Red spectral shift and enhanced quantum efficiency in phonon-free photoluminescence from silicon nanocrystals

Crystalline silicon is the most important semiconductor material in the electronics industry. However, silicon has poor optical properties because of its indirect bandgap, which prevents the efficient emission and absorption of light. The energy structure of silicon can be manipulated through quantum confinement effects, and the excitonic emission from silicon nanocrystals increases in intensity and shifts to shorter wavelengths (a blueshift) as the size of the nanocrystals is reduced. Here we report experimental evidence for a short-lived visible band in the photoluminescence spectrum of silicon nanocrystals that increases in intensity and shifts to longer wavelengths (a redshift) with smaller nanocrystal sizes. This higher intensity indicates an increased quantum efficiency, which for 2.5-nm-diameter nanocrystals is enhanced by three orders of magnitude compared to bulk silicon. We assign this band to the radiative recombination of non-equilibrium electron-hole pairs in a process that does not involve phonons.     

Putting nanocrystals to work: from solutions to devices

The colloidal route to semiconductor nanocrystals is extremely flexible, with a high degree of control over size, size distribution, surface passivation and internal structure of the nanoparticles. Simple chemically controlled techniques can be used to assemble these particles into dense films or other microscopic structures, suitable for photonic devices. Working with semiconductors or semi-metals which in the bulk form have low or inverted bandgaps, and taking advantage of the blue shift in the quantum confinement regime, nanocrystals can readily be tuned to the infrared wavelengths of interest for telecommunications. Design flexibility is far greater than with conventional compound semiconductors or rare-earth-doped glasses. Preliminary results demonstrating optical gain from II-VI nanocrystal films at room temperature are reported.     

Mechanical-contact-induced transformation from the amorphous to the partially crystalline state in metallic glass

Sliding friction and wear experiments and electron microscopy and diffraction studies were conducted to examine the metallurgical microstructure of a metallic glass surface strained in sliding contact. Friction and wear experiments were conducted with aluminium oxide spheres 3.2 and 6.4 mm in diameter sliding, in reciprocating motion, on a metallic foil with a composition of Fe₆₇Co₁₈B₁₄Si₁ at a sliding velocity of 1.5 mm s^-1 (frictional heating is negligible) with a load of 2.5 N at room temperature and in a laboratory air atmosphere.The results of the investigation indicate that the amorphous alloy (metallic glass) can be crystallized during mechanical contact. Crystallites with a size range of 10–150 nm are produced on the wear surface of the amorphous alloy. A diffused honeycomb-shaped structure formed by dark gray bands is also produced during sliding. Considerable plastic flow occurs on an amorphous alloy surface with sliding and the flow film of the alloy transfers to the aluminium oxide pin surface. Multiple slip bands due to shear deformation are observed on the side of the wear track. Two distinct types of wear debris were observed as a result of sliding: an alloy wear debris and/or powdery and whiskery oxide debris. The wear rate of Fe₆₇Co₁₈B₁₄Si₁ was 5 × 10^-9 mm³ N^-1.     

Innovation output and state ownership: empirical evidence from China’s listed firms

Abstract

China has experienced a surge in innovation output in which state-owned enterprises (SOE) play an essential role. Using panel data of Chinese listed firms, this paper examines the influence of state ownership on innovation output at the firm level. Controlling for size, we analyse the effects of central and local government control on the number of firms’ patent applications in different time periods. Doing so, standard assumptions on state ownership’s inhibiting character are confirmed. However, we then qualify these findings by running separate models for different regions and sectors finding that the impact of state-control on innovation performance depends on a number of conditions. More precisely, state control of firms has a negative impact on innovation output in particular in China’s Northeast region and in mid-tech sectors whereas under other circumstances it does either not matter or can even exert a positive influence.     

Metal nitride cluster fullerenes: their current state and future prospects

The world of endohedral fullerenes was significantly enlarged over the past seven years by the cluster fullerenes, which contain structures such as the M(2)C(2) carbides and the M(3)N nitrides. While the carbide clusters are generated under the standard arc-burning conditions according to stabilization conditions, the nitride cluster fullerenes (NCFs) are formed by varying the composition of the cooling gas atmosphere in the arc-burning process. The special conditions for NCF synthesis is described in detail and the optimum conditions for the production of NCFs as the main product in fullerene syntheses are given. A general review of all NCFs reported to date consists of the structures, properties, and stability of the NCFs as well as the abundance of the NCFs in the fullerene soot. It is shown that all cages with even carbon atoms from C(68) to C(98) are available as endohedral nitride cluster structures (with the exception of C(72), C(74), and C(76)). Specifically, the NCFs form the largest number of structures that violate the isolated pentagon rule (IPR). Finally some practical applications of these cluster fullerenes are illustrated and an outlook is given, taking the superior stability of these endohedral fullerenes into account.     

Size and distribution: a comparison of XRD, SAXS and SANS study of II-VI semiconductor nanocrystals

The uniqueness of size dependent functional properties of II-VI semiconductor nanocrystals have led to the development of various techniques for determination of shape, size and distributions, although the accurate measurements of the particle sizes has always been a fundamental task in nanoscience and even become more crucial with the discovery of quantum confinement effect. A comparison of the well established techniques X-ray diffraction (XRD), small angle X-ray scattering (SAXS) and small angle neutron scattering (SANS) with an emphasis on size and distribution of the prepared samples are reported in order to elaborate more precise techniques for the analysis of particles sizes. Modified Scherrer formula for spherical particles has been used to calculate the particle sizes from XRD spectra. Analysis of SAXS data has been reported using Guinier model. Small angle neutron scattering measurements has been performed for ZnO nanocrystals and the scattering data obtained is simulated for polydisperse sphere. The bare ZnO, ZnS and CdS and doped with Mn2+ systems are taken within the framework of our discussion. These materials were synthesized by chemical precipitation route and found to have size distribution from 2 to 6 nm for spherical particles. Sizes determined from various techniques are in good agreement with each other however small angle scattering technique is more reliable than XRD to determine the sizes of the nanoparticles.     

Evolution of nonlinear optical properties: from gold atomic clusters to plasmonic nanocrystals

Atomic clusters of metals are an emerging class of extremely interesting materials occupying the intermediate size regime between atoms and nanoparticles. Here we report the nonlinear optical (NLO) characteristics of ultrasmall, atomically precise clusters of gold, which are smaller than the critical size for electronic energy quantization (～2 nm). Our studies reveal remarkable features of the distinct evolution of the optical nonlinearity as the clusters progress in size from the nonplasmonic regime to the plasmonic regime. We ascertain that the smallest atomic clusters do not show saturable absorption at the surface plasmon wavelength of larger gold nanocrystals (>2 nm). Consequently, the third-order optical nonlinearity in these ultrasmall gold clusters exhibits a significantly lower threshold for optical power limiting. This limiting efficiency, which is superior to that of plasmonic nanocrystals, is highly beneficial for optical limiting applications.     

Generalized spectral decomposition: a theory and practice to spectral reconstruction

The generalized spectral decomposition (GSD) theorem is introduced, and the generalized fundamental stimulus and metameric black are analyzed to show how they convey the valuable features in terms of color information. The suggestion would be considered as the generalization of Cohen and Kappauf's matrix R theory and its later application in parameric correction by Fairman. The GSD theorem provides a modular model whose arguments can be elaborately set up for high-performance spectral recovery. It is also shown that the suggested methods for spectral decomposition and/or spectral reconstruction proposed by different researchers could be considered as special cases of GSD.     

The different roles of proximity in multiple informal network relationships: evidence from the cluster of high technology applied to cultural goods in Tuscany

The role of proximity in innovation and inter-organisational networks has received increasing attention over the past decade. Despite the rich literature, most contributions principally focus on only one type of relationship and mainly consider formal relationships such as R&;D partnerships, EU projects or patents. The aim of the study is to investigate the role of various forms of proximity in multiple informal inter-organisational relationships. The article focuses on two research questions: (i) How do the various forms of proximity influence the formation of different informal relationships? and (ii) What is the impact of social ties on relationships for innovation? ERGM is applied to measure the different impact of the proximities on three network relationships operating in the cluster of High Technology applied to Cultural Goods. The results underline the heterogeneous impact of various forms of proximity on the different relationships and the strong impact of social ties on innovation.     

Dimension-controlled synthesis of CdS nanocrystals: from 0D quantum dots to 2D nanoplates

The dimension-controlled synthesis of CdS nanocrystals in the strong quantum confinement regime is reported. Zero-, one-, and two-dimensional CdS nanocrystals are selectively synthesized via low-temperature reactions using alkylamines as surface-capping ligands. The shape of the nanocrystals is controlled systematically by using different amines and reaction conditions. The 2D nanoplates have a uniform thickness as low as 1.2 nm. Furthermore, their optical absorption and emission spectra show very narrow peaks indicating extremely uniform thickness. It is demonstrated that 2D nanoplates are generated by 2D assembly of CdS magic-sized clusters formed at the nucleation stage, and subsequent attachment of the clusters. The stability of magic-sized clusters in amine solvent strongly influences the final shapes of the nanocrystals. The thickness of the nanoplates increases in a stepwise manner while retaining their uniformity, similar to the growth behavior of inorganic clusters. The 2D CdS nanoplates are a new type of quantum well with novel nanoscale properties in the strong quantum confinement regime.     

Melting and superheating of crystalline solids: From bulk to nanocrystals

Melting of solids is a common phenomenon in nature. It is also one of the most important phase transformations in materials science and engineering. In recent years, extensive experimental and theoretical investigations in conjunction with computer simulations on melting of solids, with various geometries ranging from bulk forms to nanometer-sized clusters, have greatly enhanced our understanding of the nature of melting. This paper reviewed the up-to-date research results on this classical and cutting-edge topic. Emphasis was made on melting and superheating of nano-sized particles and thin films including thermodynamic and kinetic analyses of the size effect and the interfacial structure effect on melting processes.     

Greener supplier selection: state of the art and some empirical evidence

In recent years, an increasing environmental awareness has favoured the emergence of the new green supply chain paradigm; thus, also in the supplier selection problem, green criteria were incorporated. The aim of this paper is twofold. First, a careful scrutiny of the papers appearing in international scientific journals in recent years on the greener supplier selection problem is provided, highlighting utilised methodologies and current issues; second, a verification of the penetration of environmental and green criteria for the supplier selection in corporate practice is performed, using a questionnaire survey targeting the top 100 manufacturing companies operating in South Yorkshire (UK) and two in-depth interviews at large MNE firms operating in complex industries. Results show that, while interest in the literature is growing, there is little empirical evidence of the transfer of these applications into the real world, highlighting a persistent dichotomy between theory and practice. The reasons for this dichotomy are also investigated.     

Temperature-dependent near-infrared spectra of bovine serum albumin in aqueous solutions: spectral analysis by principal component analysis and evolving factor analysis

Fourier transform near-infrared (FT-NIR) spectra have been measured for bovine serum albumin (BSA) in an aqueous solution (pH 6.8) with a concentration of 5.0 wt% over a temperature range of 45-85 degrees C. Not only conventional spectral analysis methods, such as second-derivative spectra and difference spectra, but also chemometrics, such as principal component analysis (PCA) and evolving factor analysis (EFA), have been employed to analyze the temperature-dependent NIR spectra in the 7500-5500 and 4900-4200 cm-1 regions of the BSA aqueous solution. Intensity changes of bands in the 7200-6600 cm-1 and 4650-4500 cm-1 regions in the difference spectra indicate variations of the hydration and secondary structure of BSA in the aqueous solution, respectively. The plot of a band intensity at 7080 cm-1 in the different spectra shows a clear turning point at 63 degrees C, revealing that a significant change in the hydration occurs at about 63 degrees C. The forward and backward eigenvalues (EVs) from EFA suggest that marked changes in the hydration and secondary structure of BSA take place in the temperature ranges of 61-65 degrees C and 59-63 degrees C, respectively. In addition, the temperature of 71 degrees C marked in the EFA plots may correspond to the onset temperature of increase in the intermolecular beta-sheet structure.     

Size effects on concrete fracture energy: dimensional transition from order to disorder

The nominal fracture energy of concrete structures is constant for relatively large structures, whereas it increases with size for relatively small structures. If the energy dissipation space is modeled as a monofractal domain, with a non-integer dimension comprised between 2 and 3, a unique slope in the bilogarithmic fracture energy versus size diagram is found, as was stated in a previous paper [1]. On the other hand, when the scale range extends over more than one order of magnitude, a continuous transition from slope+1/2 to zero slope may appear, according to the hypothesis of multifractality of the fracture surface [1]. This means that, at small scales, a Brownian microscopic disorder is prevalent whereas, at large scales, the effect of disorder vanishes, yielding a macroscopical homogeneous behavior. The dimensional transition from disorder to order may be synthesized by a Multifractal Scaling Law (MFSL) valid for toughness, in perfect correspondence with the MFSL valid for strength, which has been described in a previous paper [2]. The MFSL for fracture energy is applied, as a bestfitting method, to relevant experimental results in the literature, allowing for the extrapolation of fracture energy values valid for real-sized structures.     

Atomic state teleportation: from internal to external degrees of freedom

We suggest a simple method to teleport an unknown superposition of the atomic internal state of a two-level atom onto transverse atomic momenta of another atom during its flight. The scheme relies on the standard cavity QED techniques and is inherently deterministic with sufficiently high fidelity for the teleported state. It is further shown that the procedure can be straightforwardly extended to remotely tune in the probability amplitudes of any atomic momenta multipartite entangled state.     

Direct solar spectral irradiance and transmittance measurements from 350 to 2500 nm

A radiometrically stable, commercially available spectroradiometer was used in conjunction with a simple, custom-designed telescope to make spectrally continuous measurements of solar spectral transmittance and directly transmitted solar spectral irradiance. The wavelength range of the instrument is 350-2500 nm and the resolution is 3-11.7 nm. Laboratory radiometric calibrations show the instrument to be stable to better than 1.0% over a nine-month period. The instrument and telescope are highly portable, can be set up in a matter of minutes, and can be operated by one person. A method of absolute radiometric calibration that can be tied to published top-of-the-atmosphere (TOA) solar spectra in valid Langley channels as well as regions of strong molecular absorption is also presented. High-altitude Langley plot calibration experiments indicate that this technique is limited ultimately by the current uncertainties in the TOA solar spectra, approximately 2-3%. Example comparisons of measured and modtran-modeled direct solar irradiance show that the model can be parameterized to agree with measurements over the large majority of the wavelength range to the 3% level for the two example cases shown. Side-by-side comparisons with a filter-based solar radiometer are in excellent agreement, with a mean absolute difference of tau = 0.0036 for eight overlapping wavelengths over three experiment days.     

Diverse nanocelluloses prepared from TEMPO-oxidized wood cellulose fibers: Nanonetworks,nanofibers, and nanocrystals

When wood cellulose fibers are oxidized with NaClO and catalytic amounts of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and NaBr in water at pH 10, significant amounts of sodium carboxylate groups (≤1.7 mmol/g) are introduced into the oxidized celluloses. The original fibrous morphologies and cellulose I crystal structures are unchanged by oxidation. The TEMPO-oxidized cellulose fibers can be converted to partially fibrillated nanonetworks, completely individualized cellulose nanofibers with high aspect ratios, and needle-like cellulose nanocrystals with low aspect ratios by controlling the conditions of mechanical disintegration in water. It is therefore possible to prepare diverse nanocelluloses with different morphologies and properties from the same TEMPO-oxidized cellulose fibers, for various end uses and applications. All TEMPO-oxidized nanocelluloses contain large amounts of carboxylate groups. These provide scaffolds for versatile surface modification of nanocelluloses by simple ion exchange of sodium for other metal ions and alkylammonium ions.     

Visible tunable lighting system based on polymer composites embedding ZnO and metallic clusters: from colloids to thin films

The development of phosphor devices free of heavy metal or rare earth elements is an important issue for environmental reasons and energy efficiency. Different mixtures of ZnO nanocrystals with Cs₂Mo₆I₈(OOC₂F₅)₆ cluster compound (CMIF) dispersed into polyvinylpyrrolidone matrix have been prepared by very simple and low cost solution chemistry. The resulting solutions have been used to fabricate highly transparent and luminescent films by dip coating free of heavy metal or rare earth elements. The luminescence properties of solution and dip-coated films were investigated. The luminescence of such a system is strongly dependent on the ratios between ZnO and CMIF amounts, the excitation wavelength and the nature of the system. By varying these two parameters (ratio and wavelength), a large variety of colors, from blue to red as well as white, can be achieved. In addition, differences in the luminescence properties have been observed between solutions and thin films as well as changes of CMIF emission band maximum wavelength. This may suggest some possible interactions between the different luminophore centers, such as energy transfer or ligands exchange on the Mo₆ clusters.