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.     

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.     

SHINERS and plasmonic properties of Au Core SiO2 shell nanoparticles with optimal core size and shell thickness

Shell‐isolated nanoparticles (NPs)‐enhanced Raman spectroscopy (SHINERS) can be potentially applied to virtually any substrate type and morphology. How to take a step forward to prepare SHINERS NPs (SHINs) with superior performance is critical for the practical applications of surface‐enhanced Raman scattering (SERS) in the breadth and depth. Here, we present a method to obtain 120 nm diameter gold NPs coated with ultrathin silica shells (1–4 nm). The silica shell can be controlled growth through carefully tuning a series of parameters, such as amount of 3‐aminopropyl triethoxysilane used, pH, reaction time, and reaction temperature. We compare the enhancement factor of the obtained 120 nm Au with a 4 nm silica shell NPs to the 55 nm Au with a 4 nm silica shell NPs, and the activity of a 120 nm SHINs is nearly 24 times that the 55 nm SHIN from a single particle view. We also compare the enhancement factor of 1 nm silica shell Au@SiO₂ NPs with the bare Au NPs. The enhancement factor of 1 nm silica shell Au@SiO₂ NPs was found to be about twice that of the bare particles. For a deeper understanding of the source of the giant enhanced electrical field of the 1 nm silica shell Au@SiO₂ NPs, we study the plasmonic property of single 1 nm silica shell Au@SiO₂ NP on a gold film substrate through correlation of the structure of single NP using SEM with its SPR spectroscopy. We find that the multipolar interaction between the single Au@SiO₂ NP and gold film substrate is important for the SERS. Our studies on the performance of 120 nm SHINs and the plasmonic property of these particles can significantly expand the applications of SHINERS technique and improve the understanding of physical nature of SHINs. Copyright © 2013 John Wiley & Sons, Ltd.     

Layered MoS2 grown on c ‐sapphire by pulsed laser deposition

Layered growth of molybdenum disulphide (MoS₂) was successfully achieved by pulsed laser deposition (PLD) method on c ‐plane sapphire substrate. Growth of monolayer to a few monolayer MoS₂, dependent on the pulsed number of excimer laser in PLD is demonstrated, indicating the promising controllability of layer growth. Among the samples with various pulse number deposition, the frequency difference (A_1g–E¹_2g) in Raman analysis of the 70 pulse sample is estimated as 20.11 cm^–1, suggesting a monolayer MoS₂ was obtained. Two‐dimensional (2D) layer growth of MoS₂ is confirmed by the streaky reflection high energy electron diffraction (RHEED) patterns during growth and the cross‐sectional view of transmission electron microscopy (TEM). The in‐plane relationship, (0006) sapphire//(0002)MoS₂and sapphire//MoS₂ is determined. The results imply that PLD is suitable for layered MoS₂ growth. Additionally, the oxide states of Mo 3d core level spectra of PLD grown MoS₂, analysed by X‐ray photoelectron spectroscopy (XPS), can be effectively reduced by adopting a post sulfurization process. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Mean Particle Diameters. Part VIII. Computer Program to Decompose Mixtures of (Truncated) Lognormal Particle Size Distributions Using Differential Evolution to Generate Starting Values for Nonlinear Least Squares

Multimodal size distributions can result from a mixing of two or more component distributions and arise in quite different application areas. Physical and statistical approaches are described for decomposition of a multimodal particle size distribution into a number of lognormal components. These approaches, incorporated in the Fortran computer program FitDist, use a nonlinear least‐squares (NLLS) optimization, requiring initial parameter estimates. A hybrid deconvolution method has been developed. Differential Evolution (DE), is used for generation of initial parameter values, followed by an NLLS optimization to derive precise parameter values at the local optimum. The DE algorithm is required to decide on the proper number of modes to be fitted. Mathematical relationships have been derived to convert the parameter values of one multimodal lognormal moment distribution, e.g., a number distribution, to those of another moment distribution, e.g., a volume distribution. Moreover, mathematical relationships have been derived to compute mean diameters (Moment‐Ratio notation) from the parameters of a multimodal lognormal size distribution. Fitting a 1.5th moment distribution, being just in between a number and a volume distribution, has been introduced as an instrument to balance inaccuracies in both tails of a distribution due to sampling inaccuracies or truncation of these tails. The program fits a truncated size distribution by fitting its frequency density distribution, whereas a complete size distribution is fitted by fitting the cumulative distribution. Some guidelines are given for fitting Number, Diameter, Surface area, and Volume distributions to measured size distributions. Although fitting of multimodal normal distributions is an option, higher moment distributions will not be fitted as these distributions are not normally distributed. Practical examples demonstrate the validity of the method to decompose multimodal particle size distributions by use of DE.     

Three‐dimensional ultra‐broadband integrated tapered mode multiplexers

The demonstration of a three‐dimensional tapered mode‐selective coupler in a photonic chip is reported. This waveguide‐based, ultra‐broadband mode multiplexer was fabricated using the femtosecond laser direct‐write technique in a boro‐aluminosilicate glass chip. A three‐core coupler has been shown to enable the multiplexing of the LP₀₁, LP and LP spatial modes of a multimode waveguide, across an extremely wide bandwidth exceeding 400 nm, with low loss, high mode extinction ratios and negligible mode crosstalk. Linear cascades of such devices on a single photonic chip have the potential to become a definitive technology in the realization of broadband mode‐division multiplexing for increasing optical fiber capacity.     

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.     

Peptide‐Targeted Gold Nanoparticles for Photodynamic Therapy of Brain Cancer

Targeted drug delivery using epidermal growth factor peptide‐targeted gold nanoparticles (EGF_pep‐Au NPs) is investigated as a novel approach for delivery of photodynamic therapy (PDT) agents, specifically Pc 4, to cancer. In vitro studies of PDT show that EGF_pep‐Au NP‐Pc 4 is twofold better at killing tumor cells than free Pc 4 after increasing localization in early endosomes. In vivo studies show that targeting with EGF_pep‐Au NP‐Pc 4 improves accumulation of fluorescence of Pc 4 in subcutaneous tumors by greater than threefold compared with untargeted Au NPs. Targeted drug delivery and treatment success can be imaged via the intrinsic fluorescence of the PDT drug Pc 4. Using Pc 4 fluorescence, it is demonstrated in vivo that EGF_pep‐Au NP‐Pc 4 impacts biodistribution of the NPs by decreasing the initial uptake by the reticuloendothelial system (RES) and by increasing the amount of Au NPs circulating in the blood 4 h after IV injection. Interestingly, in vivo PDT with EGF_pep‐Au NP‐Pc 4 results in interrupted tumor growth when compared with EGF_pep‐Au NP control mice when selectively activated with light. These data demonstrate that EGF_pep‐Au NP‐Pc 4 utilizes cancer‐specific biomarkers to improve drug delivery and therapeutic efficacy over untargeted drug delivery.     

Investigation of the vibrational modes of ZnO grown by MOCVD on different orientation planes

Wurtzite ZnO thin films were prepared on sapphire substrate by metal organic chemical vapor deposition (MOCVD). Raman scattering studies on different crystallographic textures were performed in the backscattering geometry, and polarization effect is investigated in different configurations and . ZnO Raman modes are investigated in each texture. In the case of ZnO thin film deposed on r‐() sapphire plane and using backscattering geometry, new Raman line was observed at 390 cm⁻¹ because this mode has not been noticed in this geometry. It is shown that the frequencies of the quasi‐phonon modes of the examined thin film are in good agreement with the theoretical values calculated within the framework of Loudon model. Copyright © 2014 John Wiley & Sons, Ltd.     

Relic photon temperature versus redshift and the cosmic neutrino background

Presuming that CMB photons are described by the deconfining phase of an SU(2) Yang‐Mills theory with the critical temperature for the deconfining‐preconfining phase transition matching the present CMB temperature K (SU(2)_CMB), we investigate how CMB temperature T connects with the cosmological scale factor a in a Friedmann‐Lemaître‐Robertson‐Walker Universe. Owing to a violation of conformal scaling at late times, the tension between the (instantaneous) redshift of reionisation from CMB observation () and quasar spectra () is repealed. Also, we find that the redshift of CMB decoupling moves from to which questions ΛCDM cosmology at high redshifts. Adapting this model to the conventional physics of three flavours of massless cosmic neutrinos, we demonstrate inconsistency with the value N_eff ～ 3.36 extracted from Planck data. Interactions between cosmic neutrinos and the CMB implies a common temperature T of (no longer separately conserved) CMB and neutrino fluids. N_eff ～ 3.36 then entails a universal, temperature induced cosmic neutrino mass with . Our above results on z_re and z_dec, derived from SU(2)_CMB alone, are essentially unaffected when including such a neutrino sector.

     

Higher‐Dimensional Unification with continuous and fuzzy coset spaces as extra dimensions

We first review the Coset Space Dimensional Reduction (CSDR) programme and present the best model constructed so far based on the , 10‐dimensional E₈ gauge theory reduced over the nearly‐Kähler manifold with the additional use of the Wilson flux mechanism. Then we present the corresponding programme in the case that the extra dimensions are considered to be fuzzy coset spaces and the best model that has been constructed in this framework too. In both cases the best model appears to be the trinification GUT .     

Organic‐inorganic hybrids based on phenanthrene‐functionalized gold nanoparticles for OLEDs

The electroluminescence intensity of the phenanthrene‐functionalized gold nanoparticles, PMPT‐Au nanoparticles/CPB: Ir(PIA)₂ (acac) film, was increased by 4.9 times compared with control device, CPB: Ir(PIA)₂ (acac) due to coupling between the excitons of emissive layer and localized surface plasmonic resonance of PMPT‐Au NPs. The maximum luminous efficiencies of devices II to IV with PMPT‐Au NPs were 39.2 cd A^?1 (11.8 V), 40.1 cd A^?1 (10.5 V), and 43.1 cd A^?1 (9.0 V), respectively. The increment of current efficiency with PMPT‐Au NP coated devices was strongly related to the energy transfer between the radiated light generated from CBP: Ir(PIA)₂ (acac) emissive layer and localized surface plasmonic resonance excited by PMPT‐Au NP layer.     

Studies on multivalent interactions of quantum dots–protein self-assemble using fluorescence coupled capillary electrophoresis

A method is presented for using a single laser pulse to transform polymorphic polycrystalline gold nanoparticles (Au NPs) into crystalline nanospheres. Transmission electron microscope analysis of the nominally 60-nm-diameter Au NP starting material and the product suspension confirms the production of slightly smaller particles that exhibit greater crystallinity and feature reduced caliper diameter aspect ratios and anisotropy. Centrifugation followed by ultrasonic resuspension into citrate solution separates the nanospheres from the <15 nm ablation fragments, providing a route to monodisperse spherical crystalline Au NPs.     

Nonlinear optical characteristics of monolayer MoSe2

In this study, we utilized picosecond pulses from an Nd:YAG laser to investigate the nonlinear optical characteristics of monolayer MoSe₂. Two‐step growth involving the selenization of pulsed‐laser‐deposited MoO₃ film was employed to yield the MoSe₂ monolayer on a SiO₂/Si substrate. Raman scattering, photoluminescence (PL) spectroscopy, and atomic force microscopy verified the high optical quality of the monolayer. The second‐order susceptibility χ⁽²⁾ was calculated to be ～50 pm V^?1 at the second harmonic wavelength ～810 nm, which is near the optical gap of the monolayer. Interestingly, our wavelength‐dependent second harmonic scan can identify the bound excitonic states including negatively charged excitons much more efficiently, compared with the PL method at room temperature. Additionally, the MoSe₂ monolayer exhibits a strong laser‐induced damage threshold ～16 GW cm^?2 under picosecond‐pulse excitation_. Our findings suggest that monolayer MoSe₂ can be considered as a promising candidate for high‐power, thin‐film‐based nonlinear optical devices and applications.     

Polyvinylpyrrolidone (PVP) assisted single‐step synthesis of kesterite Cu2ZnSnS4 nanoparticles by solvothermal process

Quaternary kesterite‐type Cu₂ZnSnS₄ (CZTS) nanoparticles (NPs) were successfully synthesized by a single‐step solvothermal process. Semiconductor CZTS nanoparticles were obtained from ethylene glycol (EG) and CZTS precursor after solvothermal process at 180 °C for 30 h in polyvinylpyrrolidone (PVP) medium. The synthesized CZTS NPs were further annealed at 450 °C in nitrogen atmosphere and used for further characterizations. The CZTS NPs were characterized using X‐ray powder diffraction (XRD), field emission scanning electron microscopy (FESEM), micro Raman spectroscopy, high resolution transmission electron microscopy (HRTEM) and X‐ray photoelectron spectroscopy (XPS). The optical properties of the CZTS NPs were recorded by UV–vis absorption spectroscopy. The results showed that the synthesized CZTS nanoparticles are kesterite‐type CZTS, with good crystallinity and a stoichiometric composition. Moreover, the prepared nanoparticles have a size ranging from 5–7 nm and a band gap of ～1.5 eV.

     

London penetration depth and thermal fluctuations in the sulphur hydride 203 K superconductor

Recently, compressed H₂S has been shown to become superconducting at 203 K under a pressure of 155 GPa. One might expect fluctuations to dominate at such temperatures. Using the magnetisation critical current, we determine the ground‐state London penetration depth, λ₀=189 nm, and the superconducting energy gap, Δ₀=27.8 meV, and find these parameters are similar to those of cuprate superconductors. We also determine the fluctuation temperature scale, K, which shows that, unlike the cuprates, of the hydride is not limited by fluctuations. This is due to its three dimensionality and suggests the search for better superconductors should refocus on three‐dimensional systems where the inevitable thermal fluctuations are less likely to reduce the observed .

     

Observation of optomechanical coupling in a microbottle resonator

In this work, we report optomechanical coupling, resolved sidebands and phonon lasing in a solid‐core microbottle resonator fabricated on a single mode optical fiber. Mechanical modes with quality factors (Q_m) as high as 1.57 × 10⁴ and 1.45 × 10⁴ were observed, respectively, at the mechanical frequencies and . The maximum  Hz is close to the theoretical lower bound of 6 × 10¹² Hz needed to overcome thermal decoherence for resolved‐sideband cooling of mechanical motion at room temperature, suggesting microbottle resonators as a possible platform for this endeavor. In addition to optomechanical effects, scatter‐induced mode splitting and ringing phenomena, which are typical for high‐quality optical resonances, were also observed in a microbottle resonator.

     

Quantum states and vortex patterns in nanosuperconductors

The quanum levels and corresponding vortex states in nanoscale superconductors are investigated within generalized Bogolubov‐de Gennes theory. For symmetric (square‐shaped) samples thermodynamically stable vortex phases form symmetry‐consistent patterns and no transition to conventional Abrikosov‐like vortex patterns occurs till T=0K for sizes not exceeding 25 nm. For vorticity a giant vortex is stabilized at temperatures in the vicinity of , which transforms into a giant antivortex and four normal vortices with lowering the temperature. On the other hand, the vortex pattern for vorticity corresponds to an antivortex and four normal vortices in the whole temperature domain.     

Beryllium Silicate,Be2SiO4 (phenakite) – a Novel Trigonal SRS‐Active Crystal

In single crystals of the beryllium silicate Be₂SiO₄ with trigonal symmetry , known also as the mineral phenakite, χ⁽³⁾‐nonlinear lasing by stimulated Raman scattering (SRS) is investigated. All observed Stokes and anti‐Stokes lasing components are identified and ascribed to a single SRS‐promoting vibration mode with ω_SRS ≈876 cm⁻¹. With picosecond single‐wavelength pumping at one micrometer the generation of an octave‐spanning Stokes and anti‐Stokes comb is observed.