Size and Shape Effect of Gold Nanoparticles in “Far‐Field” Surface Plasmon Resonance

The “far‐field” surface plasmon resonance (FSPR) of metal nanoparticles, which have built a facile way to emission enhancement of red, green, blue, and white with nice reproducibility, has big potential application in solution‐processed organic light‐emitting diodes (OLEDs). According to the theory of the “far‐field” effect, the reflectivity of the metal surface and the phase shift at the reflection play an important role in enhancing ratio, which strongly relate to the size and shape of nanoparticles. In this work, gold nanospheres with different sizes and nanorods are synthesized in order to determine the size and shape effect of FSPR. The results demonstrate that the one with higher reflectivity in a certain range induces a better emission enhancement in the luminous efficiency and the maximum brightness. The nanoparticles with bigger sizes and shape of rods have higher reflectivity, which is consistent with the simulation based on FSPR effect. The phase shifts of different nanoparticles are optimized by the distance between gold nanoparticles and emitters. The metal NPs with a high reflectivity and the applicable phase shift will have big potential for the emission enhancement in OLEDs.     

Enhanced Device Performances of Blue‐Emitting PLEDs Coupled with Silver‐Nanoicosahedrons

Silver‐nanoicosahedron particles (AgNIPs) are produced by chemical reduction and photochemical methods and doped into the hole transport layer (HTL) or emissive layer (EML) of blue‐emitting polymer light‐emitting diodes (PLEDs) to improve their luminous efficiency. The optimal distributed‐densities of the AgNIPs are determined from current density–voltage–luminance measurements at different doping concentrations. The AgNIP dopant doses that maximize the average luminous efficiency of the proposed PLED are 6.71 µg cm^?2 in EML (achieving 3.48 cd A^?1) and 6.88 µg cm^?2 in HTL (achieving 3.35 cd A^?1). Although the luminous efficiencies of the blue‐emitting PLEDs fabricated by both doping methods are not significantly different, the maximum plasmonic enhancement (around 30‐fold) of the blue‐emitting PLED with AgNIPs in EML is red‐shifted to the green region (≈530 nm in the electroluminescence spectrum), seriously degrading the luminescent monochromaticity of the blue‐emitting PLED. The maximum plasmonic enhancement (around 33‐fold) of blue‐emitting PLED with AgNIPs in HTL occurred at 430 nm, overlapping the localized surface‐plasmon resonance extinctions of the AgNIPs in HTL (425 nm), thus favoring the enhancement of fluorescence emission. Therefore, to enhance the large‐area emission of blue‐emitting PLEDs, the AgNIPs should be doped in the HTL rather than the EML.     

Near‐field optical enhancement by lead‐sulfide quantum dots and metallic nanoparticles for SERS

There is a growing interest in using quantum dots (QDs) and metallic nanoparticles (NPs), both for luminescence enhancement and surface‐enhanced Raman scattering (SERS). Here, we study the electromagnetic‐field enhancement that can be generated by lead‐sulfide (PbS) QDs using three‐dimensional finite‐element simulations. We investigate the field enhancement associated with combinations of PbS QDs with metallic NPs and substrates. The results show that high field enhancement can be achieved by combining PbS QDs with metallic NPs of larger sizes. The ideal size for Ag NPs is 25 nm, providing a SERS enhancement factor of ~5*10⁸ for light polarization parallel to the NP dimer axis and a gap of 0.6 nm. For Au NPs, the bigger the size, the higher is the field for the studied diameters, up to 50 nm. The near‐field values for PbS QDs above metallic substrates were found to be lower compared to the case of PbS QD‐metal NP dimers. This study provides the understanding for the design and application of QDs for the enhancement of near‐field phenomena. Copyright © 2013 John Wiley & Sons, Ltd.     

Highly Enhanced Emission of Visible Light from Core–Dual‐Shell‐Type Hybridized Nanoparticles

Core–dual‐shell‐type hybridized nanoparticles (NPs) having Au‐core/dye‐doped silica inner shell/Au outer shell are successfully fabricated by developing a biphasic process that is a kind of so‐called “one‐pot” method. The resulting hybridized NPs exhibit evidently about 20‐fold enhancement of fluorescence intensity, increase in fluorescence quantum yield, and decrease in fluorescence lifetime. These effects depend on the metal nanostructure being optimized, compared with the reference hybridized NPs with neither a Au‐core nor a Au outer shell, due to the gap‐mode effect induced by localized surface plasmon resonance in the core–dual‐shell‐type MIM‐like nanostructure. More detailed elucidation concerning the enhancement mechanism will provide the possibility of photonic device application, for example as a high‐performance point light source, nanolaser, or sensor for bioimaging in the visible region in the near future.     

Dual plasmonic‐enhanced bulk‐heterojunction solar cell incorporating gold nanoparticles into solution‐processed anode buffer layer and active layer

A dual plasmonic resonance effect on the performance of poly(3‐hexylthiophene) (P3HT):phenyl C61‐butyricacid methyl ester (PC61BM) based polymer solar cells (PSCs) has been demonstrated by selectively incorporating 25 nm colloidal gold nanoparticles (Au NPs) in a solution‐processed molybdenum oxide (MoO₃) anode buffer layer and 5 nm colloidal Au NPs in the active P3HT:PCBM layer. The devices exhibit up to ～20% improvement in power conversion efficiency which is attributed to the dual effect of localized surface plasmon resonance (LSPR) of Au NPs with enhanced light absorption and exciton generation. Our report shows a guideline on the usage of dual LSPR effect for the solution‐processed polymer solar cells to achieve high efficiencies. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Silver‐Based Nanoparticles for Surface Plasmon Resonance in Organic Optoelectronics

Organic optoelectronic devices including organic light‐emitting diodes (OLEDs) and polymer solar cells (PSCs) have many advantages, including low‐cost, mechanical flexibility, and amenability to large‐area fabrication based on printing techniques, and have therefore attracted attention as next‐generation flexible optoelectronic devices. Although almost 100% internal quantum efficiency of OLEDs has been achieved by using phosphorescent emitters and optimizing device structures, the external quantum efficiency (EQE) of OLEDs is still limited due to poor light extraction. Also, although intensive efforts to develop new conjugated polymers and device architectures have improved power conversion efficiency (PCE) up to 8%–9%, device efficiency must be improved to >10% for commercialization of PSCs. The surface plasmon resonance (SPR) effect of metal nanoparticles (NPs) can be an effective way to improve the extraction of light produced by decay of excitons in the emission layer and by absorption of incident light energy within the active layer. Silver (Ag) NPs are promising plasmonic materials due to a strong SPR peak and light‐scattering effect. In this review, different SPR properties of Ag NPs are introduced as a function of size, shape, and surrounding matrix, and review recent progress on application of the SPR effect of AgNPs to OLEDs and PSCs.     

High–Yield Production of Uniform Gold Nanoparticles with Sizes from 31 to 577 nm via One‐Pot Seeded Growth and Size‐Dependent SERS Property

In this work, uniform, quasi‐spherical gold nanoparticles (Au NPs) with sizes of 31–577 nm are prepared via one‐pot seeded growth with the aid of tris‐base (TB). Distinct from the seeded growth methods available in literature, the present method can be simply implemented by subsequently adding the aqueous dispersion of the 17 nm Au‐NP seeds and the aqueous solution of HAuCl₄ into the boiling aqueous TB solution. It is found that at the optimal pH range, the sizes of the final Au NPs and their concentrations are simply controlled by either the particle number of the Au seed dispersion or the concentration of the HAuCl₄ solution, while the latter enables us to produce large Au NPs at very high concentration. Moreover, as‐prepared Au NPs of various sizes are coated on glass substrates to test their surface‐enhanced Raman scattering (SERS) activities by using 4‐aminothiophenol (4‐ATP) molecules as probes, which exhibit “volcano type” dependence on the Au NP sizes at fixed excitation wavelength. Furthermore, the Au NPs with sizes of ≈97 and 408 nm exhibit the largest SERS enhancement at the excitation wavelength of 633 and 785 nm, respectively.     

Poly(3‐hexylthiophene)/Gold Nanoparticle Hybrid System with an Enhanced Photoresponse for Light‐Controlled Electronic Devices

Light‐controlled electrical behavior of polymer/nanoparticle hybrid system in ambient condition is demonstrated. By embedding gold nanoparticles (Au NPs) in a poly(3‐hexylthiophene) (P3HT) matrix, the photoresponses of the nanocomposite films are enhanced. The electrical behavior of the P3HT/Au NPs nanocomposite transistors and inverters are tuned over a wide range in depletion mode. UV‐visible absorption spectroscopy, ultraviolet photoelectron spectroscopy (UPS), and steady‐state photoluminescence (PL) spectroscopy are used to analyze the nanocomposite films. The findings provide a better understanding of light‐induced threshold voltage shifts of P3HT‐based field‐effect transistors and inverters and demonstrate their potential applications in electronic signal modulation for solution‐processed integrated circuits.     

Comparing the Contribution of Visible‐Light Irradiation,Gold Nanoparticles,and Titania Supports in Photocatalytic Nitroaromatic Coupling and Aromatic Alcohol Oxidation

Under visible‐light irradiation, gold nanoparticles (Au NPs) supported by titania (TiO₂) nanofibers show excellent activity and high selectivity for both reductive coupling of nitroaromatics to corresponding azobenzene or azoxylbenzene and selective oxidation of aromatic alcohols to corresponding aldehydes. The Au NPs act as active centers mainly due to their localized surface plasmon resonance (LSPR) effect. They can effectively couple the photonic energy and thermal energy to enhance reaction efficiency. Visible‐light irradiation has more influence on the reduction than on the oxidation, lowering the activation energy by 24.7 kJ mol^?1 and increasing the conversion rate by 88% for the reductive coupling, compared to merely 8.7 kJ mol^?1 and 46% for the oxidation. Furthermore, it is found that the conversion of nitroaromatics significantly depends on the particle size and specific surface area of supported Au NPs; and the catalyst on TiO₂(B) support outperforms that on anatase phase with preferable ability to activate oxygen. In contrast, for the selective oxidation, the effect of surface area is less prominent and Au NPs on anatase exhibit higher photo‐catalytic activity than other TiO₂ phases. The catalysts can be recovered efficiently because the Au NPs stably attach to TiO₂ supports by forming a well‐matched coherent interface observed via high‐resolution TEM.     

Fabrication of NIR‐Excitable SERS‐Active Composite Particles Composed of Densely Packed Au Nanoparticles on Polymer Microparticles

A simple fabrication method is demonstrated for surface‐enhanced Raman scattering (SERS)‐active plasmonic nanoballs, which consisted of Au nanoparticles (NPs) and core–shell polystyrene and amino‐terminated poly(butadiene) particles, by heterocoagulation and Au NP diffusion. The amount of Au NPs introduced into the core–shell particles increases with the concentration of Au NPs added to the aqueous dispersion of the core–shell particles. When the amount of Au NPs increases, closely packed, three‐dimensionally arranged and close‐packed Au NPs arrays are formed in the shells. Strong SERS signals from para‐mercaptophenol adsorbed onto composite particles with multilayered Au NPs arrays are obtained by near‐infrared (NIR) light illumination.     

Simple method to prepare size‐controllable gold nanoparticles in solutions and their applications on surface‐enhanced Raman scattering

We report here, for the first time, a simple method to prepare size‐controllable Au nanoparticles (NPs) in aqueous solutions from bulk Au substrates. First, chitosan (Ch)‐capped Au‐containing complexes were prepared by electrochemical oxidation–reduction cycles in 0.1 N NaCl and 1 g/l Ch solutions. Then the solutions were heated from room temperature to boiling at different heating rates to synthesize size‐controllable Au NPs. The particle sizes of the prepared Au(111) NPs could be controlled from 5 to 30 nm with an increase of the heating rate during preparation. Experimental results indicate that the prepared Au(111) NPs with diameters ranging from 10 to 30 nm can serve as surface‐enhanced Raman scattering active probes for molecules of rhodamine 6G. Copyright © 2010 John Wiley & Sons, Ltd.     

Improving efficiency roll-off in phosphorescent OLEDs by modifying the exciton lifetime

Studies on phosphorescent organic light emitting devices (PhOLEDs) with phosphorescent emitter, fac-tris (2-phenylpyridine) iridium (Ir(ppy)(3)), show that the lifetime of triplet exciton is modified by surface plasmon coupling of Au nanoparticles (NPs). Interactions between the triplet exciton and gold (Au) nanoparticles (NPs) lead to a decrease in the exciton lifetime and result in the spontaneous emission decay rate of triplet exciton faster as the distance between the phosphorescent material and the Au NPs becomes smaller. This interaction reduces the efficiency roll-off of Au NPs containing device. These results provide new guides for device design to improve efficiency performance.     

Bandgap engineering of GaxZn1–xO nanowire arrays for wavelength‐tunable light‐emitting diodes

Wavelength‐tunable light‐emitting diodes (LEDs) of Ga_xZn_1–xO nanowire arrays are demonstrated by a simple modified chemical vapor deposition heteroepitaxial growth on p‐GaN substrate. As a gallium atom has similar electronegativity and ion radius to a zinc atom, high‐level Ga‐doped Ga_xZn_1–xO nanowire arrays have been fabricated. As the x value gradually increases from 0 to 0.66, the near‐band‐edge emission peak of Ga_xZn_1–xO nanowires shows a significant shift from 378 nm (3.28 eV) to 418 nm (2.96 eV) in room‐temperature photoluminescence (PL) measurement. Importantly, the electroluminescence (EL) emission of Ga_xZn_1–xO nanowire arrays LED continuously shifts with a wider range (∼100 nm), from the ultraviolet (382 nm) to the visible (480 nm) spectral region. The presented work demonstrates the possibility of bandgap engineering of low‐dimensional ZnO nanowires by gallium doping and the potential application for wavelength‐tunable LEDs.     

A facile high‐performance SERS substrate based on broadband near‐perfect optical absorption

Plasmonic systems based on metal nanoparticles on a metal film with high optical absorption have generated great interests for surface‐enhanced Raman scattering (SERS). In this study, we prepare a broadband‐visible light absorber consisting Au nanotriangles on the surface of a continuous optically opaque gold film separated with a dielectric SiO₂ layer, which is a typical metal‐insulator‐metal (MIM) system, and demonstrate it as an efficient SERS substrate. The MIM nanostructure, prepared using nanosphere lithography with a very large area, shows a broadband with absorption exceeding 90% in the wavelength regime of 630–920 nm. We observe an average SERS enhancement factor (EF) as large as 4.9 × 10⁶ with a 22‐fold increase compared to a single layer of Au nanotriangles directly on a quartz substrate. A maximum SERS EF can be achieved by optimizing the thicknesses of the dielectric layer to control the optical absorption. Owing to the simple, productive, and inexpensive fabrication technique, our MIM nanostructure could be a potential candidate for SERS applications. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis of a Au‐on‐Pd Heteronanostructure Stabilized by Citrate and its Catalytic Application

The preparation of Au‐on‐Pd heteronanostructure (HNS) using citrate‐stabilized polycrystalline Pd nanoparticles (NPs) as the seeds is described. The resulting Au‐on‐Pd HNS is characterized and it is found that the formation of Au‐on‐Pd HNS depends greatly on a ratio between Pd seeds and AuCl₄^? ions added and the optimal molar ratio is 10:1. If fewer AuCl₄^? ions are added (Pd/Au ratio is 100:1), the growth of Au NPs only occurs on part of the Pd seeds’ surface. The addition of more AuCl₄^? ions (Pd/Au ratio is 5:1) hinders the growth of Au NPs on the Pd seeds’ surface. To demonstrate the catalytic performance, the electrochemistry oxidation of ethanol and the reduction of p‐nitrophenol by NaBH₄ are chosen to examine the catalytic activity of Au‐on‐Pd HNS. Pd seeds, Au NPs, and poly(vinyl pyrrolidone) (PVP)‐stabilized PdAu nanoalloy are used as the references for comparison. In the first reaction, the catalytic reactivity of Au‐on‐Pd HNS is better than that of corresponding pure Pd or Au NPs, while the opposite occurs for the latter reaction. The catalytic activity of Au‐on‐Pd HNS is much higher than that of PVP‐stabilized PdAu nanoalloy.     

Multiscale electromagnetic SERS enhancement on self‐assembled micropatterned gold nanoparticle films

In this work, we demonstrate a cascaded, multiplicative electromagnetic enhancement effect in surface‐enhanced Raman scattering (SERS) on periodically micropatterned films made of colloidal gold nanoparticles, prepared by a self‐assembly approach, without implying lithography procedures. The multiplicative enhancement effect is obtained by combining surface plasmon near‐field enhancement due to nanoscale features with far‐field photonic coupling by periodic microscale features. The effect is observed for both internal Raman reporters (molecules attached to the Au colloids before their assembly) and external Raman probes (molecules adsorbed on the samples after film assembly). The ability of the patterned films for far‐field light coupling is supported by reflectivity spectra, which present minima/maxima in the visible spectral range. Finite‐difference time‐domain computer simulations of the electric field distribution also support this interpretation. The fabricated dual‐scale SERS substrates exhibit a good spot‐to‐spot reproducibility and time stability, as proved by the SERS response over a time scale longer than 1 month. The experimental demonstration of this cascaded electromagnetic enhancement effect contributes to a better understanding of SERS and can affect future design of SERS substrates. Moreover, such dual‐scale colloidal films prepared by convective self‐assembly can be of general interest for the broader field of nanoparticle‐based devices. Copyright © 2014 John Wiley & Sons, Ltd.     

Multicolor Light‐Emitting Diodes with MoS2 Quantum Dots

Molybdenum disulfide (MoS₂) quantum dots (QDs) are known for their excitation‐wavelength‐dependent photoluminescent (PL) properties. However, the mechanism of this phenomenon is still unclear. Here, small size MoS₂ QDs with a narrow size distribution are synthesized. Based on the decay study and PL dynamics, a reasonable radiation model is presented to understand the special PL properties, i.e., the carrier recombination in the localized surface defect states generated the PL. Accordingly, this optical property is used to fabricate multicolor light‐emitting devices with the same MoS₂ QDs. The emission color covers the full visible spectrum from blue to red, only by adjusting the thickness of the down‐conversion QD layers.     

Coalescence of Cluster Beam Generated Sub‐2 nm Bare Au Nanoparticles and Analysis of Au Film Growth Parameters

In this work is presented the growth model for Au films grown on a carbon substrate at room temperature by using as building blocks Au nanoparticles (NPs) with 1.4 nm mean size generated via remote cluster beam synthesis and soft landing on the substrate. The key results highlighted in this work are that 1) the deposited nanoparticles coalesce at substrate level in such a way that the film growth is 3D, 2) newly formed nanoparticles at substrate level are predominantly magic number clusters and 3) coalescensce takes place as soon as two neighboring nanopartciles come closer than a critical distance. The film growth was investigated by TEM as a function of Au load, in the range 0–1.2 μg/cm². Two distinct regimes are identified: the “landing regime” and the “coalescence regime”. During the latter the film growth is 3D with a dynamic scaling exponent z of 2.13. Particular attention was devoted to the study of the evolution of the NP population from the moment they are generated with the cluster beam generator to the moment they land on the substrate and coalesce with other NPs. Our results show that 1) the NPs generated by the cluster beam are heterogeneous in size and are made by more than 95% by Au Magic numbers, mainly Au₂₀ and Au₅₅ and 2) kinetic processes (coalescence) at substrate level is capable of producing NPs populations made of larger Au magic numbers containing up to several thousands of Au atoms. Experimental and simulation results provide insight into the coalescence mechanism and provide strong evidence that the NPs coalesce when the nearest neighbor distance is below a critical mark. The critical distance is at its minimum 0.4‐0.5 nm and it is still unclear whether it is constant or not although the best matching simulation results seem to point to a superlinear dependence from the NP size difference between two neighboring candidate coalescing NPs. The coalescence phenomenon investigated in this work pinpoints the unique self‐organization properties of these small Au NPs in creating films with a stable edge‐to‐edge mean nearest neighbor distance of the order of 1.4 nm.     

Characterization of Micro‐ and Nanoscale LuPO4:Pr3+,Nd3+ with Strong UV‐C Emission to Reduce X‐Ray Doses in Radiation Therapy

UV‐C emitting nanoscale scintillators can be used to sensitize cancer cells selectively against X‐rays during radiation therapy, due to the lethal DNA lesions caused by UV‐C photons. Unfortunately, nanoscale particles (NPs) show decreased UV‐C emission intensity. In this paper, the influence of different Nd³⁺ concentrations on the UV‐C emission of micro‐ and nanoscale LuPO₄:Pr³⁺ is investigated upon X‐ray irradiation and vacuum UV excitation (160 nm). Co‐doped LuPO₄ results in increased UV‐C emission independent of excitation source due to energy transfer from Nd³⁺ to Pr³⁺. The highest UV‐C emission intensity is observed for LuPO₄:Pr³⁺,Nd³⁺(1%,2.5%) upon X‐ray irradiation. Finally, LuPO₄ NPs co‐doped with different dopant concentrations are synthesized, and the biological efficacy of the combined approach (X‐rays and UV‐C) is assessed using the colony formation assay. Cell culture experiments confirm increased cell death compared to X‐rays alone due to the formation of UV‐specific DNA damages, supporting the feasibility of this approach.     

Design of Enhanced Catalysts by Coupling of Noble Metals (Au,Ag) with Semiconductor SnO2 for Catalytic Reduction of 4‐Nitrophenol

The reduction of 4‐nitrophenol (Nip) into 4‐aminophenol (Amp) by NaBH₄, which is catalyzed by both binary and ternary yolk–shell noble‐metal/SnO₂ heterostructures, is reported. The binary heterostructures contain individual Au or Ag nanoparticles (NPs) and the ternary heterostructures contain both Au and Ag NPs. The Au@SnO₂ yolk–shell NPs are synthesized via a silica seeds‐mediated hydrothermal method. Subsequently, the Au@SnO₂@Ag and Au@SnO₂@Au yolk–shell–shell (YSS) NPs are synthesized, whereby SnO₂ is located between the Au and Ag NPs. The morphology, composition, and optical properties of the as‐prepared samples are analyzed. For the binary heterostructures, the rate of the reduction reaction increases with decreasing particle size. The catalytic results demonstrate the synergistic effect of Au and Ag in the ternary metal–semiconductor heterostructures, which is beneficial to the catalytic reduction of Nip into Amp. Both the binary and ternary heterostructures exhibit significantly better catalytic performances than the corresponding bare Au and Ag NPs. It is envisaged that the current synthesized strategy will promote further interest in the field of bimetal NP‐based catalysis.