellular studies, it has been found that the NIR irradiation effectively enhanced the photothermal toxicity of D3-CuS NSs towards cancer cells. Moreover, these negatively charged water-dispersible D3-CuS NSs were conjugated with positively charged anticancer drug, doxorubicin hydrochloride (DOX) through electrostatic interaction. The DOX loaded D3-CuS NSs (DOX@D3-CuS NSs) revealed pH dependent drug release behaviour and their considerable uptake in breast cancer cells (MCF-7). Further, DOX@D3-CuS NSs exhibited a much higher toxicity towards cancer cells upon NIR light over individual counterparts suggesting their strong ability for chemo-photothermal therapy. Moreover, these biocompatible CuS NSs have shown excellent concentration dependent photoacoustic properties at pulse laser excitation (850 nm) and thus, they can be found potential application in chemo-photothermal therapy.

Piezoelectric-induced mechanoluminescence in centrosymmetric Lu3Al5O12: Properties of self-recoverable and tunable near-infrared luminescence

Mechanoluminescence (ML) materials with long-wavelength emission bands are essential for future in vivo bioimaging, non-destructive testing. However, most of the near-infrared (NIR) ML materials require pre-irradiation, which may limit their further applications. Generally, piezoelectric-induced ML materials were considered to be related to the piezoelectric effect from non-centrosymmetric structure. Innovatively in this work, a novel piezoelectric-induced near-infrared ML material Lu3Al5O12:Cr3+ with centrosymmetric structure is obtained. In Lu3Al5O12:Cr3+, piezoelectric effect is generated from the distortion of the centrosymmetric structure of the host due to the uneven electron distribution of Cr3+. Here, highly tunable ML FWHM from 7 nm to 118 nm is realized by introducing different content Ga3+ ions to Lu3Al5O12:Cr3+. The ML film fabricated by composite polydimethylsiloxane and Lu3Al2Ga3O12:Cr3+ can penetrate 20 mm pork tissue, which suggests the potential applications of the NIR ML material in the field of optical imaging of stress distribution in organisms. The discovery of distorted crystal structure to induce piezoelectric effect provides a new thinking for exploring ML in centrosymmetric materials. In addition, LuAl5-xGaxO:Cr3+ phosphors have broad prospects in self-powered sensing, temporomandibular disorders diagnosis, information security, and biomedical fields.

Yb3+-activated phosphate glasses melted with MnCO3 for solar spectral conversion

This paper reports on the physical and optical properties of phosphate glasses containing red-emitting Mn2+ and near-infrared (NIR)-emitting Yb3+ ions of interest for solar spectral conversion. The glasses were prepared by melting with 50P2O5-(48 – x)BaCO3-2Yb2O3-xMnCO3 (x = 0, 1, 2, 3, 4 mol%) formulas, and characterized by X-ray diffraction (XRD), Fourier transform-infrared (FT-IR) spectroscopy, differential scanning calorimetry (DSC), UV-Vis-NIR spectrophotometry, and photoluminescence (PL) spectroscopy. The glasses were X-ray amorphous with the various characteristic features of phosphate glasses being evident in the FT-IR spectra. The thermal properties of the co-doped glasses assessed by DSC appeared similar despite the variation in manganese content. The optical absorption spectra supported the occurrence of Mn2+ ions while Mn3+ was detected at high MnCO3 content. The NIR absorption due to Yb3+ ions was nonetheless consistent with the fixed Yb2O3 content. The PL evaluation showed that sensitized Yb3+ PL was attained under Mn2+ excitation at 410 nm where the NIR emission increased with MnCO3 content in connection with Mn2+ → Yb3+ energy transfer. However, the NIR emission output realized with 4 mol% MnCO3 was just marginally higher than the obtained with 3 mol% MnCO3. On the other hand, the red Mn2+ emission was highest for 3 mol% MnCO3. Thus, considering the optimized red and NIR emissions while minimizing absorption by Mn3+, the Yb-containing glass melted with 3 mol% MnCO3 was put in perspective with the concept of solar spectral conversion.

Near-infrared Spectral Homogeneity of the Didymos System Before and After the DART Impact* * Based on observations made with the Italian Telescopio Nazionale Galileo (TNG) operated on the island of La Palma by the Fundación Galileo Galilei of the Istituto Nazionale di Astrofisica (INAF) at the Spanish Observatorio del Roque de los Muchachos of the Instituto de Astrofisica de Canarias

We spectroscopically characterized the Didymos system, target of the Double Asteroid Redirection Test (DART)/Light Italian Cubesat for Imaging of Asteroids (LICIACube) space mission, close in time to the DART impact event, during six nights between 2022 August and November at Telescopio Nazionale Galileo. Here, we show that near-infrared (NIR) spectra (0.75–2.25 μm) look mostly similar within the same night and between different nights. They are in good agreement with the only spectrum previously available in the literature, observed almost 20 years before those reported in this paper. During one of the observing nights we also obtain spectroscopy information on the ejecta tail induced by the DART impact. The spectrum of the ejecta tail is also very similar to Didymos/Dimorphos itself. All of these aspects seem to suggest that the Didymos system in the NIR looks mostly homogeneous, with very subtle spectral variations.

Structure regulation and luminescence improvement of Gd3Ga5O12:Cr3+: An anti-thermal quenching NIR phosphor for multifunctional applications

Near-infrared (NIR) phosphors converted light emitting diodes (LEDs) are booming as next NIR light sources. But the quantum efficiency and thermal stability of the NIR phosphors need to be improved. Here, thermally stable garnet Gd3Ga5O12 is selected as the matrix and Cr3+ as the luminescent center to obtain Gd3Ga5O12:Cr3+ NIR phosphor. Equivalent smaller Lu3+ was adopted to regulate the structure of Gd3Ga5O12 to further improve the luminescence performance. By regulating the structure the emission spectra shift toward blue region and the intensity is improved. Optimized GdLu2Ga5O12:Cr3+ exhibits anti-thermal quenching behavior and the internal quantum efficiency reaches 73.69 %. Relative sensitivity value of the phosphor GdLu2Ga5O12:Cr3+ reaches 3.353 % K−1 at 423 K based on lifetime mode. LED device is fabricated by combining the phosphor GdLu2Ga5O12:Cr3+ and the commercial red phosphor with blue chip. Electroluminescence spectrum can cover the absorption spectra of the plant dyes well. The lettuce grow faster by adopting this LED device as compensating light source. This work provides an anti-thermal quenching NIR phosphor for multiple applications.

Characterizing the Rapid Hydrogen Disappearance in SN 2022crv: Evidence of a Continuum between Type Ib and IIb Supernova Properties

We present optical and near-infrared (NIR) observations of SN 2022crv, a stripped-envelope supernova in NGC 3054, discovered within 12 hr of explosion by the Distance Less Than 40 Mpc Survey. We suggest that SN 2022crv is a transitional object on the continuum between Type Ib supernovae (SNe Ib) and Type IIb supernovae (SNe IIb). A high-velocity hydrogen feature (∼ −20,000 to −16,000 km s−1) was conspicuous in SN 2022crv at early phases, and then quickly disappeared. We find that a hydrogen envelope of ∼10−3 M ⊙ can reproduce the observed behavior of the hydrogen feature. The lack of early envelope cooling emission implies that SN 2022crv had a compact progenitor with an extremely low amount of hydrogen. A nebular spectral analysis shows that SN 2022crv is consistent with the explosion of a He star with a final mass of ∼4.5–5.6 M ⊙ that evolved from a ∼16 to 22 M ⊙ zero-age main-sequence star in a binary system with ∼1.0–1.7 M ⊙ of oxygen finally synthesized in the core. In order to retain such a small amount of hydrogen, the initial orbital separation of the binary system is likely larger than ∼1000 R ⊙. The NIR spectra of SN 2022crv show a unique absorption feature on the blue side of the He i line at ∼1.005 μm. This is the first time such a feature has been observed in SNe Ib/IIb, and it could be due to Sr II. Further detailed modeling of SN 2022crv can shed light on the progenitor and the origin of the mysterious absorption feature in the NIR.

Luminescence enhancement of near-infrared Cr3+ doped solid solution phosphor via Al3+ substitution for light-emitting diode applications

The luminescence enhancement of near-infrared (NIR) emissive material is critical in emerging applications. In this work, we have prepared an NIR-emitting K2NaSc1-x-yAlxF6:yCr3+ (denoted as KNS1-x-yAxF:yCr) solid solution phosphor via the introduction of Al3+, enhancing luminescence in a high-temperature solid-state reaction. The resultant solid solution phosphor exhibited a broad NIR emission band with a high internal quantum efficiency (IQE = 81.1 %) and an enhanced photoluminescence thermal stability (93 % at 423 K) under 432 nm excitation. When compared with the Al-free sample, the IQE and thermal stability are increased by 45.9 % and 22.4 %, respectively. The optimal Cr3+ and Al3+ doping content has been determined and a composition-optimized KNS0.70A0.25F6:0.05Cr phosphor is demonstrated by fabricating an NIR pc-LED device as a light source for light-emitting diode applications.

M giants with IGRINS

Context. Neutron-capture elements represent an important nucleosynthetic channel in the study of the Galactic chemical evolution of stellar populations. For stellar populations behind significant extinction, such as those in the Galactic centre and along the Galactic plane, abundance analyses based on near-infrared (NIR) spectra are necessary. Previously, spectral lines from the neutron-capture elements, such as copper (Cu), cerium (Ce), neodymium (Nd), and ytterbium (Yb), have been identified in the H band, while yttrium (Y) lines have been identified in the K band. Aims. Due to the scarcity of spectral lines from neutron-capture elements in the NIR, the addition of useful spectral lines from other neutron-capture elements is highly desirable. The aim of this work is to identify and characterise a spectral line suitable for abundance determination from the most commonly used s-process element, namely barium. Methods. We observed the NIR spectra of 37 M giants in the solar neighbourhood at high spectral resolution and with a high signal-to-noise ratio using the IGRINS spectrometer on the GEMINI South telescope. The full H- and K-bands were recorded simultaneously at R = 45 000. Using a manual spectral synthesis method, we determined the fundamental stellar parameters for these stars and derived the barium abundance from the Ba line (6s5d 3D2 → 6s6p 3P2o) at λair = 23 253.56 Å in the K band. Results. We demonstrate that the Ba line in the K band at 2.33 μm (λ23 253.56) is useful for abundance analyses from the spectra of M giants. The line becomes progressively weaker at higher temperatures and is only useful in M giants and the coolest K giants at supersolar metallicities. Conclusions. We can now add Ba to the trends of the heavy elements Cu, Zn, Y, Ce, Nd, and Yb, which can be retrieved from high-resolution H- and K-band spectra. This opens up the study of nucleosynthetic channels, including the s-process and the r-process, in dust-obscured populations. Thus, these elements can be studied for heavily dust-obscured regions of the Galaxy, such as the Galactic centre.

Lipid analysis of human primary dermal fibroblasts and epidermal keratinocytes after near-infrared exposure using mass spectrometry imaging

Photobiomodulation (PBM) therapy is the application of near-infrared (NIR) exposure to injuries or lesions to (among others) improve wound healing, reduce inflammation, and decreases acute and chronic pain. However, the understanding of the molecular mechanism of PBM, more specifically the effects of NIR on skin cells is still lacking behind. Lipids are essential components of cellular membranes that are integral to skin structure and function. This study aims to elucidate the impact of NIR exposure on the skin’s lipidome by investigating the molecular effect of NIR exposure on single skin cells. Primary human dermal fibroblasts (NHDFa) and human epidermal keratinocytes (HEKa) were exposed to NIR (850nm) with a dose of 6.5J/cm2 for 5 consecutive days between 09.00 and 12.00 am. A workflow utilizing matrix-assisted laser desorption/ionization mass spectrometry imaging combined with liquid chromatography tandem mass spectrometry for lipidomics analysis was performed. This study provides evidence that adequate exposure of NIR influences lipid metabolism in NHDFa, whereas no alterations were found in HEKa. This work lays the groundwork in explaining the beneficial properties on both skin-related effects and systemic health benefits as seen in clinical studies.

Proximal High-Index Metamaterials based on a Superlattice of Gold Nanohexagons Targeting the Near-Infrared Band.

Plasmonic nanoparticles can be assembled into a superlattice, to form optical metamaterials, particularly targeting precise control of optical properties such as refractive index (RI). The superlattices exhibit enhanced near-field, given the sufficiently narrow gap between nanoparticles supporting multiple plasmonic resonance modes only realized in proximal environments. Herein, the planar superlattice of plasmonic Au nanohexagons (AuNHs) with precisely controlled geometries such as size, shape, and edge-gaps is reported. The proximal AuNHs superlattice realized over a large area with selective edge-to-edge assembly exhibited the highest-ever-recorded RI values in the near-infrared (NIR) band, surpassing the upper limit of the RI of the natural intrinsic materials (up to 10.04 at λ = 1.5µm). The exceptionally enhanced RI is derived from intensified in-plane surface plasmon coupling across the superlattices. Precise control of the edge-gap of neighboring AuNHs systematically tuned the RI as confirmed by numerical analysis based on the plasmonic percolation model. Furthermore, a 1D photonic crystal, composed of alternating layers of AuNHs superlattices and low-index polymers, is constructed to enhance the selectivity of the reflectivity operating in the NIR band. It is expected that the proximal AuNHs superlattices can be used as new optical metamaterials that can be extended to the NIR range.

Optical resonant cavities carving pathways in tunable wavelength sensitive visible-NIR organic photodetectors

Enhancing the photodetection capabilities of organic photodetectors (OPDs) is crucial for advancing applications in medical monitoring, optical communications, image sensing, and robotics, where a strong, focused peak response at a specific designed wavelength is essential for improving sensitivity, wavelength selectivity, and resolution in imaging systems. By controlled integration of ZnO layers within PBDBT:BTP-4F-based OPDs to form a Fabry-Pérot optical cavity, we developed a cost-effective approach to fabricating highly sensitive OPDs by utilizing PBDBT:BTP-4F organic bulk heterojunctions, and extended its detection wavelengths into the near-infrared (NIR) range. Our design integrates a single silver (Ag) layer that significantly enhances peak detection at a wavelength of 830 ​nm, resulting in a remarkably narrow full-width at half maximum (FWHM) wavelength of 30 ​nm and yielding a photoresponse ten times greater than that of non-resonant devices. Furthermore, by varying the thickness of the ZnO layer from 77 ​nm to 620 ​nm, we achieve high spectral tunability, allowing fine adjustments of the resonant peak across a spectrum ranging from ultraviolet (UV) and visible to NIR wavelengths. This sensitive photodetector is also well-suited for applications in photoplethysmography (PPG), effectively detecting pulse signals in the NIR spectrum which has significant potential in medical diagnostics. This work advances the integration of cost-effective, wavelength-selective spectroscopic visible-NIR OPDs, paving the way for the next generation of sensitive photodetectors.

Finely tuned energy gaps in host-guest complexes: Insights from belt[14]pyridine and fullerene-based nano-Saturn systems

Over the past few decades, doping, physisorption and chemisorption remained some of the commonly utilized methods to modify the energy gaps and electronic properties of materials. Yet, achieving precise control over tuning the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels within these systems persisted as a remarkable challenge. Therefore, there is a growing need for systems that facilitate exact adjustments of energy gaps and HOMO/LUMO levels. Here, in this research work, the nano-Saturn host-guest complex systems are designed based on belt[14]pyridine as a host and fullerene nanocages (C20, C32, C34 and C36) as guests. The greater thermodynamic stability of the complexes is revealed by the higher values of interaction energies (Eint) for these complexes, ranging from −45.50 to −56.81 kcal/mol. The frontier molecular orbital (FMO) analysis revealed the contribution of HOMO of fullerenes and LUMO of belt[14]pyridine towards the HOMO and LUMO of the designed complexes, respectively. The energy gaps of the complexes also decrease compared to the constituents, with the least Egap of 0.52 eV observed for C20@N-belt. Moreover, the charge transfer from the host towards the guests is predicted and confirmed via natural bond orbital (NBO) and electron density difference (EDD) analyses. The non-covalent interaction index (NCI) and quantum theory of atoms in molecules (QTAIM) analyses determine the nature and strength of interactions in the host-guest complexes. Moreover, it is noticed through the UV–vis analysis that the bare fullerenes show the maximum absorption in ultraviolet (UV) region, but after complexation, maximum absorption is observed in visible and near infrared (NIR) regions, with highest λmax of 927 nm for C36@N-belt. These findings highlight the successful development of nano-Saturn host-guest complexes with precise control over HOMO-LUMO levels and energy gaps. This work aims to address the challenges in fine-tuning the electronic properties and demonstrates potential applications in optoelectronics, photovoltaics, and NIR-based sensors. Moreover, the ability to tune the electronic properties can guide future material design strategies for advanced energy storage and photonic devices.