Efficient plasmon-enhanced perovskite solar cells by molecularly isolated gold nanorods

Perovskite solar cells(PSCs)are becoming a promising candidate for next-generation photovoltaic cells due to their attractive power conversion efficiency(PCE).Plasmonic enhancement is regarded as an optical tuning approach for further improving the PCE of single-junction PSCs toward Shockley-Queisser limit.Herein,we introduce molecularly isolated gold nanorods(Au NRs),bearing relatively stronger scattering ability and localized surface plasmonic resonance(LSPR)effect,in the rear side of perovskites in PSCs,for promoting light harvesting and for electrical enhancement.Owing to the larger refractive index and better matched energy level alignment,the 4-mercaptobenzoic acid molecules coated on Au NRs prove to play important dual roles:isolating the metallic Au NRs from contacting with perovskite,and facilitating more efficient charge separation and transport across the interface under the synergetic LSPR effect of Au NRs.Our work highlights the capability of the plasmonic approach by nanorods and by molecular isolation,extending nanoparticle-based plasmonic approaches,toward highly efficient plasmon-enhanced PSCs.

Surface plasmon-enhanced photochemical reactions on noble metal nanostructures

Nanoscale noble metals can exhibit excellent photochemical and photophysical properties, due to surface plasmon resonance(SPR) from specifically collective electronic excitations on these metal surfaces. The SPR effect triggers many new surface processes, including radiation and radiationless relaxations. As for the radiation process, the SPR effect causes the significant focus of light and enormous enhancement of the local surface optical electric field, as observed in surface-enhanced Raman spectroscopy(SERS) with very high detection sensitivity(to the single-molecule level). SERS is used to identify surface species and characterize molecular structures and chemical reactions. For the radiationless process, the SPR effect can generate hot carriers, such as hot electrons and hot holes, which can induce and enhance surface chemical reactions. Here, we review our recent work and related literature on surface catalytic-coupling reactions of aromatic amines and aromatic nitro compounds on nanostructured noble metal surfaces. Such reactions are a type of novel surface plasmon-enhanced chemical reaction. They could be simultaneously characterized by SERS when the SERS signals are assigned. By combining the density functional theory(DFT) calculations and SERS experimental spectra, our results indicate the possible pathways of the surface plasmonenhanced photochemical reactions on nanostructures of noble metals. To construct a stable and sustainable system in the conversion process of the light energy to the chemical energy on nanoscale metal surfaces, it is necessary to simultaneously consider the hot electrons and the hot holes as a whole chemical reaction system.

NIR-II driven plasmon-enhanced cascade reaction for tumor microenvironment-regulated catalytic therapy based on bio-breakable Au-Ag nanozyme

Emerging nanozymes with natural enzyme-mimicking catalytic activities have inspired extensive research interests due to their high stability,low cost,and simple preparation,especially in the field of catalytic tumor therapy.Here,bio-breakable nanozymes based on glucose-oxidase(GOx)-loaded biomimetic Au–Ag hollow nanotriangles(Au–Ag–GOx HTNs)are designed,and they trigger an near-infrared(NIR)-II-driven plasmon-enhanced cascade catalytic reaction through regulating tumor microenvironment(TME)for highly efficient tumor therapy.Firstly,GOx can effectively trigger the generation of gluconic acid(H+)and hydrogen peroxide(H2O2),thus depleting nutrients in the tumor cells as well as modifying TME to provide conditions for subsequent peroxidase(POD)-like activity.Secondly,NIR-II induced surface plasmon resonance can induce hot electrons to enhance the catalytic activity of Au–Ag–GOx HTNs,eventually boosting the generation of hydroxyl radicals(•OH).Interestingly,the generated H2O2 and H+can simultaneously induce the degradation of Ag nanoprisms to break the intact triangle nanostructure,thus promoting the excretion of Au–Ag–GOx HTNs to avoid the potential risks of drug metabolism.Overall,the NIR-II driven plasmon-enhanced catalytic mechanism of this bio-breakable nanozyme provides a promising approach for the development of nanozymes in tumor therapy.

Modulation of hot regions in waveguide-based evanescent-field-coupled localized surface plasmons for plasmon-enhanced spectroscopy

Coupling efficiency between the localized surface plasmons(LSPs) of metal nanoparticles(NPs) and incident light dominates the sensitivities of plasmon-based sensing spectroscopies and imaging techniques, e.g., surfaceenhanced Raman scattering(SERS) spectroscopy. Many endogenous features of metal NPs(e.g., size, shape,aggregation form, etc.) that have strong impacts on their LSPs have been discussed in detail in previous studies.Here, the polarization-tuned electromagnetic(EM) field that facilitates the LSP coupling is fully discussed.Numerical analyses on waveguide-based evanescent fields(WEFs) coupled with the LSPs of dispersed silver nanospheres and silver nano-hemispheres are presented and the applicability of the WEF-LSPs to plasmon-enhanced spectroscopy is discussed. Compared with LSPs under direct light excitation that only provide 3–4 times enhancement of the incidence field, the WEF-LSPs can amplify the electric field intensity about 30–90 times(equaling the enhancement factor of 10~6–10~8 in SERS intensity), which is comparable to the EM amplification of the SERS"hot spot" effect. Importantly, the strongest region of EM enhancement around silver nanospheres can be modulated from the gap region to the side surface simply by switching the incident polarization from TM to TE, which widely extends its sensing applications in surface analysis of monolayer of molecule and macromolecule detections. This technique provides us a unique way to achieve remarkable signal gains in many plasmon-enhanced spectroscopic systems in which LSPs are involved.

Light-field modulation and optimization near metal nanostructures utilizing spatial light modulators

Plasmonic modes within metal nanostructures play a pivotal role in various nanophotonic applications.However,a significant challenge arises from the fixed shapes of nanostructures post-fabrication,resulting in limited modes under ordinary illumination.A promising solution lies in far-field control facilitated by spatial light modulators(SLMs),which enable on-site,real-time,and non-destructive manipulation of plasmon excitation.Through the robust modulation of the incident light using SLMs,this approach enables the generation,optimization,and dynamic control of surface plasmon polariton(SPP)and localized surface plasmon(LSP)modes.The versatility of this technique introduces a rich array of tunable degrees of freedom to plasmon-enhanced spectroscopy,offering novel approaches for signal optimization and functional expansion in this field.This paper provides a comprehensive review of the generation and modulation of SPP and LSP modes through far-field control with SLMs and highlights the diverse applications of this optical technology in plasmon-enhanced spectroscopy.

Optical Trapping of a Single Molecule of Length Sub-1 nm in Solution

Plasmonic optical manipulation has emerged as an affordable alternative to manipulate single chemical and biological molecules in nanoscience.Although the theoretical models of sub-5 nm single-molecule trapping have been considered promising,the experimental strategies remain a challenge due to the Brownian motions and weak optical gradient forces with significantly reduced molecular polarizability.Herein,we address direct trapping and in situ sensing of single molecules with unprecedented size,down to∼5Åin solution,by employing an adjustable plasmonic optical nanogap and single-molecule conductance measurement.The theoretical simulations demonstrate that local fields with a high enhancement factor,over 103,were generated at such small nanogaps,resulting in optical forces as large as several piconewtons to suppress the Brownian motion and trap a molecule of length sub-1 nm.This work demonstrates a strategy for directly manipulating the small molecule units,promising a vast multitude of applications in chemical,biological,and materials sciences at the single-molecule level.

Plasmonic enhancement and polarization dependence of nonlinear upconversion emissions from single gold nanorod@SiO_(2)@CaF2:Yb^(3+),Er^(3+)hybrid core–shell–satellite nanostructures

Lanthanide-doped upconversion nanocrystals(UCNCs)have recently become an attractive nonlinear fluorescence material for use in bioimaging because of their tunable spectral characteristics and exceptional photostability.Plasmonic materials are often introduced into the vicinity of UCNCs to increase their emission intensity by means of enlarging the absorption cross-section and accelerating the radiative decay rate.Moreover,plasmonic nanostructures(e.g.,gold nanorods,GNRs)can also influence the polarization state of the UC fluorescence—an effect that is of fundamental importance for fluorescence polarization-based imaging methods yet has not been discussed previously.To study this effect,we synthesized GNR@SiO_(2)@CaF2:Yb^(3+),Er^(3+)hybrid core–shell–satellite nanostructures with precise control over the thickness of the SiO_(2) shell.We evaluated the shell thicknessdependent plasmonic enhancement of the emission intensity in ensemble and studied the plasmonic modulation of the emission polarization at the single-particle level.The hybrid plasmonic UC nanostructures with an optimal shell thickness exhibit an improved bioimaging performance compared with bare UCNCs,and we observed a polarized nature of the light at both UC emission bands,which stems from the relationship between the excitation polarization and GNR orientation.We used electrodynamic simulations combined with Förster resonance energy transfer theory to fully explain the observed effect.Our results provide extensive insights into how the coherent interaction between the emission dipoles of UCNCs and the plasmonic dipoles of the GNR determines the emission polarization state in various situations and thus open the way to the accurate control of the UC emission anisotropy for a wide range of bioimaging and biosensing applications.

Silver nanoislands on cellulose fibers for chromatographic separation and ultrasensitive detection of small molecules

High-throughput small-molecule assays play essential roles in biomedical diagnosis,drug discovery,environmental analysis,and physiological function research.Nanoplasmonics holds a great potential for the label-free detection of small molecules at extremely low concentrations.Here,we report the development of nanoplasmonic paper(NP-paper)for the rapid separation and ultrasensitive detection of mixed small molecules.NP-paper employs nanogap-rich silver nanoislands on cellulose fibers,which were simply fabricated at the wafer level by using low-temperature solid-state dewetting of a thin silver film.The nanoplasmonic detection allows for the scalable quantification and identification of small molecules over broad concentration ranges.Moreover,the combination of chromatographic separation and nanoplasmonic detection allows both the highly sensitive fluorescence detection of mixed small molecules at the attogram level and the label-free detection at the sub-nanogram level based on surface-enhanced Raman scattering.This novel material provides a new diagnostic platform for the high-throughput,low-cost,and label-free screening of mixed small molecules as an alternative to conventional paper chromatography.