Size and Interface Control of Novel Nanocrystalline Materials Using Pulsed Laser Deposition

We have developed a novel method based upon pulsed laser deposition to produce nanocrystalline materials with an accurate grain size and interface control. Using this method, the grain size in the case of Cu thin films was controlled by introducing a few monolayers of insoluble elements having high surface energy such as W, which increases interfacial energy and provides more nucleation sites. The grain size is determined by the thickness of Cu layer and the substrate temperature at which it transforms into islands (nanocrystalline grains) of fairly uniform size which we desgnate as self-assembling approach. Using this approach, the grain size was reduced from 160nm (Cu or Si (100) substrate) to 70–80nm for a simple W layer (Cu/W/Si (100)) to 4nm for a multilayer (Cu/W/Cu/W/Si (100)) thin film. The hardness of these films was evaluated using a nanoindentation technique, a significant increase in hardness from 2.0GPa for coarse-grained 180nm to 12.5GPa for 7nm films was observed. However, there is decrease in hardness below 7nm for copper nanocrystals. The increase in hardness with the decrease in grain size can be rationalized by Hall–Petch model. However, the decrease in slope and eventually the decrease in hardness below a certain grain size can be explained by a new model based upon grain-boundary deformation (sliding). We also used a similar materials processing approach to produce quantum dots in semiconductor heterostructures consisting of Ge and ZnO dots or nanocrystals in AlN or Al₂O₃ matrix. The latter composites exhibit novel optoelectronic properties with quantum confinement of phonons, electrons, holes and excitons. Similarly, we incorporated metal nanocrystals in ceramics to produce improved mechanical and optical properties.     

Q-switched mode-locking with Cr4+ : YAG in a diode pumped Nd : GdVO4 laser

We have demonstrated passively Q-switched mode-locking in a laser-diode-pumped Nd:GdVO₄ laser with an intracavity Cr⁴⁺:YAG saturable absorber. At a pump power of 19.4 W, the Q-switched mode-locked laser produced an average output power of 3.22 W, and the repetition rates of the Q-switched envelope and the mode-locked laser pulse were 227 kHz and 144 MHz, respectively. The duration of the mode-locked pulse was within the sub-nanosecond range. PACS 42.55.Xi; 42.60.Fc; 42.60.Gd; 42.55.Rz     

Unusual Behavior of Nanocrystalline Strontium Oxide Toward Hydrogen Sulfide

The thermodynamically favored reaction of solid strontium oxide with gaseous hydrogen sulfide is kinetically enhanced to a large degree by the use of higher surface area nanocrystalline SrO in the form of brush-like collections of metal oxide fibers. An unusual feature is that the reaction SrO + H₂S SrS + H₂O proceeds stoichiometrically at room temperature, but at higher temperatures the reaction efficiency goes down, apparently due to rapid temperature induced crystal growth of the nanocrystalline SrO. The samples studied vary in crystallite size from 20 to 27nm, while average particle size (nanocrystal aggregates) varies in the following order; aerogel prepared SrO (100nm) 相似文献   

Microstructure and Chemical States of Hydroxyapatite/silk Fibroin Nanocomposites Synthesized via A Wet-mechanochemical Route

Hydroxyapaptite (HAp)/silk fibroin (SF) nanocomposites were prepared via a wet-mechanochemical route at room temperature. The results reveal that the inorganic phase in the composites is carbonate-substituted HAp containing 2.9–3.1 wt% of carbonate ions. The primary HAp crystals are rod-like in shape with a typical size of 20–30nm in length and 8–10nm in width, and lattice parameters a = 9.423, c = 6.888. The self-assembled HAp crystals along their c-axes aggregate into bundles, which are connected with SF fibrils. Consequently, a three-dimensional porous network is formed in the composite, which is beneficial to inducing new bone formation in practical implantation.     

Iron Nanoparticles in Severe-plastic-deformed Copper

Superparamagnetic iron nanoparticles with a size of a few nanometers were produced in copper by severe plastic deformation. In a isochronal annealing experiment near a temperature of 450K, which corresponds to the temperature of structural relaxation and the first step of grain growth (from 128 to 150nm) of submicrocrystalline copper, an abrupt increase in the magnetic susceptibility is detected. This increase is shown to be due to iron nanoparticles increasing in size from 2.8 to 3.3nm. The vanishing of the ferromagnetic contribution by iron nanoparticles observed at 850K, well below the Curie temperature of iron, is due to the dissolution of nanoparticles in plastically deformed copper.     

Luminescent CdS Nanoparticles Embedded in Polyethylene Glycol (PEG 300) Matrix Thin Film

A simple method for synthesis of well dispersed cadmium sulphide (CdS) nanoparticles embedded in a polyethylene glycol matrix (PEG 300) in thin film form is presented. The molar ratio of PEG and CdS was varied within the range 70:30 to as high as 50:50. Films with controllable sizes (r 3 –8nm) of nanocrystals could be obtained by adjusting post-deposition annealing temperature (T) and time (t). The obtained films showed systematic variation in optical properties with decreasing crystal size due to quantum confinement. Transmission electron micrographs (TEM) indicated well resolved nanoparticles for films annealed at lower temperature (T = 373K) and time (t < 45 min). Photoluminescence (PL) studies indicated blue shift with decreasing particle size. The films did not degrade with aging in a humid atmosphere (relative humidity 40%) for several weeks.     

Diode-pumped passively Q-switched Nd : YAG laser at 1123 nm

A diode-pumped Nd:YAG laser at 1123 nm is passively Q-switched by using a low doping concentration Cr⁴⁺:YAG crystal as a saturable absorber. When pumped by a 1.5-W laser diode, the laser produces pulses of 50-ns duration with a pulse energy of as much as 15 J and a peak power of 300 W at a pulse-repetition rate of 10 kHz. PACS 42.60.Gd; 42.55.Rz; 42.55.Xi     

The Q-switched Nd : YAG and Yb : YAG microchip lasers optimization and comparative analysis

The microchip lasers based on the neodymium or the ytterbium doped yttrium-aluminium garnet crystal and Q-sw itched by the Cr⁴⁺:YAG film are considered. The optimal (maximizing of energy) values of the pumping beam radius, the absorber parameters (the thickness and tetravalent chromium ion concentration), and the output mirror reflectivity are determined. The possibility of higher values of energy in the Yb:YAG laser pulse, in comparison with a more traditional Nd:YAG laser, is also substantiated. PACS 42.60.Gd     

Influence of Hydrothermal Temperature on Structures and Photovoltaic Properties of SnO2 Nanoparticles

Two SnO₂ nanoparticles were synthesized by hydrothermal method at 170°C and 180°C, respectively. Transmission electron microscope observations reveal that the diameters of both the nanoparticles are around 6nm. At the same time, surface photovoltage spectroscopy measurements show that the nanoparticle synthesized at 180°C has more surface electronic states at 0.3eV below the conduction band than the one synthesized at 170°C. This means that the temperatures chosen in hydrothermal synthesis have significant influence on the surface electronic characteristics of resultant SnO² nanoparticles but the effect on their sizes is not obvious. However, after being calcined at 500°C for 2h, the diameter of the nanoparticle synthesized at 180°C increased to 23nm and that of the nanoparticle synthesized at 170°C increased to 32nm as calculated from X-ray diffraction pattern.     

Substructure of Titanium Dioxide Agglomerates from Dry Ball-milling Experiments

The calciner discharge of TiO₂ white pigments from the sulphate process is ground batchwise in a planetary ball mill, varying the energy of comminution between 0 and 5.1 times the earth's gravitational constant. Particle sizes and specific surfaces of the ground products reveal that the calciner discharge consists of aggregates of 430nm diameter built from 160–210nm TiO₂ crystals. The contact area of a primary particle in an aggregate is about 15% of its surface. The success in comminution of aggregates as a function of grinding energy follows Kick's law. The theory by Rose and Weichert is used to quantify the mechanical strength of the aggregates. Ca. 20% of the aggregates are further agglomerated to granules of ca. 35µm. At all energy levels above a certain threshold, agglomerates break directly into aggregates.     

Synthesis and Properties of Layered Organic–inorganic Hybrid Material: Zn-Al Layered Double Hydroxide–dioctyl Sulfosuccinate Nanocomposite

A layered organic–inorganic hybrid nanocomposite was prepared by using a surfactant, dioctyl sulphosuccinate (DSS) as a guest in Zn-Al layered double hydroxide (LDH) inorganic host by a self-assembly technique. The Zn-Al ratio of the mother liquor was kept constant at 4 at the beginning of the synthesis. Powder X-ray diffractogram shows that the basal spacing of the Zn-Al LDH with sulphate as the intergallery anion (ZASUL) expanded from 11.0 to 26.3Å to accommodate the DSS surfactant anion for the formation of the Zn-Al LDH–DSS layered organic–inorganic hybrid nanocomposite (ZADON). It was also found that the BET surface area reduced by about 90%, from 22.5 to 2.2m²/g, for ZASUL and ZADON, respectively if 0.1M DSS was used for the synthesis of the latter.     

Nanoparticle Formation by Laser Ablation

The properties of nanoparticle aerosols of size ranging from 4.9nm to 13nm, generated by laser ablation of solid surfaces are described. The experimental system consisted of a pulsed excimer laser, which irradiated a rotating target mounted in a cylindrical chamber 4cm in diameter and 18-cm long. Aerosols of oxides of aluminum, titanium, iron, niobium, tungsten and silicon were generated in an oxygen carrier gas as a result of a reactive laser ablation process. Gold and carbon aerosols were generated in nitrogen by non-reactive laser ablation. The aerosols were produced in the form of aggregates of primary particles in the nanometer size range. The aggregates were characterized using a differential mobility analyzer and electron microscopy. Aggregate mass and number concentration, electrical mobility size distribution, primary particle size distribution and fractal dimension were measured. System operating parameters including laser power (100mJ/pulse) and frequency (2Hz), and carrier gas flow rate (1l/min) were held constant.A striking result was the similarity in the properties of the aerosols. Primary particle size ranged between 4.9 and 13nm for the eight substances studied. The previous studies with flame reactors produced a wider spread in primary particle size, but the order of increasing primary particle size follows the same trend. While the solid-state diffusion coefficient probably influences the size of the aerosol in flame reactors, its effect is reduced for aerosols generated by laser ablation. It is hypothesized that the reduced effect can be explained by the collision-coalescence mechanism and the very fast quenching of the laser generated aerosol.     

The Formation of Porous Membranes by Filtration of Aerosol Nanoparticles

Flame-generated aerosol particles of Al₂O₃ were deposited by gas filtration on two types of porous and ceramic tubes of -Al₂O₃ with mean pore diameters of 450 and 2700nm, respectively. The particles were aggregates with average mobility diameters in the range of 30–100nm and primary particle diameters of 4–8nm. The particles are characterized by differential mobility analysis, transmission electron microscopy, and by their specific surface area. The deposited membranes are characterized by gas permeability measurements, scanning electron microscopy, and by their pore size distribution from nitrogen capillary condensation. The particles form a distinct, homogeneous membrane layer with a porosity of 90% on top of the substrate surface and only penetrate slightly into the substrate structure. The mean pore sizes of the deposited membranes determined by nitrogen condensation agree approximately with those determined by gas permeation and the specific surface area. The mean pore diameter varies in the range of 30–70nm. The gas permeability of the deposited membranes is related to the specific surface area but influenced by the high porosity. The mean pore size and the permeability of the membranes are almost independent of the substrate structure.The development of a membrane with uniform properties is preceded by a short initial period in which the deposited particles, with an equivalent membrane thickness of roughly 2m, have a significantly lower permeability than the ultimately developed uniform membrane layer. This effect is particularly significant for the aerosol particles with the lowest mean size, probably due to particles deposited in the pore mouths of the substrate.The particles and the deposited membranes are X-ray amorphous but retain their specific surface area on heating to even high temperatures. When the membranes are heated to 1473K for 10h, X-ray diffraction shows a mixture of - and -alumina, accompanied by a partial disintegration of the membrane and a considerable loss of surface area.     

The Effect of Nanoscale Roughness on Long Range Interaction Forces

A model was developed to calculate the long range van der Waals and electrostatic energies between a rough colloidal particle and a smooth solid plate in aqueous solutions. The particle roughness was modeled as hemispherical asperities distributed uniformly over the surface. Because of the assumption of additive potentials used in calculating the electrostatic force, the model is most accurate when the particle/plate separation is larger than several Debye screening lengths, such as near the location of the secondary minimum. The model predicts that such roughness reduces the depth of the secondary minimum and pushes it to larger separation distances. The model also predicts that the height of the primary energy barrier, which controls the dispersion stability, is substantially lowered by the asperities.Experimental validation of the model was achieved by measuring the potential energy profile between individual, 15µm diameter polystyrene latex spheres and a smooth glass plate around the location of the secondary energy minimum using the optical technique of total internal reflection microscopy (TIRM). When compared to predictions made assuming perfectly smooth surfaces, the measured well depths are consistently found to be lower than expected. Excellent agreement can be achieved, however, by adding asperities with a height of order 25nm to the particle surface. These measurements are some of the first direct measurements of the effect of roughness on interaction energies.     

Nanometer Calibration Particles: What is Available and What is Needed?

Information on available polystyrene calibration spheres is presented regarding the particle diameter, uncertainty in the size, and the width of the size distribution for particles in a size range between 20 and 100nm. The use of differential mobility analysis for measuring the single primary calibration standard in this size range, 100nm NIST Standard Reference Material®1963, is described along with the key factors in the uncertainty assessment. The issues of differences between international standards and traceability to the NIST Standard are presented. The lack of suitable polystyrene spheres in the 20–40nm size range will be discussed in terms of measurement uncertainty and width of the size distributions. Results on characterizing a new class of molecular particles known as dendrimers will be described and the possibilities of using these as size calibration standards for the size range from 3 to 15nm will be discussed.     

Mode-locking of neodymium lasers by glasses doped with PbS nanocrystals

Nonlinear optical absorption properties of silicate glasses doped by the PbS nanocrystals were investigated by means of the picosecond pump-probe absorption spectroscopy and absorption bleaching technique. The glass samples were used as saturable absorbers for passive mode-locking of Nd:YAG and Nd:glass lasers. Application of the PbS doped glass together with the active mode-locking and laser cavity quality control enabled the stable of generation of 28 ps and 5 ps duration pulses in Nd:YAG and Nd:glass lasers respectively. PACS 42.60.Fc; 42.70.Hj; 78.47.+p     

Compact efficient intracavity optical parametric oscillator with a passively Q-switched Nd : YVO<Subscript>4</Subscript>/Cr<Superscript>4+</Superscript> : YAG laser in a hemispherical cavity

A compact eye-safe optical parametric oscillator (OPO) using a noncritically phase-matched KTP crystal intracavity pumped by a passively Q-switched Nd:YVO₄ laser is experimentally demonstrated. To enhance the performance of passive Q-switching, a Cr⁴⁺:YAG saturable absorber crystal is coated as an OPO output coupler in a nearly hemispherical cavity. With an incident pump power of 2.5 W, the compact intracavity OPO cavity, operating at 62.5 kHz, produces average powers at 1573 nm up to 255 mW and peak powers higher than 1 kW. PACS 42.60.Gd; 42.65.Yj; 42.55.Xi     

Excitation of Intra-4f Shell Luminescence of Rare Earth Ions (Er3+ and Yb3+) by the Energy Transfer from Si Nanocrystals

Photoluminescence (PL) properties of SiO₂ films containing Si nanocrystals (nc-Si) and Er³⁺ (Yb³⁺) were studied. PL peaks attributable to the recombination of electron–hole pairs in nc-Si (1.5eV) and the intra-4f shell transition of Er³⁺ (0.81eV) (Yb³⁺ (1.26eV)) were observed simultaneously at room temperature. Correlation of the two peaks was studied as a function of nanocrystalline size. It was found that the intensity of the Er³⁺-related (Yb³⁺-related) peak increases drastically as the size of nc-Si decreases. Temperature dependence of PL spectra was studied. In the case of Yb-doped samples, temperature quenching of the PL became small as the size decreased, while in the case of Er-doped samples, no remarkable temperature dependence was observed. Two major features of the quantum size effects of nc-Si, i.e., the band-gap widening and the increase in the PL efficiency with decreasing the size, are thought to contribute to the improvement of room temperature PL efficiency of Er³⁺ (Yb³⁺).     

Characteristics of Fe2O3 Nanoparticles from Doped Low-pressure H2/O2/Ar Flames

A burner stabilized premixed low-pressure flame has been used to generate iron-oxide (Fe₂O₃) nanoparticles with sizes in the range 7–20nm. The H₂/O₂/Ar flames were doped with different amounts of iron-pentacarbonyl (Fe(CO)₅) with concentrations in the range 524–2096ppm. The influence of precursor concentration on composition, structure, morphology, and size have been studied utilizing transmission electron microscopy (TEM), X-ray powder diffraction (XRD), measurements of the specific surface area (BET), and infrared spectroscopy (FT-IR). The product particles consist of both, the - and the -phase of Fe₂O₃. Average particle sizes were measured in the range 7.4–16nm depending on precursor concentration and flame conditions.     

Generalized Transvectants-Rankin–Cohen Brackets

We introduce o(p+1q+1)-invariant bilinear differential operators on the space of tensor densities on Rⁿ generalizing the well-known bilinear sl₂-invariant differential operators in the one-dimensional case, called Transvectants or Rankin–Cohen brackets. We also consider already known linear o(p+1q+1)-invariant differential operators given by powers of the Laplacian.