基于石墨烯Tamm等离子体激元的太赫兹强耦合效应

设计了一种全新的一维石墨烯-光子晶体(PhC)复合谐振结构,使用传输矩阵法(TMM)对其所支持的太赫兹Tamm等离子体激元(TPP)和腔体模式(CM)之间的强耦合效应进行理论研究。研究表明,用于表征耦合强度的Rabi分裂能随着光子晶体周期数的减小而增大;改变间隔层和腔体厚度以及石墨烯的费米能级时,也会影响Rabi分裂能。最后通过入射角度对耦合模式进行主动调控,当入射角处于0°~60°时,耦合模式的特性与偏振无关。本文的研究结果为太赫兹强耦合效应的研究和应用提供了新的思路。     

基于SSPPs的低剖面宽带八木天线阵列设计

提出了一种基于新型人工表面等离子体激元(Spoof Surface Plasmon Polaritons, SSPPs)馈电带有引向器的低剖面宽带八木天线阵列。天线阵列包括两部分:基于人工表面等离子体激元波导的四路宽带功分器和八木天线阵列。人工表面等离子体激元具有高的场局限性,将信号束缚在人工表面等离子体激元的凹槽结构中保证了信号的高效传输,减少了传输损耗。八木天线通过进一步加载引向器结构能够实现端射辐射特性。测试结果表明:天线阵列的回波损耗在4.5 ~6.05 GHz 频率范围内小于-10 dB。天线阵列实际增益在4.5 ~ 6.05 GHz 范围内最高可达11.1 dBi。     

Exciton Dynamics and Effects of Structural Order in Morphology‐Controlled J‐Aggregate Assemblies

Narrow‐band photoluminescence (PL) together with high quantum efficiency from organic molecules is essential for high‐color‐purity emitters. Supramolecular assemblies like J‐aggregates are promising materials due to their narrow PL signal with full‐width at half maximum <20 nm. However, their microcrystalline nature and coherent exciton migration results in strong nonradiative exciton recombination at the grain boundaries that diminish the photoluminescence quantum yield (PLQY), and possibilities for improving the crystallinity by tuning the growth mechanism are limited. Here, two distinct routes to grow different J‐aggregate morphologies like platelets and lamellar crystals with improved crystallinity by surface‐guided molecular assembly are demonstrated, thereby suppressing nonradiative decay and improving PLQY. Both platelets and lamellar crystals show similar absorbance at room temperature. However, temperature‐dependent PL studies show sevenfold (twofold) higher PLQY for lamellar films compared to platelets at 6 K (300 K). Using time‐resolved PL spectroscopy, different nonradiative decay pathways are identified. The dependence of exciton diffusion on energetic disorder and nonradiative decay is discussed. The results suggest that the difference in domain size and order gives rise to significantly enhanced radiative decay from lamellar films as compared to platelets or films formed by spin‐coating.     

Induced SER‐Activity in Nanostructured Ag–Silica–Au Supports via Long‐Range Plasmon Coupling

A novel Ag–silica–Au hybrid device is developed that displays a long‐range plasmon transfer of Ag to Au leading to enhanced Raman scattering of molecules largely separated from the optically excited Ag surface. A nanoscopically rough Ag surface is coated by a silica spacer of variable thickness from ～1 to 21 nm and a thin Au film of ～25 nm thickness. The outer Au surface is further functionalized by a self‐assembled monolayer (SAM) for electrostatic binding of the heme protein cytochrome c (Cyt c) that serves as a Raman probe and model enzyme. High‐quality surface‐enhanced resonance Raman (SERR) spectra are obtained with 413 nm excitation, demonstrating that the enhancement results exclusively from excitation of Ag surface plasmons. The enhancement factor is estimated to be 2 × 10⁴–8 × 10³ for a separation of Cyt c from the Ag surface by 28–47 nm, corresponding to an attenuation of the enhancement by a factor of only 2–6 compared to Cyt c adsorbed directly on a SAM‐coated Ag electrode. Upon immobilization of Cyt c on the functionalized Ag–silica–Au device, the native structure and redox properties are preserved as demonstrated by time‐ and potential‐dependent SERR spectroscopy.     

Enhanced Delayed Fluorescence in Tetracene Crystals by Strong Light‐Matter Coupling

An enhanced delayed fluorescence is demonstrated experimentally in tetracene single crystals strongly coupled to optical modes in open cavities formed by arrays of plasmonic nanoparticles. Hybridization of singlet excitons with collective plasmonic resonances in the arrays leads to the splitting of the material dispersion into a lower and an upper polariton band. This splitting significantly modifies the dynamics of the photoexcited tetracene crystal, resulting in an increase of the delayed fluorescence by a factor of 4. The enhanced delayed fluorescence is attributed to the emergence of an additional radiative decay channel, where the lower polariton band harvests long‐lived triplet states. There is also an increase in total emission, which is wavelength dependent, and can be explained by the direct emission from the lower polariton band, the more efficient light out‐coupling, and the enhancement of the excitation intensity. The observed enhanced fluorescence opens the possibility of efficient radiative triplet harvesting in open optical cavities, to improve the performance of organic light emitting diodes.     

Poly[oligo(ethylene glycol) methacrylate‐co‐glycidyl methacrylate] Brush Substrate for Sensitive Surface Plasmon Resonance Imaging Protein Arrays

Surface plasmon resonance imaging (SPRi) is a unique microarray method for label‐free and multiplexed bio‐assays. However, it currently cannot be used to detect human serum samples due to its low sensitivity and poor specificity. A poly[oligo(ethylene glycol) methacrylate‐co‐glycidyl methacrylate] (POEGMA‐co‐GMA) brush was synthesized by surface‐initiated atom transfer radical polymerization (SI‐ATRP) and used as a unique supporting matrix for SPRi arrays to efficiently load probe proteins for high sensitivity while reducing nonspecific adsorptions for good selectivity. Results indicate that the polymer brush has a high protein loading capacity (1.8 protein monolayers), low non‐specific protein adsorption (below the SPR detection limit), and high immobilization stability. Three model biomarkers, α‐fetoprotein, carcinoembryonic antigen, and hepatitis B surface antigen were simultaneously detected in human serum samples by a SPRi chip for the first time, showing detection limits of 50, 20, and 100 ng mL^?1, respectively. This work demonstrates great potential for a SPRi biochip as a powerful label‐free and high‐throughput detection tool in clinical diagnosis and biological research. Since the SPR detection is limited by the sensing film thickness, this approach particularly offers a unique way to significantly improve the sensitivity in the SPR detecting thickness range.     

Size‐Controlled Synthesis of Cu2‐xE (E = S,Se) Nanocrystals with Strong Tunable Near‐Infrared Localized Surface Plasmon Resonance and High Conductivity in Thin Films

A facile method for preparing highly self‐doped Cu_2‐xE (E = S, Se) nanocrystals (NCs) with controlled size in the range of 2.8–13.5 nm and 7.2–16.5 nm, for Cu_2‐xS and Cu_2‐xSe, respectively, is demonstrated. Strong near‐infrared localized surface plasmon resonance absorption is observed in the NCs, indicating that the as‐prepared particles are heavily p‐doped. The NIR plasmonic absorption is tuned by varying the amount of oleic acid used in synthesis. This effect is attributed to a reduction in the number of free carriers through surface interaction of the deprotonated carboxyl functional group of oleic acid with the NCs. This approach provides a new pathway to control both the size and the cationic deficiency of Cu_2‐xSe and Cu_2‐xS NCs. The high electrical conductivity exhibited by these NPs in metal‐semiconductor‐metal thin film devices shows promise for applications in printable field‐effect transistors and microelectronic devices.     

Biologically Enabled Syntheses of Freestanding Metallic Structures Possessing Subwavelength Pore Arrays for Extraordinary (Surface Plasmon‐Mediated) Infrared Transmission

A scalable wet chemical process has been used to convert the intricate silica microshells (frustules) of diatoms into gold structures that retained the three‐dimensional (3‐D) frustule shapes and fine patterned features. Combined use of an amine‐enriching surface functionalization protocol and electroless deposition yielded thin (<100 nm) conformal nanocrystalline gold coatings that, upon selective silica dissolution, were converted into freestanding gold structures with frustule‐derived 3‐D morphologies. By selecting a diatom frustule template with a quasi‐regular hexagonal pore pattern (Coscinodiscus asteromphalus, CA), gold replica structures possessing such pore patterns were produced that exhibited infrared transmission maxima/reflection minima that were not observed for the starting silica diatom frustules or for flat nonporous gold films; that is, such extraordinary optical transmission (EOT) resulted from the combined effects of the quasi‐periodic hexagonal hole structure (inherited from the CA diatom frustules) and the gold chemistry. Calculated and measured IR transmission spectra obtained from planar gold films with quasi‐periodic hexagonal CA‐derived hole patterns, or with short‐range periodic hexagonal hole patterns, indicated that the enhanced IR transmission exhibited by the gold CA frustule replicas was enabled by the generation and transmission of surface plasmons. This scalable bio‐enabled process provides a new and attractive capability for fabricating self‐supporting, responsive, 3‐D metallic structures for use as dispersible/harvestable microparticles tailored for EOT‐based applications.     

Enhancement of Phosphorescence by Surface‐Plasmon Resonances in Colloidal Metal Nanoparticles: The Role of Aggregates

The spectroscopic and near‐field scanning optical microscopy (NSOM) studies of phosphorescent films doped with colloidal gold nanoparticles (NPs) are presented. Films with a high concentration of 2,3,7,8,12,13,17,18‐octaethyl‐21H,23H‐porphine platinum(II ) dispersed in a neutral polymer poly[(methyl methacrylate)‐co‐(ethyl acrylate)] demonstrate a twofold increase of the phosphorescence quantum yield after the addition of aggregated NPs. In materials doped with unaggregated particles, a decrease of the emission yield is observed. Theoretical modeling of the phosphorescence transients suggests a minimization of the triplet–triplet quenching owing to the presence of fast processes that decrease the concentration of chromophores in the excited state and may be both of radiative and non‐radiative origin. NSOM examination of the films reveals increased light emission around large NP clusters. This observation demonstrates significant enhancement of the spontaneous emission rates by the large aggregates, although unaggregated NPs introduce mostly phosphorescence quenching sites.     

Enhancement of Green Emission from InGaN/GaN Multiple Quantum Wells via Coupling to Surface Plasmons in a Two‐Dimensional Silver Array

A novel approach to enhancing the emission efficiency of InGaN/GaN multiple quantum wells via coupling to surface plasmons (SPs) in a periodic two‐dimensional silver array is demonstrated. A higher internal quantum efficiency and a higher light extraction efficiency are simultaneously achieved by engraving an array of nanoholes into the p‐GaN cladding layer, followed by partial filling with silver. By top excitation and collection from the top of the Ag‐incorporated light emitting diodes (LEDs), a 2.8‐fold enhancement in peak photoluminescence intensity is demonstrated. The proposed nanoengraving technique offers a practical approach to overcoming the limitation of the exponentially decayed SP field without sacrificing the thickness of the p‐GaN layer and to controlling the effective coupling energy. The approach is feasible for high‐power lighting applications.     

Modulation of Spin Dynamics via Voltage Control of Spin‐Lattice Coupling in Multiferroics

Motivated by the most recent progresses in both magnonics (spin dynamics) and multiferroics fields, this work aims at magnonics manipulation by the magnetoelectric coupling effect. Here, voltage control of magnonics, particularly the surface spin waves, is achieved in La_0.7Sr_0.3MnO₃/0.7Pb(Mg_1/3Nb_2/3)O₃‐0.3PbTiO₃ multiferroic heterostructures. With the electron spin resonance method, a large 135 Oe shift of surface spin wave resonance (≈7 times greater than conventional voltage‐induced ferromagnetic resonance shift of 20 Oe) is determined. A model of the spin‐lattice coupling effect, i.e., varying exchange stiffness due to voltage‐induced anisotropic lattice changes, has been established to explain experiment results with good agreement. Additionally, an “on” and “off” spin wave state switch near the critical angle upon applying a voltage is created. The modulation of spin dynamics by spin‐lattice coupling effect provides a platform for realizing energy‐efficient, tunable magnonics devices.     

Surface Design in Solid‐State Dye Sensitized Solar Cells: Effects of Zwitterionic Co‐adsorbents on Photovoltaic Performance

In solid‐state dye sensitized solar cells (SSDSCs) charge recombination at the dye‐hole transporting material interface plays a critical role in the cell efficiency. For the first time we report on the influence of dipolar co‐adsorbents on the photovoltaic performance of sensitized hetero‐junction solar cells. In the present study, we investigated the effect of two zwitterionic butyric acid derivatives differing only in the polar moiety attached to their common 4 carbon‐chain acid, i.e., 4‐guanidinobutyric acid (GBA) and 4‐aminobutyric acid (ABA). These two molecules were implemented as co‐adsorbents in conjunction with Z907Na dye on the SSDSC. It was found that a Z907Na/GBA dye/co‐adsorbent combination increases both the open circuit voltage (V_oc) and short‐circuit current density (J_sc) as compared to using Z907Na dye alone. The Z907Na/ABA dye/co‐adsorbent combination increases the J_sc. Impedance and transient photovoltage investigations elucidate the cause of these remarkable observations.     

Synthesis of Dumbbell‐Like Gold–Metal Sulfide Core–Shell Nanorods with Largely Enhanced Transverse Plasmon Resonance in Visible Region and Efficiently Improved Photocatalytic Activity

The metallic nanostructures with unique properties of tunable plasmon resonance and large field enhancement have been cooperated with semiconductor to construct hetero‐nanostructures for various applications. Herein, a general and facile approach to synthesize uniform dumbbell‐like gold–sulfide core–shell hetero‐nanostructures is reported. The transformation from Au nanorods (NRs) to dumbbell‐like Au NRs and coating of metal sulfide shells (including Bi₂S₃, CdS, Cu_xS, and ZnS) are achieved in a one‐pot reaction. Due to the reshaping of Au core and the deposition of sulfide shell, the plasmon resonances of Au NRs are highly enhanced, especially the about 2 times enhancement for the visible transverse plasmon resonance compared with the initial Au NRs. Owing to the highly enhanced visible light absorption and strong local electric field, we find the photocatalytic activity of dumbbell‐like Au–Bi₂S₃ NRs is largely enhanced compared with pure Bi₂S₃ and normal Au–Bi₂S₃ NRs by testing the photodegradation rate of Rhodamine B (RhB). Moreover, the second‐layer sulfide can be coated and the double‐shell Au–Bi₂S₃–CdS hetero‐nanostructures show further improved photodegradation rate, especially about 2 times than that of Degussa P25 TiO₂ (P25) ascribing to the optimum band arrangement and then the prolonged lifetime of photo‐generated carriers.     

Investigation of Optical and Structural Stability of Localized Surface Plasmon Mediated Light‐Emitting Diodes by Ag and Ag/SiO2 Nanoparticles

Localized surface plasmon (LSP) effects due to Ag and Ag/SiO₂ nanoparticles (NPs) deposited on GaN/InGaN multiquantum well (MQW) light‐emitting diode (LED) structures are studied. The colloidal NPs are synthesized by a sol‐gel method and drop‐cased on the LED structures. The surface density of NPs its controlled by the concentration of the NP solution. Theoretical modeling is performed for the emission spectrum and the electric field distribution of LSP resonance for Ag/SiO₂ NPs. Enhanced photoluminescence (PL) efficiency is observed in the LED structures and the amount of PL enhancement increases with increasing the surface density of Ag and Ag/SiO₂ NPs. These effects are attributed to resonance coupling between the MQW and LSP in the NPs. It is also shown that the PL enhancement attainable with Ag NPs and Ag/SiO₂ NPs is comparable, but the latter displays a much higher stability with respect to long‐term storage and annealing due to a barrier for NP agglomeration, Ag oxidation, and impurity diffusion provided by the SiO₂ shell.