Cooperative plasmon enhanced organic solar cells with thermal coevaporated Au and Ag nanoparticles

Cooperative plasmon enhanced small molecule organic solar cells are demonstrated based on thermal coevaporated Au and Ag nanoparticles (NPs). The optimized device with an appropriate molar ratio of Au:Ag NPs shows a power conversion efficiency of 3.32%, which is 22.5% higher than that of the reference device without any NPs. The improvement is mainly contributed to the increased short-circuit current which resulted from the enhanced light harvesting due to localized surface plasmon resonance of Au:Ag NPs and the increased conductivity of the device. Besides, factors that determining the performance of the Au:Ag NPs cooperative plasmon enhance organic solar cells are investigated, and it finds that the thickness of MoO₃ buffer layer plays a crucial role. Owing to the different diameter of the thermal evaporated Au and Ag NPs, a suitable MoO₃ buffer layer is required to afford a large electromagnetic enhancement and to avoid significant exciton quenching by the NPs.     

Power conversion efficiency enhancement of organic solar cells by addition of gold nanostars,nanorods, and nanospheres

The effects of gold (Au) nanoparticles (NPs) with different morphologies (star, rod, sphere) incorporated into buffer layer, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), of polymer-based organic solar cells (OSCs) were investigated. Solar cells having gold nanoparticles exhibited significant improvement in device efficiency relative to the reference device. The observed improvement is most likely due to the surface plasmon and enhanced light reflection and scattering properties of the Au NPs. The power conversion efficiency (PCE) is increased ca. 29% with Au nanostars, ca. 14% with Au nanorods and 11% with Au nanospheres compared to the device with no Au NP (reference device). Au nanostars provide the strongest contribution to the efficiency among all NP morphologies studied as they have large size, sharp features, and strongest localized surface plasmon resonance effect associate with their morphology.     

Realizing both improved luminance and stability in organic light-emitting devices based on a solution-processed inter-layer composed of MoOX and Au nanoparticles mixture

We report on the solution-processed mixture of Au nanoparticles (NPs) and MoO_X as an inter-layer in organic light-emitting devices (OLEDs), leading to the enhanced light emission and good stability. An impressive enhancement in current efficiency and power efficiency is achieved up to 70% and 100%, respectively. A systematic study to the effect of the Au NPs:MoO_X inter-layer on OLEDs demonstrates that the improved electrical properties is mainly ascribed to the enhanced hole injection due to the high work function of MoO_X and the good conductivity of Au NPs, and the enhanced optical properties is mainly attributed to the localized surface plasmon induced by Au NPs, which makes a great contribution to the improved efficiency. Besides, Au NPs:MoO_X inter-layer also behaves superior to the frequently-used polyethylene dioxythiophene:polystyrene sulfonate (PEDOT:PSS) in device stability. The decay ratio for Au NPs:MoO_X based device is 60% after 80 h, while it is nearly dying out for the device with PEDOT:PSS inter-layer.     

TiN Nanoparticles for Enhanced THz Generation in TDS Systems

By virtue of the surface plasmon resonance effect, plasmonic nanoparticles (NPs) can localize the light field and significantly enhance the performance of some optoelectronic devices. In this work, NPs are employed for an enhanced generation of terahertz radiation from LT-GaAs-based antennas. Therefore, we have prepared plasmonic TiN NPs by direct ultrasonication (ULS) and pulsed laser ablation (PLA) techniques. The zeta potential, particle size, and absorbance were used to characterize the NPs in their colloidal forms in a comparison to commercial Au NPs. A layer of polydispersed titanium nitride (TiN) NPs prepared by PLA and deposited on the surface of an LT-GaAs device shows a significant improvement of terahertz signal generation from these devices with an enhancement of the peak to peak amplitude of 100%.     

金属表面等离激元增强聚合物太阳电池

研究了Au纳米颗粒表面等离激元增强聚噻吩(P3HT)与富勒烯衍生物(PCBM)共混体系聚合物太阳电池的光电转换效率。Au纳米颗粒表面由双十烷基二甲基溴化铵(DDAB)修饰,能够均匀分散在活性层中。研究了Au纳米颗粒的质量分数对电池性能的影响,发现质量分数为1.2%时,电池性能最佳,转换效率高达3.76%,较未掺杂的参比电池相对提高约20%。掺入Au纳米颗粒后P3HT和PCBM共混膜光吸收显著增强,从而使电池外量子效率大大增加。电池效率的提升主要归结于Au纳米颗粒表面等离激元激发所引起的近场增强。     

Supported Faceted Gold Nanoparticles with Tunable Surface Plasmon Resonance for NIR‐SERS

A novel dry plasma methodology for fabricating directly stabilized substrate‐supported gold nanoparticle (NP) ensembles for near infrared surface enhanced Raman scattering (NIR SERS) is presented. This maskless stepwise growth exploits Au‐sulfide seeds by plasma sulfidization of gold nuclei to produce highly faceted Au NPs with a multiple plasmon resonance that can be tuned from the visible to the near infrared, down to 1400 nm. The role of Au sulfidization in modifying the dynamics of Au NPs and of the corresponding plasmon resonance is discussed. The tunability of the plasmon resonance in a broad range is shown and the effectiveness as substrates for NIR SERS is demonstrated. The SERS response is investigated by using different laser sources operating both in the visible and in the NIR. SERS mapping of the SERS enhancement factor is carried out in order to evaluate their effectiveness, stability, and reproducibility as NIR SERS substrates, also in comparison with gold NPs fabricated by conventional sputtering and with the state‐of‐the‐art in the current literature.     

Controlled positioning of metal nanoparticles in an organic light-emitting device for enhanced quantum efficiency

It is shown that there exists an optimum distance between the plane where nanoparticles (NPs) are positioned and the active layer of Au-NP-embedded organic light-emitting devices (OLEDs) for the maximum external quantum efficiency. Au NPs are precisely positioned in a specific plane in the hole-transport layer using a dry, room-temperature aerosol technique at atmospheric pressure. By controlling the position of the Au NPs and their density, we optimize the external quantum efficiency of the Au-NP-embedded OLEDs, with the maximum efficiency being 38% larger than that of the control device without Au NPs. In contrast to commonly employed methods to incorporate metal NPs in an organic layer, such as vacuum thermal evaporation or spin coating, the aerosol-deposited Au NPs do not penetrate into the underlying organic layer, not only allowing for precise control of the vertical (perpendicular to the substrate surface) position of the Au NPs, but also minimizing damage to the hole-transport organic material. Our electrical and optical characterizations show that the existence of the optimal distance occurs by the competition between the increased electron–hole recombination probability caused by the electrostatic effects of holes trapped in the Au NPs and the metal induced quenching.     

Enhanced ultraviolet emission of ZnO microrods array based on Au surface plasmon

In this work, the Au/ZnO hybrid microstructure was fabricated by assembling Au nanoparticles (NPs) onto the surface of ZnO microrods, and an obviously improved ultraviolet (UV) emission of ZnO is observed in the hybrid microstructure. About 27-fold enhancement ratio of the UV emission to the green band emission of ZnO is achieved. The underlying enhanced mechanism of the UV emission intensities can be ascribed to the charge transfer and the efficient coupling between ZnO excitons and Au surface plasmon (SP).     

Large Upconversion Enhancement in the “Islands” Au–Ag Alloy/NaYF4: Yb3+, Tm3+/Er3+ Composite Films,and Fingerprint Identification

The surface plasmon (SP) modulation is a promised way to highly improve the strength of upconversion luminescence (UCL) and expand its applications. In this work, the “islands” Au–Ag alloy film is prepared by an organic removal template method and explored to improve the UCL of NaYF₄: Yb3+, Tm³⁺/Er³⁺. After the optimization of Au–Ag molar ratio (Au_1.25–Ag_0.625) and the size of NaYF₄ nanoparticles (NPs, ≈7 nm), an optimum enhancement as high as 180 folds is obtained (by reflection measurement) for the overall UCL intensity of Tm³⁺. Systematic studies indicate that the UCL enhancement factor (EF) increases with the increased size of metal NPs and the increase of diffuse reflection, with the decreased size of NaYF₄ NPs, with the decreased power density of excitation light and with improving order of multiphoton populating. The total decay rate varies only ranging of about 20% while EF changes significantly. All the facts above indicate that the UCL enhancement mainly originates from coupling of SP with the excitation electromagnetic field. Furthermore, the fingerprint identification based on SP‐enhanced UCL is realized in the metal/UC system, which provides a novel insight for the application of the metal/UC device.     

Enhancement of the power conversion efficiency due to the plasmonic resonant effect of Au nanoparticles in ZnO nanoripples

Au-ZnO nanoripples (NRs) were synthesized by using a sol-gel method for utilization as an electron transport layer (ETL) in inverted organic photovoltaic (OPV) cells. Absorption spectra showed that the plasmonic broadband light absorption of the ZnO NRs was increased due to the embedded Au nanoparticles (NPs). In particular, as compared to regular inverted OPV cells with a ZnO NR ETL, the incident photon-to-current efficiency of the inverted OPV cells with a Au-ZnO NR ETL was significantly enhanced due to the localized surface plasmon resonance (LSPR) effect of the Au NRs. The enhancement of the short-circuit current density (10.05 mA/cm²) of the inverted OPV cells with a Au-ZnO NR ETL was achieved by the insertion of the Au NPs into the ZnO NRs. The power conversion efficiency (PCE) of the OPV cells with Au-ZnO NRs was 3.25%. The PCE of the inverted OPV cells fabricated with a Au-ZnO NR ETL was significantly improved by 20.37% in comparison with that of inverted OPV cells fabricated with a ZnO NR ETL. This improvement can mainly be attributed to an increase in light absorption in the active layer due to the generation of the LSPR effect resulting from the existence of the Au NPs embedded in the ZnO NRs.     

等离激元共振增强多晶硅薄膜太阳电池性能研究

采用磁控溅射方法,在多晶硅薄膜太阳电池表面沉积了不同粒径大小的Au纳米粒子,利用粒径大小可调控的Au纳米粒子的局域表面等离激元共振增强效应(LSPR),对入射光中的可见光区域实现“光俘获”;采用UV-vis吸收光谱对LSPR进行了研究,结果表明,LSPR能够有效拓展Au纳米粒子的光谱响应范围(400～800 nm),并且,随着Au纳米粒子粒径的增大,LSPR共振吸收峰呈现出明显“红移”;同时,通过SERS表征,证实LSPR能够有效增强Au纳米粒子周围的局域电磁场强度;最后,多晶硅太阳电池的J-V特性曲线表明,当Au纳米粒子溅射时间为50 s时,多晶硅太阳电池光电转换效率(η)最高为14.8％,比未修饰Au纳米粒子的电池η提高了42.3％.     

The dual localized surface plasmonic effects of gold nanodots and gold nanoparticles enhance the performance of bulk heterojunction polymer solar cells

In this study, we investigated the effects of plasmonic resonances induced by gold nanodots (Au NDs), thermally deposited on the active layer, and octahedral gold nanoparticles (Au NPs), incorporated within the hole transport layer, on the performance of bulk heterojunction polymer solar cells (PSCs) based on poly(3-hexyl thiophene) (P3HT) and [6,6]-phenyl-C₆₁butyric acid methyl ester (PC₆₁BM). Thermal deposition of 5.3-nm Au NDs between the active layer and the cathode in a P3HT:PC₆₁BM device resulted in the power conversion efficiency (PCE) of 4.6%—that is 15% greater than that (4.0%) for the P3HT:PC₆₁BM device without Au NDs. The Au NDs provided near-field enhancement through excitation of the localized surface plasmon resonance (LSPR), thereby enhancing the degree of light absorption.     

Surface plasmon spectroscopy of thin composite films of Au nanoparticles and PEDOT:PSS conjugated polymer

We studied the effect of Au nanoparticles (NPs) on optical properties of composite films of poly(3,4-ethylenedioxythiophene): poly (styrenesulfonate) (PEDOT:PSS) mixed with Au NPs of 20, 40 and 60 nm in diameter by surface plasmon resonance (SPR) spectroscopy. The excitation wavelength of SPR redshifts with increasing the concentration of Au NPs in the Au/PEDOT:PSS composite films. The SPR spectra were simulated by using transfer matrix method (TMM) and effective medium approximation (EMA). The SPR wavelength redshift was ascribed to the film thickness increase of Au/PEDOT:PSS composites rather than effective permittivity variation of the composite films induced with Au NPs inclusion.     

Thermo-optical Responses of Nanoparticles: Melting of Ice and Nanocalorimetry Approach

The thermo-optical properties of gold nanoparticles (NPs) embedded in an ice matrix were investigated using photoluminescence and Raman spectroscopy. An intense laser beam alone will not melt ice, but the addition of embedded Au NPs allows for melting with resonant laser light of relatively weak intensity. This is due to the strong absorption of Au NPs in the plasmon resonance regimen. We can determine the threshold melting power, P _melting(T), where T is the background temperature by recording time-resolved Raman scattering signals of the system. A resultant loss of ice signal indicates melting and an absence of conversion to water implicates an irreversible loss of water molecules to the gas phase due to the location of the Au NP agglomerate at or near the ice/vapor surface. For fully embedded NP agglomerates, the ice/water phase transition can be monitored through Raman spectroscopy and the number of NPs in an agglomerate and their interactions can have a greater effect on localized heat generation. The local temperature inside and around the NP agglomerate depends strongly on its geometry and leads to a large scatter in the measured P _melting as a function of the reduced temperature for different agglomerates. Immobilized Au NP agglomerates can also be characterized using single-particle spectroscopy, and results show that the plasmon emission of Au NPs scales with the number of NPs in an agglomerate.     

Reusing of transmitted light by localized surface plasmon enhancing of Ag nanoparticles in organic solar cells

Silver nanoparticles(Ag NPs)are synthesized with chemical method,which are introduced into the traditional organic photovoltaic(OPV)structure.The experimental results show that both the optical and photoelectric properties are en-hanced because of localized surface plasmon(LSP)effects of Ag NPs.The advantage of adding Ag NPs behind active layer in incident direction is discussed.We believe this route can avoid absorption shadow and enhance the reusing of transmitted light of active layer.The average short-circuit current(J SC)of the optimum device can be raised from 9.23mA/cm2 to 10.84mA/cm2,and the energy converting efficiency(PCE)can be raised from 3.22% to 3.85%.     

Localized Surface Plasmon Resonance Promotes Metal–Organic Framework-Based Photocatalytic Hydrogen Evolution

Combining metal nanoparticles (NPs) featured with localized surface plasmon resonance (LSPR) with metal–organic framework (MOF)-based photocatalysts is a novel means for achieving efficient separation of electron–hole pairs. Herein, the Au@NH₂-UiO-66/CdS composites are successfully synthesized by encapsulating Au NPs with LSPR into the NH₂-UiO-66 nanocage, further growing CdS NPs on the surface of the NH₂-UiO-66, which exhibits higher photocatalytic activity in hydrogen evolution reaction under visible-light irradiation than that of NH₂-UiO-66/CdS and CdS, respectively. Transient absorption measurements reveal that MOF is not only a transit station for electrons generated from CdS to Au, but also a receiver for hot electrons generated from plasmonic Au in Au@MOF/CdS composites. Thus, the LSPR-induced hot electron transfer from Au NPs is an important manifestation to prolong the carrier lifetime and enhance the photocatalytic performance. This work provides insights into investigating the photoinduced carrier dynamics of nanomaterials with LSPR effects for enhancing the MOF-based photocatalytic performance.     

Au/TiO2复合纳米结构增强热电子光电探测器宽谱响应性能

宽谱响应光电探测器在图像传感和光通信等领域应用前景广阔。金属微纳结构通过激发表面等离激元共振效应可高效产生热载流子,将它们与宽带隙半导体构成异质结构,便可利用热载流子开发出低成本宽谱响应光电探测器。研究设计了一种基于Au/TiO₂复合纳米结构的热电子光电探测器。其中TiO₂层经退火后形成尺度约为百纳米的凹凸结构,Au纳米颗粒层与用作电极的保形Au膜共同组成了激发表面等离激元共振的纳米结构。由于Au/TiO₂复合纳米结构的协同作用,该器件在400～900 nm范围内具有宽谱光吸收性能,器件的平均光吸收效率为33.84%。在此基础上,该器件能够探测TiO₂本征吸收波段以外的入射光子。例如,在600 nm波长处,器件的响应率为9.67μA/W,线性动态范围为60 dB,器件的上升/下降响应速度分别为1.6 ms和1.5 ms。此外,利用有限元法进行了仿真计算,通过电场分布图验证了Au/TiO₂复合纳米结构中所激发的丰富表面等离激元共振效应是其实现宽谱高效探测的原因所在。     

A plasmonically enhanced polymer solar cell with gold–silica core–shell nanorods

We report the use of chemically synthesized gold (Au)–silica core–shell nanorods with the length of 92.5 ± 8.0 nm and diameter of 34.3 ± 4.0 nm for the efficiency enhancement of bulk heterojunction (BHJ) polymer solar cells. Silica coated Au nanorods were randomly blended into the BHJ layers of these solar cells. This architecture inhibits the carrier recombination at the metal/polymer interface and effectively exploits light absorption at the surface plasmon resonance wavelengths of the Au–silica nanorods. To match the two plasmon resonant peaks of the Au–silica nanorods, we employed a low bandgap polymer, poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′] dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (PCPDTBT) to construct a solar cell. The absorption spectrum of PCPDTBT:[6,6]-phenyl-C₇₁-butyric acid methyl ester (PC₇₀BM) is relatively wide and matches the two plasmon resonance peaks of Au–silica nanorods, which leads to greater plasmonic effects. We also constructed the poly(3-hexylthiophene):[6,6]-phenyl-C₆₁-butyric acid methyl ester (P3HT:PC₆₀BM) cells for comparison. The absorption spectrum of P3HT:PC₆₀BM only overlaps one of the plasmon resonance peak of Au–silica nanorods. The efficiency of the P3HT:PC₆₀BM device incorporating optimized Au–silica nanorods is enhanced by 12.9% from 3.17% to 3.58%, which is due to the enhanced light absorption. Compared with the P3HT:PC₆₀BM device with Au–silica nanorods, the PCPDTBT:PC₇₀BM device with 1 wt% Au–silica nanorods concentration has a higher efficiency of 4.4% with an increase of 26%.     

Broadband Photoresponse Enhancement of a High‐Performance t‐Se Microtube Photodetector by Plasmonic Metallic Nanoparticles

Broadband responsivity enhancement of single Se microtube (Se‐MT) photodetectors in the UV–visible region is presented in this research. The pristine Se‐MT photodetector demonstrates broadband photoresponse from 300 to 700 nm with peak responsivity of ≈19 mA W^?1 at 610 nm and fast speed (rise time 0.32 ms and fall time 23.02 ms). To further enhance the responsivity of the single Se‐MT photodetector, Au and Pt nanoparticles (NPs) are sputtered on these devices. In contrast to only enhancement of responsivity in UV region by Pt NPs, broadband responsivity enhancement (≈600% to ≈800%) of the Se‐MT photodetector is realized from 300 to 700 nm by tuning the size and density of Au NPs. The broadband responsivity enhancement phenomena are interpreted by both the surface modification and surface plasmon coupling. The experimental results of this work provide an additional opportunity for fabricating high‐performance UV–visible broadband photodetectors.     

Novel Method of Preparation of Gold‐Nanoparticle‐Doped TiO2 and SiO2 Plasmonic Thin Films: Optical Characterization and Comparison with Maxwell–Garnett Modeling

SiO₂ and TiO₂ thin films with gold nanoparticles (NPs) are of particular interest as photovoltaic materials. A novel method for the preparation of spin‐coated SiO₂–Au and TiO₂–Au nanocomposites is presented. This fast and inexpensive method, which includes three separate stages, is based on the in situ synthesis of both the metal‐oxide matrix and the Au NPs during a baking process at relatively low temperature. It allows the formation of nanocomposite thin films with a higher concentration of Au NPs than other methods. High‐resolution transmission electron microscopy studies revealed a homogeneous distribution of NPs over the film volume along with their narrow size distribution. The optical manifestation of localized surface plasmon resonance was studied in more detail for TiO₂‐based Au‐doped nanocomposite films deposited on glass (in absorption and transmittance) and silicon (in specular reflectance). Maxwell–Garnett effective‐medium theory applied to such metal‐doped nanocomposite films describes the peculiarities of the experimental spectra, including modification of the antireflective properties of bare TiO₂ films deposited on silicon by varying the concentration of metal NPs. The antireflective capabilities of the film are increased after a wet etching process.