Ultrasensitive nanosensors based on localized surface plasmon resonances:From theory to applications

The subwavelength confinement feature of localized surface plasmon resonance（LSPR） allows plasmonic nanostructures to be functionalized as powerful platforms for detecting various molecular analytes as well as weak processes with nanoscale spatial resolution. One of the main goals of this field of research is to lower the absolute limit-of-detection（LOD）of LSPR-based sensors. This involves the improvement of（i） the figure-of-merit associated with structural parameters such as the size, shape and interparticle arrangement and,（ii） the spectral resolution. The latter involves advanced target identification and noise reduction techniques. By highlighting the strategies for improving the LOD, this review introduces the fundamental principles and recent progress of LSPR sensing based on different schemes including 1） refractometric sensing realized by observing target-induced refractive index changes, 2） plasmon rulers based on target-induced relative displacement of coupled plasmonic structures, 3） other relevant LSPR-based sensing schemes including chiral plasmonics,nanoparticle growth, and optomechanics. The ultimate LOD and the future trends of these LSPR-based sensing are also discussed.

Tunable localized surface plasmon resonances in MoO_(3-x)-TiO_(2) nanocomposites with enhanced catalytic activity for CO_(2) photoreduction under visible light

The photocatalytic reduction of CO2 with H2O to fuels and chemicals using solar energy is one of the most attractive but highly difficult routes.Thus far,only a very limited number of photocatalysts has been reported to be capable of catalyzing the photocatalytic reduction of CO2 under visible light.The utilization of the localized surface plasmon resonance(LSPR)phenomenon is an attractive strategy for developing visible-light photocatalysts.Herein,we have succeeded in synthesizing plasmonic MoO3?x-TiO2 nanocomposites with tunable LSPR by a simple solvothermal method.The well-structured nanocomposite containing two-dimensional(2D)molybdenum oxide(MoO3?x)nanosheets and one-dimensional(1D)titanium oxide nanotubes(TiO2-NT)showed LSPR absorption band in the visible-light region,and the incorporation of TiO2-NT significantly enhanced the LSPR absorption band.The MoO3?x-TiO2-NT nanocomposite is promising for application in the photocatalytic reduction of CO2 with H2O under visible light irradiation.

Manipulated localized surface plasmon resonances in silver nanoshells coated with a spherical anisotropic layer

The influences of the anisotropy of the outer spherically anisotropic （SA） layer on the far-field spectra and near- field enhancements of the silver nanoshells are investigated by using a modified Mie scattering theory. It is found that with the increase of the anisotropic value of the SA layer, the dipole resonance wavelength of the silver nanoshell first increases and then decreases, while the local field factor （LFF） reduces. With the decrease of SA layer thickness, the dipole wavelength of the silver nanoshell shows a distinct blue-shift. When the SA layer becomes very thin, the modulations of the anisotropy of the SA layer on the plasmon resonance energy and the near-field enhancement are weakened. We further find that the smaller anisotropic value of the SA layer is helpful for obtaining the larger near-field enhancement in the Ag nanoshell. The geometric average of the dielectric components of the SA layer has a stronger effect on the plasmon resonance energy of the silver nanoshell than on the near-field enhancement.

Polydopamine-Assisted Fabrication of Fiber-Optic Localized Surface Plasmon Resonance Sensor Based on Gold Nanoparticles

A fast and facile method of fabricating fiber-optic localized surface plasmon resonance sensors baseff on spherical gold nanoparticles was introduced in this study. The gold nanoparticles with an average diameter of 55 nm were synthesized via the Turkevich method and were then immobilized onto the surface of an uncladded sensor probe using a polydopamine layer. To obtain a sensor probe with high sensitivity to changes in the refractive index, a set of key optimization parameters, including the sensing length, coating time of the potydopamine layer, and coating time of the gold nanoparticles, were investigated. The sensitivity of the optimized sensor probe was 522.80 nm per refractive index unit, and the probe showed distinctive wavelength shifts when the refractive index was changed from 1.328 6 to 1.398 7. When stored in deionized water at 4 ℃, the sensor probe proved to be stable over a period of two weeks. The sensor also exhibited advantages, such as low cost, fast fabrication, and simple optical setup, which indicated its potential application in remote sensing and real-time detection.

Engineering a Localized Surface Plasmon Resonance Platform for Molecular Biosensing

In this work, we introduce a new perspective on the development of Localized Surface Plasmon Resonance (LSPR) optical biosensors. Computational simulations, focused on the assessment of the LSPR spectrum and spatial distribution of the electromagnetic field enhancement near a metallic nanoparticle, elucidated the behavior of crucial parameters, as figure of merit, bulk and molecular sensitivity, which governs a LSPR sensor performance. Gold and silver nanospheres were explored as starting point to assess plasmonic optical characteristics of the nanostructured sensor platform. Here, for the first time in the literature, Campbell’s model was evaluated exploiting a NP size-dependence approach. The theoretical analyses indicate a nonlinear behavior of the bulk and molecular sensitivity as function of the NP size. Substantial LSPR peak shifts due to the adsorption of molecules layer on a NP surface were observed for nanoparticles with ~5 nm and ~40 nm radius. Moreover, on molecular sensing, LSPR peak shift is also determined by the thickness of adsorbed molecular shell layers. We observed that for 40 nm radius gold and silver nanospheres, significant LSPR peak shift could be induced by small (few nm) thickness change of the adsorbate shell layer. Moreover, this work provides insights on the LSPR behavior due to adsorption of molecular layer on a NP surface, establishing a new paradigm on engineering LSPR biosensor. Furthermore, the proposed approach can be extended to engineer an efficiently use of different nanostructures on molecular sensing.

Effects of thickness & shape on localized surface plasmon resonance of sexfoil nanoparticles

Localized surface plasmon （LSPR） resonance and sensing properties of a novel nanostructure （sexfoil nanoparticle） are studied using the finite-difference time-domain method. For the sandwich sexfoil nanoparticle, the calculated extinction spectrum shows that with the thickness of the dielectric layer increasing, long-wavelength peaks blueshift, while short- wavelength peaks redshift. Strong near-field coupling of the upper and lower metal layers leads to electric and magnetic field resonances; as the thickness increases, the electric field resonance gradually increases, while the magnetic field resonance decreases. The obtained refractive index sensitivity and figure of merit are 332 nm/RIU and 3.91 RIU^-1, respectively. In order to obtain better sensing ability, we further research the LSPR character of monolayer Ag sexfoil nanoparticle. After a series of trials to optimize the thickness and shape, the refractive index sensitivity approximates 668 nm/RIU, and the greatest figure of merit value comes to 14.8 RIU^-1.

Tunable and stable localized surface plasmon resonance in SrMoO_(4) for enhanced visible light driven nitrogen reduction

Photocatalytic nitrogen reduction for the green synthesis of ammonia at ambient conditions has been slowed by the narrow light harvesting range,low activity and high charge recombination of photocatalysts.Plasmonic semiconducting nanomaterials are becoming the promising candidates for nitrogen photofixation because of the broad absorption spectrum,rich defects and hot carriers.In the present study,plasmonic SrMoO_(4) is developed by regulating the concentration of oxygen vacancies that are accompanied in the reduction process from Mo^(6+) to Mo^(5+).The stable and tunable localized surface plasmon resonance(LSPR)absorption in visible and near infrared light range makes the wide bandgap SrMoO_(4) utilize the solar energy more efficiently.Energetic electrons from both the intrinsic band excitation and the LSPR excitation enable the reduction of dinitrogen molecules thermodynamically in ultrapure water to ammonia.This work provides a unique clue to design efficient photocatalysts for nitrogen fixation.

Toward transparent projection display:recent progress in frequency‐selective scattering of RGB light based on metallic nanoparticle’s localized surface plasmon resonance

A transparent display simultaneously enables visualization of the images displayed on it as well as the view behind it,and therefore can be applied to,for instance,augmented reality(AR),virtual reality(VR),and head up display(HUD).Many solutions have been proposed for this purpose.Recently,the idea of frequency-selective scattering of red,green and blue light while transmitting visible light of other colours to achieve transparent projection display has been proposed,by taking advantage of metallic nanoparticle’s localized surface plasmon resonance(LSPR).In this article,a review of the recent progress of frequency-selective scattering of red,green and blue light that are based on metallic nanoparticle’s LSPR is presented.A discussion of method for choosing appropriate metal(s)is first given,followed by the definition of a figure of merit used to quantify the performance of a designed nanoparticle structure.Selective scattering of various nanostructures,including sphere-shaped nanoparticles,ellipsoidal nanoparticles,super-sphere core-shell nanoparticles,metallic nanocubes,and metallic nanoparticles combined with gain materials,are discussed in detail.Each nanostructure has its own advantages and disadvantages,but the combination of the metallic nanoparticle with gain materials is a more promising way since it has the potential to generate ultra-sharp scattering peaks(i.e.,high frequency-selectivity).

Protein Based Localized Surface Plasmon Resonance Gas Sensing

We apply the localized surface plasrnon resonance （LSPR） of gold nanoparticles （GNPs） covalently coupled with cytochrorne c （cyt c） to create a nanobiosensor for detecting hydrogen sulfide （H2S） in the range of 15 lOOppb. Monolayer formation of GNPs on glass surface functionalized with 3-aminopropyltrirnethoxysilane （APTMS） is performed for fabricating a chip-based format of the optical transducer. By chemical introduction of short-chain thiol derivatives on cyt c protein shell via its lysine residues, a very fast self-assembled rnonolayer （SAM） of cyt c is formed on the GNPs. Significant shifts in the LSPR peak （△λLSPR） are observed by reacting H2S with cyt c. Results show a linear relationship between △λLSPR and H2S concentration. Furthermore, shifts in the LSPR peak are reversible and the peak positions return to their pre-exposure values once the H2S is removed. The experirnental results strongly indicate that the protein based LSPR chip can be successfully used as a simple, fast, sensitive and quantitative sensor for H2S detection.

Photocurrent improvement of an ultra-thin silicon solar cell using the localized surface plasmonic effect of clustering nanoparticles

The cluster-shaped plasmonic nanostructures are used to manage the incident light inside an ultra-thin silicon solar cell.Here we simulate spherical,conical,pyramidal,and cylindrical nanoparticles in a form of a cluster at the rear side of a thin silicon cell,using the finite difference time domain(FDTD)method.By calculating the optical absorption and hence the photocurrent,it is shown that the clustering of nanoparticles significantly improves them.The photocurrent enhancement is the result of the plasmonic effects of clustering the nanoparticles.For comparison,first a cell with a single nanoparticle at the rear side is evaluated.Then four smaller nanoparticles are put around it to make a cluster.The photocurrents of 20.478 mA/cm2,23.186 mA/cm2,21.427 mA/cm2,and 21.243 mA/cm2 are obtained for the cells using clustering conical,spherical,pyramidal,cylindrical NPs at the backside,respectively.These values are 13.987 mA/cm2,16.901 mA/cm2,16.507 mA/cm2,17.926 mA/cm2 for the cell with one conical,spherical,pyramidal,cylindrical NPs at the backside,respectively.Therefore,clustering can significantly improve the photocurrents.Finally,the distribution of the electric field and the generation rate for the proposed structures are calculated.

Photothermal properties of Cu@polycarbonate composites with strong localized surface plasmon resonances

Copper is relatively low cost and highly abundant compared with the well-studied noble metals such as gold and silver.However,the poor plasmonic and high susceptibility towards oxidation limit the study of its optical properties and applications as well.Herein,copper nanoparticles@polycarbonate(Cu@PC)composites were prepared by using a facile one-step solvothermal method.The Cu@PC composites have strong localized surface plasmon resonances(LSPR)due to that the PC shell can induce the particles to form many-particles system with different particle numbers,which not only lead to overlap and hybridize of the LSPR modes,but also shift the LSPR away from the interband transitions,and the PC layer also prevents the oxidation of Cu nanoparticles.The photothermal conversion efficiency of Cu@PC composites reaches 41.1%under 808 nm continuous wave(CW)laser irradiation which is higher than previously reported Cu nanomaterials that have been reported.Meanwhile,the composites also have high photothermal stability.Moreover,interfacial evaporator is prepared by assembling the Cu@PC composites on scouring sponge as light absorption layer which has>92.8%absorption in entire solar spectrum range.Its seawater evaporation rate is 3.177 kg·m^(-2)·h^(-1)with a E_(evaporator)/E_(water)of 5.2.The high evaporation rate interfacial evaporator with low cost,simple,and scalable approach shows great application value in the field of photothermal evaporation.

Review of Fiber-Optic Localized Surface Plasmon Resonance Sensors:Geometries,Fabrication Technologies,and Bio-Applications

Localized surface plasmon resonance(LSPR)biosensors,which enable nanoscale confinement and manipulation of light,offer the enhanced sensitivity and electromagnetic energy localization.The integration of LSPR with the fiber-optic technology has led to the development of compact and versatile sensors for miniaturization and remote sensing.This comprehensive review explores various sensor configurations,fiber types,and geometric shapes,highlighting their benefits in terms of sensitivity,integration,and performance improvement.Fabrication techniques such as focused non-chemical bonding strategies and self-assembly of nanoparticles are discussed,providing control over nanostructure morphology and enhancing sensor performance.Bio-applications of fiber-optic LSPR(FOLSPR)sensors are detailed,specifically in biomolecular interactions and analysis of proteins,pathogens and cells,nucleic acids(DNA and RNA),and other small molecules(organic compounds and heavy metal ions).Surface modification and detection schemes are emphasized for their potential for label-free and real-time biosensing.The challenges and prospects of FOLSPR sensors are addressed,including the developments in sensitivity,fabrication techniques,and measurement reliability.Integration with emerging technologies such as nanomaterials is highlighted as a promising direction for future research.Overall,this review provides insights into the advancements and potential applications of FOLSPR sensors,paving the way for sensitive and versatile optical biosensing platforms in various fields.

Enhanced organic solar cell performance: Multiple surface plasmon resonance and incorporation of silver nanodisks into a grating‐structure electrode

In this study, plasmonic nanostructures were examined to enhance the light harvesting of organic thin-film solar cells (OSCs) by multiple surface plasmon resonance (SPR) phenomena originating from the grating-coupled configuration with a Blu-ray Disc recordable (BD-R)-imprinted aluminum (Al) grating structure and the incorporation of a series of silver nanodisks (Ag NDs). The devices with such a configuration maximize the light utilization inside OSCs via light absorption, light scattering, and trapping via multiple surface plasmon resonances. Different types and sizes of metallic nanoparticles (NPs), i.e., gold nanoparticles (Au NPs), Ag nanospheres (Ag NSs), and Ag NDs, were used, which were blended separately in a PEDOT:PSS hole transport layer (HTL). The device structure comprised of grating- imprinted-Al/P3HT:PCBM/Ag ND:PEDOT:PSS/ITO. Results obtained from the J–V curves revealed that the power conversion efficiency (PCE) of grating-structured Al/P3HT:PCBM/PEDOT:PSS/ITO is 3.16%;this value is ~6% higher than that of a flat substrate. On the other hand, devices with flat Al and incorporated Au NPs, Ag NSs, or Ag NDs in the HTL exhibited PCEs ranging from 3.15% to 3.37%. Furthermore, OSCs with an Al grating substrate were developed by the incorporation of the Ag ND series into the PEDOT:PSS layer. Compared with that of a reference device, the PCEs of the devices increased to 3.32%–3.59%(11%–20% improvement), indicating that the light absorption enhancement at the active layer corresponds to the grating-coupled surface plasmon resonance and localized surface plasmon resonance excitations with strong near-field distributions penetrating into the active layer leading to higher efficiencies and subsequent better current generation.

Tunable multiple plasmon resonances and local field enhancement of nanocrescent/nanoring structure

According to the plasmon hybridization theory, the plasmon resonance characteristics of the gold nanocrescent/nanoring(NCNR) structure are systematically investigated by the finite element method. It is found that the extinction spectra of NCNR structure exhibit multiple plasmon resonance peaks, which could be attributed to the result of the plasmon couplings between the multipolar plasmon modes of nanocrescent and the dipolar, quadrupolar, hexapolar, octupolar,decapolar plasmon modes of nanoring. By changing the geometric parameters, the intense and separate multiple plasmon resonance peaks are obtained and can be tuned in a wide wavelength range. It is further found that the plasmon coupling induces giant multipole electric field enhancements around the tips of the nanocrescent. The tunable and intense multiple plasmon resonances of NCNR structure may provide effective applications in multiplex biological sensing.

Deep-ultraviolet surface plasmon resonance of Al and Al_(core)/Al_2O_(3shell) nanosphere dimers for surface-enhanced spectroscopy

The localized surface plasmon resonance properties of Al and Alcore/Al2O3shell nanosphere dimers with Al and Al core nanosphere radii of 20 nm and Al2O3 shell of 2 nm in the deep-ultraviolet region have been studied using the finite difference time domain method. The extinction spectra and the electric field distribution profiles of the two dimers for various gap distances between two individual nanospheres are compared with those of the corresponding monomers to reveal the extent of plasmon coupling. It is found that with the interparticle distance decreasing, a strong plasmon coupling between two Al or Alcore/Al2O3shell nanospheres is observed accompanied by a significant red shift in the extinction spectra at the parallel polarization direction of the incident light related to the dimer axis, while for the case of the perpendicular polarization direction, a weak plasmon coupling arises characterized by a slight blue shift in the extinction spectra. The electric field distribution profiles show that benefiting from the dielectric Al2O3 shell, the gap distance of Alcore/Al2O3shell nanosphere dimers can be tailored to 〈 1 nm scale and results in a very high electric field enhancement. The estimated surface-enhanced Raman scattering enhancement factors suggests that the Alcore/Al2O3shell nanosphere dimers with the gap of 〈 1 nm gave rise to an enhancement as high as 8.1 × 10^7 for interparticle gap = 0.5 nm. Our studies reveal that the Alcore/Al2O3shell nanosphere dimers may be promising substrates for surface-enhanced spectroscopy in the deep-ultraviolet region.

Design and fabrication of structural color by local surface plasmonic meta-molecules

In this paper, we propose a new form of nanostructures with Al film deposited on a patterned dielectric material for generating structural color, which is induced by local surface plasmonic resonant(LSPR) absorption in sub-wavelengthindented hole/ring arrays. Unlike other reported results obtained by using focus ion beam(FIB) to create metallic nanostructures, the nano-sized hole/ring arrays in Al film in this work are replicated by high resolution electron beam lithography(EBL) combined with self-aligned metallization. Clear structural color is observed and systematically studied by numerical simulations as well as optical characterizations. The central color is strongly related to the geometric size, which provides us with good opportunities to dye the colorless Al surface by controlling the hole/ring dimensions(both diameter and radius), and to open up broad applications in display, jewelry decoration, green production of packing papers, security code,and counterfeits prevention.

Selective enhancement of green upconversion luminescence of Er-Yb:NaYF4 by surface plasmon resonance of W18O49 nanoflowers and applications in temperature sensing

The W（18）O（49） nanoflowers with a diameter of 500 nm are prepared by a facile hydrothermal method. The Er-Yb：NaYF4 nanoparticles are adsorbed on the petals（the position of the strongest local electric field on W（18）O（49） nanoflowers）.With a 976 nm laser diode（LD） as an excitation source, the selectively green upconversion luminescence（UCL） is observed to be enhanced by two orders of magnitude in Er-Yb： NaYF4/W（18）O（49） nanoflowers heterostructures. It suggests that the near infrared（NIR）-excited localized surface plasmon resonance（LSPR） of W（18）O（49） is primarily responsible for the enhanced UCL, which could be partly reabsorbed by the W（18）O（49）, thus leading to the selective enhancement of green UCL for the Er-Yb： NaYF4. The fluorescence intensity ratio is investigated as a function of temperature based on the intense green UCL, which indicates that Er-Yb： NaYF4/W（18）O（49） nanoflower heterostructures have good potential for developing into temperature sensors.

High-order plasmon resonances in an Ag/Al_2O_3 core/shell nanorice

Using numerical simulation, we investigate the high-order plasmon resonances in individual nanostructures of an Ag nanorice core surrounded by an Al2O3 shell. The peak positions of localized surface plasmon resonances （LSPRs） are red-shifted exponentially with the increase of the dielectric shell thickness. This is due to the exponential decay of electromagnetic field intensity in the direction perpendicular to the interface. This exponential red-shift depends on the wavelength of the resonance peak instead of the resonance order. In addition, we find that the LSPRs in an Ag nanorice of 60-nm width can be perfectly described by a single linear function. These features make nanorice an ideal platform for sensing applications.

LSPR效应增强碳包覆In_(2)O_(3)/W_(18)O_(49)S型异质结用于高效CO_(2)光还原

太阳能驱动的光催化CO_(2)还原(PCR)技术可以将CO_(2)转化为增值燃料,被认为是可以解决化石能源的日益减少和环境污染问题的可持续能源转换技术.CO_(2)的光催化还原涉及多种催化剂和反应途径,构建异质结催化剂是提高光催化CO_(2)还原效率的重要策略.然而,异质结催化剂的光吸收范围一直是影响其性能的重要因素.在增强近红外区光吸收的众多材料中,具有局部表面等离子体共振(LSPR)效应的非贵金属等离子体材料是合适的选择.W_(18)O_(49)具有特殊的缺陷结构和LSPR效应,可以产生高能“热电子”并促进载流子转移,进一步优化了W_(18)O_(49)敏化光催化复合材料的设计,在光催化中显示出非凡的潜力和研究价值.本文在源自In-MOF的碳包覆In_(2)O_(3)(C-In_(2)O_(3))纳米棒外表面组装一维高吸光度W_(18)O_(49)纳米线,设计和制备C-In_(2)O_(3)/W_(18)O_(49)分级S型异质结.采用X射线衍射、扫描电镜和透射电镜对样品进行了结构和形貌表征,结果表明,成功制备了C-In_(2)O_(3)/W_(18)O_(49)复合材料.通过X射线光电子能谱和密度泛函理论计算分析了电子流向,验证了S型异质结的机理.使用原位漫反射红外傅里叶变换光谱、气相色谱和同位素标定进一步确定了PCR反应中间体活化过程和反应产物,其中40%C-In_(2)O_(3)/W_(18)O_(49)复合材料的CO产率最高,达到135.82μmol·h^(-1)·g^(-1),分别是纯C-In_(2)O_(3)和W_(18)O_(49)的2.99和2.84倍.采用时间分辨瞬态光致发光光谱测定样品的荧光寿命,结果表明,C-In_(2)O/W_(18)O_(49)复合材料拥有更长的载流子衰变动力学的平均寿命(4.0707 ns),表明复合材料可以更有效地利用可见光进行光催化反应.C-In_(2)O_(3)/W_(18)O_(49)复合材料较好的催化性能主要归因于以下两个方面.(1)碳涂层的高电子电导率促进了C-In_(2)O_(3)和W_(18)O_(49)之间的电荷转移,载流子在非均相界面的均匀分布和高清的转移是光催化活性提高的重要原因;(2)S型异质结中的内部电子转移和注入C-In_(2)O_(3)的LSPR诱导的“热电子”实现了PCR的双路径电子转移,从而使得PCR反应的活性得到了显著提高.综上,本文为开发高效可见光催化剂提供了新思路和实验依据.