Plasmon-enhanced Absorption Research Articles

Spontaneous emission, collective phenomena and the efficiency of plasmon-stimulated photoexcitation

We find that the spontaneous and collective emissions have a strong influence on the excitation of two-level absorbers (atoms, molecules) interacting in resonance with the plasmonic mode near the metal nanoparticle. The spontaneous and collective emissions limit the absorption enhancement by the plasmonic mode and make the enhancement possible only with a fast, picosecond population relaxation of the upper absorbing states. Conditions for the maximum of plasmon-enhanced absorption in the presence of spontaneous and collective emissions are found. The nonlinearity in the nanoparticle-absorber interaction and in collective emission causes the bistability in the plasmon-enhanced absorption at high external field intensities and the plasmonic mode excitation.

Plasmon-enhanced chiral absorption through electric dipole–electric quadrupole interaction

Enantioselective interactions of chiral molecules include distinct absorptions to opposite-handed circularly polarized light, known as chiral absorption. Traditionally, chiral absorption has been primarily attributed to electric dipole (ED) and magnetic dipole (MD) interaction with molecular chirality. However, this approach falls short for large molecules that support high-order multipolar components, such as electric quadrupole (EQ) moment. Here, we introduce a theoretical model to study the chiral absorption of large molecules in the presence of plasmonic nanostructures. This model considers both ED–MD interaction and ED–EQ interaction enhanced by a resonant structure. We numerically study such interactions of the chiral molecular solution in the vicinity of an achiral plasmonic nano-resonator. Our results show the distinct spectral information of the chiral medium on- and off-resonance of the resonator.

Time-dependent Kohn-Sham electron dynamics coupled with nonequilibrium plasmonic response via atomistic electromagnetic model.

Computational modeling of plasmon-mediated molecular photophysical and photochemical behaviors can help us better understand and tune the bound molecular properties and reactivity and make better decisions to design and control nanostructures. However, computational investigations of coupled plasmon-molecule systems are challenging due to the lack of accurate and efficient protocols to simulate these systems. Here, we present a hybrid scheme by combining the real-time time-dependent density functional theory (RT-TDDFT) approach with the time-domain frequency dependent fluctuating charge (TD-ωFQ) model. At first, we transform ωFQ in the frequency-domain, an atomistic electromagnetic model for the plasmonic response of plasmonic metal nanoparticles (PMNPs), into the time-domain and derive its equation-of-motion formulation. The TD-ωFQ introduces the nonequilibrium plasmonic response of PMNPs and atomistic interactions to the electronic excitation of the quantum mechanical (QM) region. Then, we combine TD-ωFQ with RT-TDDFT. The derived RT-TDDFT/TD-ωFQ scheme allows us to effectively simulate the plasmon-mediated "real-time" electronic dynamics and even the coupled electron-nuclear dynamics by combining them with the nuclear dynamics approaches. As a first application of the RT-TDDFT/TD-ωFQ method, we study the nonradiative decay rate and plasmon-enhanced absorption spectra of two small molecules in the proximity of sodium MNPs. Thanks to the atomistic nature of the ωFQ model, the edge effect of MNP on absorption enhancement has also been investigated and unveiled.

Plasmonic absorption enhancement of MAPI-based perovskite solar cell with nanoparticles array

In this work, we propose a MAPI-based p-i-n perovskite solar cell with architecture ITO/PEDOT:PSS/MAPI/Rhodamine/TiO2/Ag. Although MAPI-based solar cells have prominent performance, there are some challenges for these devices. Poor optical absorption at near-infrared wavelengths is the most important challenge for MAPI-based solar cells. The effect of three kinds of periodic array nanoparticles on the absorption spectra of the perovskite layer has been investigated theoretically. The spherical bare Au nanoparticle, Au@SiO2, and Au@TiO2 core–shell nanorods have been used. Moreover, Rhodamine as a surface passivator to decrease the charge carrier recombination is used between perovskite and Electron Transport Layer (ETL). Our simulation is based on three dimensions Finite-Difference Time-Domain (FDTD) method and we use Lumerical software. The effect of these nanoparticles on electric field intensity, light absorption, short-circuit current density, and generation rate are investigated for the visible and near-infrared bands. We found that Au@TiO2 can improve light absorption more than Au and Au@SiO2 at the near-infrared band and this increment is due to the growth of plasmonic near-field of nanoparticles and light scattering enhancement from these nanoparticles.

Titanium-Based Metasurfaces for Optoelectronics.

We report on the fabrication method that enables the development of transparent conductive metasurfaces capable of the resonant absorption of light in specific frequency bands. The approach is based on embedding linear sp-carbon chains and metallic nanoparticles in a porous matrix of titanium dioxide (TiO2). We develop a blading technique for the formation of a periodical grating of TiO2 microtubes at the macroscale. The method allowed us to maintain the periodicity of an array of microtubes with an accuracy of ±5%. Tuning the diameter of the tubes and the concentration of metallic nanoparticles, we achieved the regime of strong resonant absorption of the fabricated complex metasurface in the visible range. Computer simulations helped revealthe regime of TE/TM-polarized laser pumping that allowed for the most efficient transformation of light energy into electric current flow. In the studied structures, the sp-carbon clusters embedded inside transparent titanium dioxide tubes play the role of atomic wires. The interplay between efficient conductivity through carbon wires and the plasmon-enhanced absorption of light allows the design of photodiode structures based on periodical metasurfaces and characterized by highly selective optical sensitivity.

Effect of various metallic nanoparticles on plasmon-enhanced solar absorption efficiency.

Solar thermal conversion technology has attracted significant attention because it ensures sustainable and modern clean energy generation. The usage of plasmonic nanofluids as the working media is a useful strategy to collect solar energy. In this study, the optical properties of various individual nanospheres (NPs) and nanorods (NRs)--Au, Ag, Cu, Fe, Mg, Mn, Mo, Pb, Ti, Li, and Al--and their effect on the solar absorption efficiency factor (SAEF) with a solar wavelength between 300nm and 1100nm are determined using COMSOL Multiphysics software. For NPs, the SAEF is divided into three parts. In the first part with a radius lower than 35nm, an Li NP has the highest SAEF of 1.3992. In the second part, with a radius between 35nm and 50nm, the Au and Cu NPs have the highest SAEFs of 1.1963 and 1.2469, respectively. In the third part, with a radius between 50nm and 90nm, the maximum SAEFs of Fe (1.5682 at radius of 75nm), Pt (1.4914 at radius of 90nm), Ti (1.4348 at radius of 75nm), and Mn (1.4614 at radius of 75nm) can be obtained. Compared to NPs, the SAEF of an NR greatly depends on the aspect ratio (AR) and the effective radius (r e f f ). We observe that the SAEFs of Ag, Al, Au, Cu, Fe Mg, Mn, Mo, and Ti NRs are much stronger than that of corresponding NPs with the same r e f f . The results obtained from the present study provide fundamental information and guidelines to choose optimal NPs for enhancements in solar energy harvesting.

Studying Plasmon Dispersion of MXene for Enhanced Electromagnetic Absorption.

2D metal carbides and nitrides (MXene) are promising candidates for electromagnetic (EM) shielding, saturable absorption, thermal therapy, and photocatalysis owing to their excellent EM absorption. The plasmon resonances in metallic MXene micro/nanostructures may play an important role in enhancing the EM absorption; however, their contribution has not been determined due to the lack of a precise understanding of its plasmon behavior. Here, the use of high-spatial-resolution electron energy-loss spectroscopy to measure the plasmon dispersion of MXene films with different thicknesses is reported, enabling accurate analysis of the EM absorption of complex MXene structures in a wide frequency range via a theoretical model. The EM absorption of MXene can be excited at the desired frequency by controlling the momentum (e.g., the sizes of the nanoflakes for EM excitation) as the strength can be enhanced by increasing the layer number and the interlayer distance in MXene. For example, a 3nm interlayer distance can nearly double the plasmon-enhanced EM absorption in MXene nanostructures. These findings can guide the design of advanced ultrathin EM absorption materials for a broad range of applications.

Design of a Slab Tamm Plasmon Resonator Coupled to a Multistrip Array Waveguide for the Mid Infrared.

In this work, we present and analyze a design of an absorber–waveguide system combining a highly sensitive waveguide array concept with a resonant selective absorber. The waveguide part is composed of an array of coupled strip waveguides and is therefore called a coupled strip array (CSA). The CSA is then coupled to the end of a slab Tamm plasmon (STP-) resonator, which is composed of a quasicrystal-like reflector formed by the patterning of a silicon slab and an interfacing tungsten slab. The concept describes an emitter–waveguide or waveguide–detector system featuring selective plasmon-enhanced resonant absorption or emission. These are crucial properties for corresponding optical on-chip integrated devices in context with evanescent field absorption sensing in fluids or gases, for example. Thus, the concept comprises a valuable and more cost-effective alternative to quantum cascade lasers. We designed the lateral dimensions of the STP resonator via a simple quasi-crystal approach and achieved strong narrowband resonances (emittance and Q-factors up to 85% and 88, respectively) for different silicon thicknesses and substrate materials (air and silicon oxide). Moreover, we analyze and discuss the sensitivity of the complete emitter–waveguide system in dependence on the slab thickness. This reveals the crucial correlation between the expected sensitivity assigned to the absorber–waveguide system and field confinement within the silicon.

NUMERICAL STUDY OF PLASMONIC ABSORPTION ENHANCEMENT IN SILICON SUBSTRATE WITH AG/AU NANOPARTICLE ARRAY

NUMERICAL STUDY OF PLASMONIC ABSORPTION ENHANCEMENT IN SILICON SUBSTRATE WITH AG/AU NANOPARTICLE ARRAY

Local Surface Plasmonic Resonance, Surface-Enhanced Raman Scattering, Photoluminescence, and Photocatalytic Activity of Hydrothermal Titanate Nanotubes Coated with Ag Nanoparticles

In this work, we successfully fabricated homogeneous hydrothermal titanate nanotubes (TNTs) coated with Ag nanoparticles (NPs) and elucidated the role of Ag NPs on local surface plasmonic resonance, surface-enhanced Raman scattering, and the enhanced photocatalytic activity of TNT/Ag nanocomposite. The results showed that the photodegradation process reached equilibrium in just ~5 min for the TNT/Ag nanocomposite, which was much shorter than that of the TNT sample (~90 min). TEM micrographs showed that Ag NPs were well dispersed on the walls of the nanotubes. XRD patterns and Raman spectra indicated that the TNTs were in the monoclinic structure of H2Ti3O7. Furthermore, Raman active modes of the TNTs were significantly enhanced in the TNT/Ag sample, which was attributed to surface-enhanced Raman spectroscopy. The enhanced photocatalytic activity of the TNT/Ag sample was explained by UV-vis diffuse reflectance spectroscopy and photoluminescence emission spectroscopy, which showed local surface plasmonic resonance-induced visible light absorption enhancement and effective charge separation, respectively.

Interband plasmon-enhanced optical absorption of DNA nucleobases through the graphene nanopore.

We propose a novel, to the best of our knowledge, plasmonic-based methodology for the purpose of fast DNA sequencing. The interband surface plasmon resonance and field-enhancement properties of graphene nanopore in the presence of the DNA nucleobases are investigated using a hybrid quantum/classical method (HQCM), which employs time-dependent density functional theory and a quasistatic finite difference time domain approach. In the strong plasmonic-molecular coupling regime where the plasmon and DNA absorption frequencies are degenerated, the optical response of DNA molecule in the vicinity of the nanopore is enhanced. In contrast, when the plasmon and nucleobases resonances are detuned the distinct peaks and broadening of the molecular resonances represent the inherent properties of the nucleobase. Due to the different optical properties of DNA nucleobases in the ultraviolet (UV) region of light, the signal corresponding to the replacement of nucleobases in a DNA block can be determined by considering the differential absorbance. Results show the promising capability of the present mechanism for practical DNA sequencing.

Plasmon-enhanced ultrafast and tunable thermo-optic nonlinear optical properties of femtosecond laser ablated TiO2 and Silver-doped TiO2 nanoparticles

We report the results obtained from our extensive femtosecond (fs) nonlinear optical (NLO) studies of titanium dioxide (TiO2) and silver (Ag) doped titanium dioxide (Ag-TiO2) nanoparticles. TiO2 as well as Ag-TiO2 nanoparticles (NPs) were synthesized in deionized water using the techniques of fs laser ablation and simultaneous laser induced chemical reduction through irradiation, respectively. The broadband third-order nonlinear optical (NLO) behaviour of the synthesized NPs was investigated by employing the standard open and closed aperture Z-scan experiments with fs laser pulses delivered from an oscillator (~80 MHz repetition rate at wavelengths of 700 nm, 750 nm, 800 nm, 850 nm) and amplifier pulses (1 kHz repetition rate at wavelengths of 800 nm, 1000 nm, 1100 nm, 1200 nm). The corresponding NLO coefficients [two-photon absorption (2PA) coefficients of ~10-8 cm/W and three-photon absorption (3PA) coefficients of ~10-15 cm3/W2 with MHz excitation] were retrieved from the theoretical fits to the experimental Z-scan data. It was evident from the experimental observations that the Ag-TiO2 NPs demonstrated a significant tendency towards 3PA and also crucially higher nonlinear susceptibility [χ(3)] in comparison with the pure TiO2 NPs. In this extensive investigation, not only a remarkable correlation has been established regarding the incorporation of Ag into TiO2 matrix with thermal-optic influence (MHz interaction) but also the fundamental plasmon-enhanced nonlinear absorption (NLA) in the case of 1 kHz pulse excitation has been decisively recognized. The synthesized nanocomposites were scrupulously probed in the near-IR regime, unveiling the presence of a prominent 3PA (with retrieved coefficients of ~10-23 cm3/W2 using kHz excitation), an essentially rare observation in these kinds of NPs.

Ultrathin Solar Cells Based on Atomic Layer Deposition of Cubic versus Orthorhombic Tin Monosulfide

Tin monosulfide can be grown in cubic (π-SnS) and orthorhombic (α-SnS) polymorphs by low-temperature atomic layer deposition (ALD). The optical properties of these polymorphs make them attractive for the realization of plasmonic solar cells with ultrathin absorber layers down to 10 nm in thickness. SnS is also an earth-abundant and nontoxic compound semiconductor of high interest for regular thin-film photovoltaics. To better understand the behavior of the two SnS polymorphs in ultrathin solar cell configurations, we here fabricate, characterize, and analyze a range of such devices. ALD is used to grow SnS and form heterojunctions with zinc oxysulfide [Zn(O,S)], acting as a buffer layer with a composition-tunable bandgap. Apart from the roles of the SnS polymorph and Zn(O,S) composition, the effects of the back contact material and thicknesses of buffer and absorber layers are investigated. Devices using π-SnS and pure ZnO buffers yield the highest photocurrents (3.1 mA/cm2) and higher open circuit voltage (159 mV) than similar α-SnS-based devices. Analysis of the equivalent-circuit parameters suggests that interface recombination limits the voltage for these devices. While Zn(O,S) with a higher sulfur content provides chemical passivation of the SnS interface and excessive open circuit voltages above 600 mV, it also exhibits a too high conduction band offset, which hampers current collection. A growth delay during the ALD of Zn(O,S) on SnS initially amplifies the known sulfur–oxygen exchange reaction, such that a sulfur-rich Zn(O,S) region forms next to the SnS interface. This causes a thin ZnS-like barrier to form already for low cycle fractions of the H2S precursor in the ALD super-cycle. Voltage and fill factor trends suggest an optimal SnS absorber layer thickness in the range of 15–35 nm, presenting an opportunity for plasmonic absorption enhancement. Devices with π-SnS show most promise, but interface recombination versus current-blocking is a dilemma for the SnS/Zn(O,S) heterojunction.

Enhanced PEC Water Splitting Performance of Silver Nanoparticle-Coated CdS Nanowire Photoanodes: The Role of Silver Deposition

In this work, Ag@CdS nanowires (NWs) were fabricated via a facile hydrothermal route and magnetron sputtering. The structure and morphology of the Ag@CdS NWs were characterized by field emission scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and X-ray photon spectroscopy. The synthesized Ag@CdS NWs exhibit an enhanced light sensitizing ability due to plasmon-enhanced absorption at the Ag and CdS interface. The Ag@CdS NW photoanode exhibits superior light harvesting and photoelectrochemical performance with an optimal photocurrent density of about 6.15 mA/cm2 at a 0.18 V bias versus the saturated calomel electrode (SCE) and a photocurrent density of about 4.7 times compared to that of the pure CdS NW photoanode. The photochemical conversion efficiency calculated for Ag(45 s)@CdS NWs is found to be 6.6% (potential vs SCE at 0.12 V) compared to 1.28% for CdS NWs at the same potential. The H2 generation obtained from the Ag(45 s)@CdS NW photoanode is 1.8 times higher than that from the pure CdS NW photoanode.

Fabrication of Infrared-Compatible Nanofluidic Devices for Plasmon-Enhanced Infrared Absorption Spectroscopy

Nanofluidic devices have offered us fascinating analytical platforms for chemical and bioanalysis by exploiting unique properties of liquids and molecules confined in nanospaces. The increasing interests in nanofluidic analytical devices have triggered the development of new robust and sensitive detection techniques, especially label-free ones. IR absorption spectroscopy is one of the most powerful biochemical analysis methods for identification and quantitative measurement of chemical species in the label-free and non-invasive fashion. However, the low sensitivity and the difficulties in fabrication of IR-compatible nanofluidic devices are major obstacles that restrict the applications of IR spectroscopy in nanofluidics. Here, we realized the bonding of CaF2 and SiO2 at room temperature and demonstrated an IR-compatible nanofluidic device that allowed the IR spectroscopy in a wide range of mid-IR regime. We also performed the integration of metal-insulator-metal perfect absorber metamaterials into nanofluidic devices for plasmon-enhanced infrared absorption spectroscopy with ultrahigh sensitivity. This study also shows a proof-of-concept of the multi-band absorber by combining different types of nanostructures. The results indicate the potential of implementing metamaterials in tracking several characteristic molecular vibrational modes simultaneously, making it possible to identify molecular species in mixture or complex biological entities.

Impact of Different Metals on the Performance of Slab Tamm Plasmon Resonators.

We investigate the concept of slab Tamm plasmons (STP) in regard to their properties as resonant absorber or emitter structures in the mid-infrared spectral region. In particular, we compare the selective absorption characteristics resulting from different choices of absorbing material, namely Ag, W, Mo or highly doped Si. We devised a simplified optimization procedure using finite element simulations for the calculation of the absorption together with the application of micro-genetic algorithm (GA) optimization. As characteristic for plasmonic structures, the specific choice of the metallic absorber material strongly determines the achievable quality factor (Q). We show that STP absorbers are able to mitigate the degradation of Q for less reflective metals or even non-metals such as doped silicon as plasmonic absorber material. Moreover, our results strongly indicate that the maximum achievable plasmon-enhanced absorption does not depend on the choice of the plasmonic material presuming an optimized configuration is obtained via the GA process. As a result, absorptances in the order of 50–80% could be achieved for any absorber material depending on the slab thickness (up to 1.1 µm) and a target resonance wavelength of 4.26 µm (CO2 absorption line). The proposed structures are compatible with modern semiconductor mass fabrication processes. At the same time, the optimization procedure allows us to choose the best plasmonic material for the corresponding application of the STP structure. Therefore, we believe that our results represent crucial advances towards corresponding integrated resonant absorber and thermal emitter components.

Plasmon-Enhanced Vibrational Spectroscopy of Semiconductors Nanocrystals

A review of recent results and new data on the study of the optical response from semiconductor nanocrystals obtained using plasmon-enhanced optical spectroscopy, including surface enhanced Raman scattering (SERS) and plasmon-enhanced IR absorption, is presented. These methods are based on the amplification of the phonon response of semiconductor nanocrystals located in the field of localized surface plasmon resonance (LSPR) of metal nanostructures. Owing to the choice of a specific morphology of metal nanostructures, coincidence of the LSPR energy with the laser excitation energy and / or the energy of optical phonons in nanocrystals is provided. Resonant conditions ensure a significant increase in local electric fields and, as a result, a sharp increase in the Raman signal and IR absorption at the frequencies of surface optical phonons of nanocrystals. Amplification of the optical response makes it possible not only to detect monolayer coatings of nanocrystals, but also to study their crystal structure, phase and element compositions, and internal mechanical stresses. Application of Raman scattering (RS) in combination with atomic force microscopy with the use of a metallized probe has opened up new possibilities for analyzing the vibrational and electronic spectra of nanocrystals with nanometer spatial resolution

Enhancement and Suppression of Resonance Energy Transfer Near Metal Nanoparticles

Plasmons are known to promote light–matter interaction, providing a powerful tool to increase the rate of energy transfer between donor and acceptor molecules that are appropriately located near a plasmonic particle, a phenomenon called plasmon-coupled resonance energy transfer (PC-RET). In this work, we utilize a Mie theory-based method to calculate the PC-RET rate for a donor–acceptor pair interacting with a single spherical particle, with the goal of identifying key geometrical factors in plasmonic systems that determine the RET rate. We also determine the plasmon enhancement contribution to absorption by the donor, and then combine this with the RET efficiency to determine plasmon enhancement to the overall acceptor formation rate. We find that the RET is often suppressed by coupling to plasmons on a single-molecule level although plasmon-enhanced absorption can lead to a net increase in acceptor formation rate in the presence of the nanoparticle. A quasistatic analysis reveals the dependence of multipolar contributions on the distance of the fluorophores from the metal particle. Finally, it is demonstrated from an analysis of experimental RET results that the structure of a nanophotonic system can be determined from the sensitivity of the RET rate to the system geometry.

Large plasmonic absorption enhancement effect of triangular silver nanowires in silicon.

Two-dimensional finite difference time domain (FDTD) simulations were performed for evaluating optical absorption enhancement and loss effects of triangular silver (Ag) nanowires embedded in silicon (Si) thin-film photovoltaic device structures. Near-bandgap absorption enhancement in Si was much larger than the reported values of other nanostructures from similar simulations. A nanowire with equal sides of 20 nm length showed 368-fold absorption enhancement whereas only 5× and 15× values of solid spherical and two-dimensional core-shell type nanostructures, respectively. Undesirable absorption loss in the metal of the nanowire was 3.55× larger than the absorption in Si which was comparable to the value reported for the spherical nanoparticle. Interestingly, as the height of the nanowire was increased to form a sharper tip, absorption loss showed a significant drop. For a nanowire with 20 nm base and 20 nm height, absorption loss was merely 1.91× larger than the absorption in Si at the 840 nm plasmon resonance. This drop could be attributed to weaker plasmon resonance manifested by lower metallic absorption in the spatial absorption map of the nanowire. However, absorption enhancement in Si was still large due to strong plasmonic fields at the sharper and longer tip, which was effective in enhancing absorption over a larger area in Si. Our work shows that the shape of a nanostructure and its optimization can significantly affect plasmonic absorption enhancement and loss performance in photovoltaic applications.

Graphene plasmonic devices for terahertz optoelectronics

Abstract Plasmonic excitations, consisting of collective oscillations of the electron gas in a conductive film or nanostructure coupled to electromagnetic fields, play a prominent role in photonics and optoelectronics. While traditional plasmonic systems are based on noble metals, recent work has established graphene as a uniquely suited materials platform for plasmonic science and applications due to several distinctive properties. Graphene plasmonic oscillations exhibit particularly strong sub-wavelength confinement, can be tuned dynamically through the application of a gate voltage, and span a portion of the infrared spectrum (including mid-infrared and terahertz (THz) wavelengths) that is not directly accessible with noble metals. These properties have been studied in extensive theoretical and experimental work over the past decade, and more recently various device applications are also beginning to be explored. This review article is focused on graphene plasmonic nanostructures designed to address a key outstanding challenge of modern-day optoelectronics – the limited availability of practical, high-performance THz devices. Graphene plasmons can be used as a means to enhance light–matter interactions at THz wavelengths in a highly tunable fashion, particularly through the integration of graphene resonant structures with additional nanophotonic elements. This capability is ideally suited to the development of THz optical modulators (where absorption is switched on and off by tuning the plasmonic resonance) and photodetectors (relying on plasmon-enhanced intraband absorption or rectification of charge-density waves), and promising devices based on these principles have already been reported. Novel radiation mechanisms, including light emission from electrically excited graphene plasmons, are also being explored for the development of compact narrowband THz sources.