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A special issue of Nanomaterials (ISSN 2079-4991). This special issue belongs to the section "Nanophotonics Materials and Devices".

Deadline for manuscript submissions: closed (15 November 2021) | Viewed by 38241

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Special Issue Editors

Dr. Barbara Fazio

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Guest Editor

Consiglio Nazionale delle Ricerche (CNR), Istituto per i Processi Chimico-Fisici (IPCF), Messina, Italy
Interests: photonics; plasmonics; Raman; SERS; nanomaterials

Dr. Cristiano D’Andrea

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Guest Editor

Consiglio Nazionale delle Ricerche (CNR), Istituto di Fisica Applicata “Nello Carrara” (IFAC), Sesto Fiorentino, Florence, Italy
Interests: Raman; SERS; TERS; Biomarkers, Nanomaterials, Sensors

Dr. Paolo Matteini

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Guest Editor

Consiglio Nazionale delle Ricerche (CNR), Istituto di Fisica Applicata “Nello Carrara” (IFAC), Sesto Fiorentino, Florence, Italy
Interests: biophotonics; nanohybrid materials; optical sensors; plasmon-enhanced spectroscopies; theranostics

Special Issue Information

Dear Colleagues,

Light–matter interactions at the nanoscale can lead to a plethora of optical effects, thus paving the way for a wide range of applications, from harvesting and new light sources to imaging and sensing. For this reason, interest in nanophotonics has significantly increased in modern times. On the other hand, the fabrication of nanostructures that can meet the demand for a suitable light–matter coupling, such as precise shape, size, and geometry, both ordered and disordered, is a research field in constant expansion. Moreover, metallic nanomaterials and their plasmonic properties are known to promote an increase of light–matter interactions. These occurrences have a large impact in enhanced spectroscopies, dramatically increasing their sensitivity, with important outcomes in the diagnostic and medical fields. At the same time, the modelling, synthesis, and characterization of nanomaterials are crucial to approach and deepen fundamental physics at the nanoscale.

This Special Issue of Nanomaterials concentrates on a wide range of topics, including advances in the preparation and characterization of photonics and plasmonics materials and their use in modern devices based on light–matter coupling at the nanoscale. Therefore, it is a great pleasure for us to invite you to contribute to this Special Issue, which welcomes experimental and theoretical original research papers, communications, and reviews articles.

Dr. Barbara Fazio
Dr. Cristiano D’Andrea
Dr. Paolo Matteini
Guest Editors

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Keywords

Nanostructures: synthesis and characterizations
Plasmonics materials
Photonics materials
Nanomaterials for optical devices
Nanomaterials for sensing
Enhanced spectroscopies, SERS, TERS, and SEIRA/SEIRS
Dielectric, hybrid, and carbon-based nanostructures
Modeling
Light–matter coupling
Mie scatterers
Light-induced theranostics application of nanoparticles

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Published Papers (11 papers)

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Research

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18 pages, 3733 KiB

Open AccessFeature PaperArticle

Comparing Commercial Metal-Coated AFM Tips and Home-Made Bulk Gold Tips for Tip-Enhanced Raman Spectroscopy of Polymer Functionalized Multiwalled Carbon Nanotubes

by Antonino Foti, Suriya Venkatesan, Bérengère Lebental, Gaël Zucchi and Razvigor Ossikovski

Nanomaterials 2022, 12(3), 451; https://doi.org/10.3390/nano12030451 - 28 Jan 2022

Cited by 6 | Viewed by 3219

Abstract

Tip-enhanced Raman spectroscopy (TERS) combines the high specificity and sensitivity of plasmon-enhanced Raman spectroscopy with the high spatial resolution of scanning probe microscopy. TERS has gained a lot of attention from many nanoscience fields, since this technique can provide chemical and structural information of surfaces and interfaces with nanometric spatial resolution. Multiwalled carbon nanotubes (MWCNTs) are very versatile nanostructures that can be dispersed in organic solvents or polymeric matrices, giving rise to new nanocomposite materials, showing improved mechanical, electrical and thermal properties. Moreover, MWCNTs can be easily functionalized with polymers in order to be employed as specific chemical sensors. In this context, TERS is strategic, since it can provide useful information on the cooperation of the two components at the nanoscale for the optimization of the macroscopic properties of the hybrid material. Nevertheless, efficient TERS characterization relies on the geometrical features and material composition of the plasmonic tip used. In this work, after comparing the TERS performance of commercial Ag coated nanotips and home-made bulk Au tips on bare MWCNTs, we show how TERS can be exploited for characterizing MWCNTs mixed with conjugated fluorene copolymers, thus contributing to the understanding of the polymer/CNT interaction process at the local scale. Full article

(This article belongs to the Special Issue Nanostructured Materials for Photonics and Plasmonics)

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16 pages, 1795 KiB

Open AccessArticle

Self-Assembled Metal Nanohole Arrays with Tunable Plasmonic Properties for SERS Single-Molecule Detection

by Daniela Lospinoso, Adriano Colombelli, Mauro Lomascolo, Roberto Rella and Maria Grazia Manera

Nanomaterials 2022, 12(3), 380; https://doi.org/10.3390/nano12030380 - 24 Jan 2022

Cited by 9 | Viewed by 3808

Abstract

Arrays of metal nano-holes have proved to be among of the most promising structures for applications in the field of nano-photonics and optoelectronics. Supporting both localized and propagating surface plasmons resonances, they are characterized by very high versatility thanks to the tunability of these modes, by means of the change of their periodicity, the size of the holes and metal composition. The interaction between different optical features can be exploited to modulate electromagnetic field distribution leading various hot-spots excitations on the metal surfaces. In this work, long range ordered arrays of nano-holes in thin gold films, with different geometrical characteristics, were fabricated by a modified nano-sphere lithography protocol, which allows precise control on holes’ dimensions together with the preservation of the order and of the pristine periodicity of the array. An in-depth analysis of the correlation between surface plasmon modes interference and its effect on electromagnetic field distribution is proposed, both by numerical simulations and experimentally. Finally, metal nano-holes arrays are exploited for surface enhanced Raman experiments, evaluating and comparing their performances by the estimation of the enhancement factor. Values close to the single molecule detection are obtained for most of the samples, proving their potentialities in surface enhanced spectroscopy applications. Full article

(This article belongs to the Special Issue Nanostructured Materials for Photonics and Plasmonics)

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14 pages, 5344 KiB

Open AccessFeature PaperEditor’s ChoiceArticle

Direct Plasmonic Solar Cell Efficiency Dependence on Spiro-OMeTAD Li-TFSI Content

by Xinjian Geng, Mohamed Abdellah, Robert Bericat Vadell, Matilda Folkenant, Tomas Edvinsson and Jacinto Sá

Nanomaterials 2021, 11(12), 3329; https://doi.org/10.3390/nano11123329 - 8 Dec 2021

Cited by 7 | Viewed by 3569

Abstract

The proliferation of the internet of things (IoT) and other low-power devices demands the development of energy harvesting solutions to alleviate IoT hardware dependence on single-use batteries, making their deployment more sustainable. The propagation of energy harvesting solutions is strongly associated with technical performance, cost and aesthetics, with the latter often being the driver of adoption. The general abundance of light in the vicinity of IoT devices under their main operation window enables the use of indoor and outdoor photovoltaics as energy harvesters. From those, highly transparent solar cells allow an increased possibility to place a sustainable power source close to the sensors without significant visual appearance. Herein, we report the effect of hole transport layer Li-TFSI dopant content on semi-transparent, direct plasmonic solar cells (DPSC) with a transparency of more than 80% in the 450–800 nm region. The findings revealed that the amount of oxidized spiro-OMeTAD (spiro⁺TFSI⁻) significantly modulates the transparency, effective conductance and conditions of device performance, with an optimal performance reached at around 33% relative concentration of Li-TFSI concerning spiro-OMeTAD. The Li-TFSI content did not affect the immediate charge extraction, as revealed by an analysis of electron–phonon lifetime. Hot electrons and holes were injected into the respective layers within 150 fs, suggesting simultaneous injection, as supported by the absence of hysteresis in the I–V curves. The spiro-OMeTAD layer reduces the Au nanoparticles’ reflection/backscattering, which improves the overall cell transparency. The results show that the system can be made highly transparent by precise tuning of the doping level of the spiro-OMeTAD layer with retained plasmonics, large optical cross-sections and the ultrathin nature of the devices. Full article

(This article belongs to the Special Issue Nanostructured Materials for Photonics and Plasmonics)

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12 pages, 1223 KiB

Open AccessArticle

Cost-Effective Fabrication of Fractal Silicon Nanowire Arrays

by Antonio Alessio Leonardi, Maria José Lo Faro, Maria Miritello, Paolo Musumeci, Francesco Priolo, Barbara Fazio and Alessia Irrera

Nanomaterials 2021, 11(8), 1972; https://doi.org/10.3390/nano11081972 - 31 Jul 2021

Cited by 4 | Viewed by 1980

Abstract

Silicon nanowires (Si NWs) emerged in several application fields as a strategic element to surpass the bulk limits with a flat compatible architecture. The approaches used for the Si NW realization have a crucial impact on their final performances and their final cost. This makes the research on a novel and flexible approach for Si NW fabrication a crucial point for Si NW-based devices. In this work, the novelty is the study of the flexibility of thin film metal-assisted chemical etching (MACE) for the fabrication of Si NWs with the possibility of realizing different doped Si NWs, and even a longitudinal heterojunction p-n inside the same single wire. This point has never been reported by using thin metal film MACE. In particular, we will show how this approach permits one to obtain a high density of vertically aligned Si NWs with the same doping of the substrate and without any particular constraint on doping type and level. Fractal arrays of Si NWs can be fabricated without any type of mask thanks to the self-assembly of gold at percolative conditions. This Si NW fractal array can be used as a substrate to realize controllable artificial fractals, integrating other interesting elements with a cost-effective microelectronics compatible approach. Full article

(This article belongs to the Special Issue Nanostructured Materials for Photonics and Plasmonics)

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12 pages, 3716 KiB

Open AccessFeature PaperArticle

Cost Effective Silver Nanowire-Decorated Graphene Paper for Drop-On SERS Biodetection

by Chiara Amicucci, Cristiano D’Andrea, Marella de Angelis, Martina Banchelli, Roberto Pini and Paolo Matteini

Nanomaterials 2021, 11(6), 1495; https://doi.org/10.3390/nano11061495 - 4 Jun 2021

Cited by 12 | Viewed by 3064

Abstract

The use of SERS for real-world bioanalytical applications represents a concrete opportunity, which, however, is being largely delayed by the inadequacy of existing substrates used to collect SERS spectra. In particular, the main bottleneck is their poor usability, as in the case of unsupported noble metal colloidal nanoparticles or because of the need for complex or highly specialized fabrication procedures, especially in view of a large-scale commercial diffusion. In this work, we introduce a graphene paper-supported plasmonic substrate for biodetection as obtained by a simple and rapid aerosol deposition patterning of silver nanowires. This substrate is compatible with the analysis of small (2 μL) analyte drops, providing stable SERS signals at sub-millimolar concentration and a detection limit down to the nanogram level in the case of hemoglobin. The presence of a graphene underlayer assures an even surface distribution of SERS hotspots with improved stability of the SERS signal, the collection of well-resolved and intense SERS spectra, and an ultra-flat and photostable SERS background in comparison with other popular disposable supports. Full article

(This article belongs to the Special Issue Nanostructured Materials for Photonics and Plasmonics)

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19 pages, 5665 KiB

Open AccessArticle

Dendritic Forest-Like Ag Nanostructures Prepared Using Fluoride-Assisted Galvanic Replacement Reaction for SERS Applications

by Ming-Hua Shiao, Tsunghsueh Wu, Hung Ji Huang, Ching-Yi Peng, Yung-Sheng Lin, Ting-Yu Lai and Yang-Wei Lin

Nanomaterials 2021, 11(6), 1359; https://doi.org/10.3390/nano11061359 - 21 May 2021

Cited by 13 | Viewed by 2478

Abstract

Dendritic forest-like Ag nanostructures were deposited on a silicon wafer through fluoride-assisted galvanic replacement reaction (FAGRR) in aqueous AgNO₃ and buffered oxide etchant. The prepared nanostructures were characterized using scanning electron microscopy, energy-dispersive X-ray spectroscopy, inductively coupled plasma–optical emission spectroscopy, a surface profiler (alpha step), and X-ray diffraction. Additionally, the dendritic forest-like Ag nanostructures were characterized using surface-enhanced Raman scattering (SERS) when a 4-mercaptobenzoic acid (4-MBA) monolayer was adsorbed on the Ag surface. The Ag nanostructures exhibited intense SERS signal from 4-MBA because of their rough surface, and this intense signal led to an intense local electromagnetic field upon electromagnetic excitation. The enhancement factor for 4-MBA molecules adsorbed on the Ag nanostructures was calculated to be 9.18 × 10⁸. Furthermore, common Raman reporters such as rhodamine 6G, 4-aminothiolphenol, 5,5′-dithiobis-2-nitrobenzoic acid, and carboxyfluorescein (FAM) were characterized on these dendritic forest-like Ag nanostructures, leading to the development of an ultrasensitive SERS-based DNA sensor with a limit of detection of 33.5 nM of 15-mer oligonucleotide. Full article

(This article belongs to the Special Issue Nanostructured Materials for Photonics and Plasmonics)

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13 pages, 2209 KiB

Open AccessArticle

Glucose Detection of 4-Mercaptophenylboronic Acid-Immobilized Gold-Silver Core-Shell Assembled Silica Nanostructure by Surface Enhanced Raman Scattering

by Xuan-Hung Pham, Bomi Seong, Eunil Hahm, Kim-Hung Huynh, Yoon-Hee Kim, Jaehi Kim, Sang Hun Lee and Bong-Hyun Jun

Nanomaterials 2021, 11(4), 948; https://doi.org/10.3390/nano11040948 - 8 Apr 2021

Cited by 18 | Viewed by 4572

Abstract

The importance of glucose in many biological processes continues to garner increasing research interest in the design and development of efficient biotechnology for the sensitive and selective monitoring of glucose. Here we report on a surface-enhanced Raman scattering (SERS) detection of 4-mercaptophenyl boronic acid (4-MPBA)-immobilized gold-silver core-shell assembled silica nanostructure (SiO₂@Au@Ag@4-MPBA) for quantitative, selective detection of glucose in physiologically relevant concentration. This work confirmed that 4-MPBA converted to 4-mercaptophenol (4-MPhOH) in the presence of H₂O₂. In addition, a calibration curve for H₂O₂ detection of 0.3 µg/mL was successfully detected in the range of 1.0 to 1000 µg/mL. Moreover, the SiO₂@Au@Ag@4-MPBA for glucose detection was developed in the presence of glucose oxidase (GOx) at the optimized condition of 100 µg/mL GOx with 1-h incubation time using 20 µg/mL SiO₂@Au@Ag@4-MPBA and measuring Raman signal at 67 µg/mL SiO₂@Au@Ag. At the optimized condition, the calibration curve in the range of 0.5 to 8.0 mM was successfully developed with an LOD of 0.15 mM. Based on those strategies, the SERS detection of glucose can be achieved in the physiologically relevant concentration range and opened a great promise to develop a SERS-based biosensor for a variety of biomedicine applications. Full article

(This article belongs to the Special Issue Nanostructured Materials for Photonics and Plasmonics)

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15 pages, 3072 KiB

Open AccessArticle

Doubly-Resonant Photonic Crystal Cavities for Efficient Second-Harmonic Generation in III–V Semiconductors

by Simone Zanotti, Momchil Minkov, Shanhui Fan, Lucio C. Andreani and Dario Gerace

Nanomaterials 2021, 11(3), 605; https://doi.org/10.3390/nano11030605 - 28 Feb 2021

Cited by 10 | Viewed by 3605

Abstract

Second-order nonlinear effects, such as second-harmonic generation, can be strongly enhanced in nanofabricated photonic materials when both fundamental and harmonic frequencies are spatially and temporally confined. Practically designing low-volume and doubly-resonant nanoresonators in conventional semiconductor compounds is challenging owing to their intrinsic refractive index dispersion. In this work we review a recently developed strategy to design doubly-resonant nanocavities with low mode volume and large quality factor via localized defects in a photonic crystal structure. We built on this approach by applying an evolutionary optimization algorithm in connection with Maxwell equations solvers; the proposed design recipe can be applied to any material platform. We explicitly calculated the second-harmonic generation efficiency for doubly-resonant photonic crystal cavity designs in typical III–V semiconductor materials, such as GaN and AlGaAs, while targeting a fundamental harmonic at telecom wavelengths and fully accounting for the tensor nature of the respective nonlinear susceptibilities. These results may stimulate the realization of small footprint photonic nanostructures in leading semiconductor material platforms to achieve unprecedented nonlinear efficiencies. Full article

(This article belongs to the Special Issue Nanostructured Materials for Photonics and Plasmonics)

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14 pages, 4371 KiB

Open AccessArticle

An Application of Multivariate Data Analysis to Photoacoustic Imaging for the Spectral Unmixing of Gold Nanorods in Biological Tissues

by Mirko Maturi, Paolo Armanetti, Luca Menichetti and Mauro Comes Franchini

Nanomaterials 2021, 11(1), 142; https://doi.org/10.3390/nano11010142 - 8 Jan 2021

Cited by 3 | Viewed by 2065

Abstract

Gold nanorods (GNRs) showed to be a suitable contrast agent in photoacoustics (PA), and are able to provide a tunable absorption contrast against background tissue, while a detectable PA signal can be generated from highly localized and targeted areas. A crucial issue for these imaging techniques is represented by the discrimination between exogenous and endogenous contrast and the assessment of the real PA signal magnitude. The application of image resolution/unmixing methods was implemented and optimized to recover the relative magnitude spectra and distribution maps of image constituents of the biological sample based on multivariate analysis (multivariate curve resolution—alternating least squares, MCR-ALS) in the presence of GNRs with tunable absorption properties. The proposed data analysis methodology is demonstrated on real PA images from experimental animal models and ex-vivo preparations. Full article

(This article belongs to the Special Issue Nanostructured Materials for Photonics and Plasmonics)

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10 pages, 1950 KiB

Open AccessArticle

ZnO Nanowires on Single-Crystalline Aluminum Film Coupled with an Insulating WO₃ Interlayer Manifesting Low Threshold SPP Laser Operation

by Aanchal Agarwal, Wei-Yang Tien, Yu-Sheng Huang, Ragini Mishra, Chang-Wei Cheng, Shangjr Gwo, Ming-Yen Lu and Lih-Juann Chen

Nanomaterials 2020, 10(9), 1680; https://doi.org/10.3390/nano10091680 - 27 Aug 2020

Cited by 6 | Viewed by 3036

Abstract

ZnO nanowire-based surface plasmon polariton (SPP) nanolasers with metal–insulator–semiconductor hierarchical nanostructures have emerged as potential candidates for integrated photonic applications. In the present study, we demonstrated an SPP nanolaser consisting of ZnO nanowires coupled with a single-crystalline aluminum (Al) film and a WO₃ dielectric interlayer. High-quality ZnO nanowires were prepared using a vapor phase transport and condensation deposition process via catalyzed growth. Subsequently, prepared ZnO nanowires were transferred onto a single-crystalline Al film grown by molecular beam epitaxy (MBE). Meanwhile, a WO₃ dielectric interlayer was deposited between the ZnO nanowires and Al film, via e-beam technique, to prevent the optical loss from dominating the metallic region. The metal–oxide–semiconductor (MOS) structured SPP laser, with an optimal WO₃ insulating layer thickness of 3.6 nm, demonstrated an ultra-low threshold laser operation (lasing threshold of 0.79 MW cm⁻²). This threshold value was nearly eight times lower than that previously reported in similar ZnO/Al₂O₃/Al plasmonic lasers, which were ≈2.4 and ≈3 times suppressed compared to the SPP laser, with WO₃ insulating layer thicknesses of 5 nm and 8 nm, respectively. Such suppression of the lasing threshold is attributed to the WO₃ insulating layer, which mediated the strong confinement of the optical field in the subwavelength regime. Full article

(This article belongs to the Special Issue Nanostructured Materials for Photonics and Plasmonics)

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Review

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16 pages, 2158 KiB

Open AccessFeature PaperReview

Surface-Enhanced Raman Scattering-Based Lateral-Flow Immunoassay

by Boris Khlebtsov and Nikolai Khlebtsov

Nanomaterials 2020, 10(11), 2228; https://doi.org/10.3390/nano10112228 - 10 Nov 2020

Cited by 56 | Viewed by 5398

Abstract

Lateral flow immunoassays (LFIAs) have been developed and used in a wide range of applications, in point-of-care disease diagnoses, environmental safety, and food control. However, in its classical version, it has low sensitivity and can only perform semiquantitative detection, based on colorimetric signals. Over the past decade, surface-enhanced Raman scattering (SERS) tags have been developed in order to decrease the detection limit and enable the quantitative analysis of analytes. Of note, these tags needed new readout systems and signal processing algorithms, while the LFIA design remained unchanged. This review highlights SERS strategies of signal enhancement for LFIAs. The types of labels used, the possible gain in sensitivity from their use, methods of reading and processing the signal, and the prospects for use are discussed. Full article

(This article belongs to the Special Issue Nanostructured Materials for Photonics and Plasmonics)

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