Crystallite Density Research Articles

Infrared Dielectric Function of Gold Films in Relation to Their Morphology

Though data concerning gold’s optical properties differ substantially in the literature, the causes for these discrepancies are poorly understood. Surface quality affects the optical response considerably, not only through crystal defects but also through the existing morphology. If optical data analysis is done under the assumption of ideally flat surfaces, the obtained dielectric function or dynamic conductivity and any model parameters represent an effective description that may differ from bulk values according to various preparation conditions. To show this finding in detail, we performed spectroscopic ellipsometry measurements of evaporated gold films in the mid-infrared range, below the onset of the interband transitions, and investigated the sample morphology by means of atomic force microscopy. This study yields effective Drude-model parameters that vary with film morphology over a range that includes most of the published values. Introducing a Bruggeman effective medium to model rough films as a mixture of bulk metal and empty volume makes it possible to find a relation between metal volume fraction and effective plasma frequency. In such a model, the plasma frequency and also the dielectric background resulting from interband transitions decrease as the fraction of empty volume inclusions increases. In contrast, while metal volume fraction is much less influential to relaxation time, the density of the gold crystallites’ grain boundaries yields a strong effect. We thus found a plasma frequency, relaxation rate, and dielectric background for the most ideal gold films at room temperature of 7.37(40) × 104 cm–1, 221(1) cm–1, and 9.6(3), respectively.

Crystallization of dicalcium phosphate dihydrate with presence of glutamic acid and arginine at 37 °C.

The formations of non-metabolic stones, bones and teeth were seriously related to the morphology, size and surface reactivity of dicalcium phosphate dihydrate (DCPD). Herein, a facile biomimetic mineralization method with presence of glutamic acid and arginine was employed to fabricate DCPD with well-defined morphology and adjustable crystallite size. In reaction solution containing more arginine, crystallization of DCPD occurred with faster rate of nucleation and higher density of stacked layers due to the generation of more OH(-) ions after hydrolysis of arginine at 37 °C. With addition of fluorescein or acetone, the consumption of OH(-) ions or desolvation reaction of Ca(2+) ions was modulated, which resulted in the fabrication of DCPD with adjustable crystallite sizes and densities of stacked layers. In comparison with fluorescein-loading DCPD, dicalcium phosphate anhydrate was prepared with enhanced photoluminescence properties due to the reduction of self-quenching effect and regular arrangement of encapsulated fluorescein molecules. With addition of more acetone, DCPD was prepared with smaller crystallite size via antisolvent crystallization. The simulated process with addition of amino acids under 37 °C would shed light on the dynamic process of biomineralization for calcium phosphate compounds.

Optical and electrical properties and phonon drag effect in low temperature TEP measurements of AgSbSe2 thin films

Polycrystalline thin films of silver antimony selenide have been deposited using a reactive evaporation technique onto an ultrasonically cleaned glass substrate at a vacuum of 10−5 torr. The preparative parameters, like substrate temperature and incident fluxes, have been properly controlled in order to get stoichiometric, good quality and reproducible thin film samples. The samples are characterized by XRD, SEM, AFM and a UV—vis—NIR spectrophotometer. The prepared sample is found to be polycrystalline in nature. From the XRD pattern, the average particle size and lattice constant are calculated. The dislocation density, strain and number of crystallites per unit area are evaluated using the average particle size. The dependence of the electrical conductivity on the temperature has also been studied and the prepared AgSbSe2 samples are semiconducting in nature. The AgSbSe2 thin films exhibited an indirect allowed optical transition with a band gap of 0.64 eV. The compound exhibits promising thermoelectric properties, a large Seebeck coefficient of 30 mV/K at 48 K due to strong phonon electron interaction. It shows a strong temperature dependence on thermoelectric properties, including the inversion of a dominant carrier type from p to n over a low temperature range 9–300 K, which is explained on the basis of a phonon drag effect.

Solvent Effects on the Growth Morphology and Phase Purity of CL-20

The performance and stability of the high energy secondary explosive 2,4,6,8,10,12-hexanitrohexaazaisowurtzitane (HNIW, also known as CL-20) can be affected by factors including the phase purity of the bulk material, as well as the particle size, morphology, and defect density of the individual crystallites. Slow evaporation crystallization of CL-20 from 16 different single solvent and co-solvent systems was performed. The phase purity of the bulk material obtained was analyzed by powder X-ray diffraction, optical microscopy, and differential scanning calorimetry. These complementary methods confirmed that under most of the slow evaporation conditions examined, a concomitant mixture of two or more crystalline phases was usually obtained. Numerous individual crystal morphologies were determined using single crystal X-ray goniometry and compared against calculated BFDH morphologies. Examination of the packing interactions in the different CL-20 phases via Hirshfeld surface analysis provides some insight into why concomitant polymorphism is so frequently observed.

Predicting the Effect of Pouring Temperature on the Crystallite Density, Remelting, and Crystal Growth Kinetics in the Solidification of Aluminum Alloys

In the present work, we developed an analytical model to describe the effect of pouring temperature on the crystallite density, remelting, growth kinetics, and the resultant final grain size for aluminum (Al)-based alloys synthesized using gravity casting. The model predicts that there are three regimes of pouring temperature/grain size-related behavior: (i) at low superheats, grain size is small and relatively constant; (ii) at intermediate levels of superheat, there appears to be a transitional behavior where grain size increases in a rapid, non-linear fashion; and (iii) at high superheats, grain size increases linearly with increasing temperature. This general pattern is expected to be shifted upward as distance from the bottom of the casting increases, which is likely a result of the slower cooling rates and/or longer solidification times with increasing distance from the bottom of the casting. To validate the model, a set of experiments has been conducted using Al-Cu and Al-Si alloys (i.e., Al-3.0 wt pct Cu, Al-4.5 wt pct Cu, and Al-A356.2 alloys), and the experimental measurements showed consistent results with theoretical predictions.

Electrical and Microstructural Analysis of Contact Formation on Lightly Doped Phosphorus Emitters Using Thick-Film Ag Screen Printing Pastes

Screen printing of the metallization of phosphorus diffused emitters is a well-established process for industrial silicon wafer-based solar cells. Previously, screen printed silver pastes typically required a very high phosphorus surface doping concentration to ensure a low-resistance ohmic contact. Recently, paste manufacturers have focused on the development of silver pastes capable of contacting phosphorus emitters with progressively lower surface concentrations, to minimize surface recombination losses and enable higher cell conversion efficiencies. In this paper, we report on the progress of contacting inline-diffused phosphorus emitters, of which the surface concentrations have been reduced by an etch-back process, using two different pastes. Solar cells with emitter surface concentrations ranging from 4.0 × 1020 to 1.7 × 1020 phosphorus atoms/cm 3 were made using two different silver pastes. We present a microstructural analysis of the contact formation, which indicates the possible dominant current transport mechanisms for the two pastes. A high density of silver crystallites formed with a very narrow interfacial glass layer makes the Sol 9600 paste suitable for contacting lowly doped phosphorus emitters. Efficiency gains of 0.2%-0.3% (absolute) were achieved, reaching a maximum efficiency of 18.6% on 156 mm × 156 mm p-type pseudo-square Cz mono-crystalline silicon solar cells.

Microscopic Study on Hydrogenation Mechanism of MgH<sub>2</sub> Catalyzed by Nb<sub>2</sub>O<sub>5</sub>

We propose the microstructural change model of magnesium hydride catalyzed by Nb2O5 during hydrogenation. The ball-milled composites, MgH2 and 1mol% Nb2O5, were dehydrogenated and then rehydrogenated for varied time at room temperature under 0.1MPa H2 atmosphere. The crystallite size of Mg and MgH2 was evaluated by powder X-ray diffraction (XRD) measurement and confirmed by transmission electron microscopy (TEM) observation. The crystallite size of generated MgH2 was smaller than that of Mg and did not change significantly with increasing time of hydrogenation. It is suggested that the number density of MgH2 crystallites increases during the hydrogenation process. [doi:10.2320/matertrans.MG201417]

Investigation of the Mechanism Resulting in low Resistance Ag Thick-Film Contact to Si Solar Cells in the Context of Emitter Doping Density and Contact Firing for Current-Generation Ag Paste

Screen-printed thick-film Ag metallization has become highly successful in crystalline Si (c-Si) photovoltaics. However, a complete understanding of the mechanism resulting in low resistance contact is still lacking. In order to shed light on this mechanism for current-generation Ag paste, Si solar cells were fabricated using a range of emitter doping densities and contact firing conditions. Low resistance contact was found to vary as a function of emitter surface P concentration ( [P <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">surface</sub> ]) and peak firing temperature. Scanning electron microscope (SEM) analysis revealed thin interfacial glass films (IGF) under the bulk Ag gridline. SEM analysis also showed increasing Ag crystallite density as both emitter [P <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">surface</sub> ] and peak firing temperature increased. Two mechanisms are proposed in forming low resistance contact to highly doped emitters: 1) formation of ultrathin IGF and/or nano-Ag colloids at low firing temperature, and 2) formation of Ag crystallites at high firing temperature. However, on lightly doped emitters, low resistance contact was achieved only at higher firing temperatures, concomitant with increasing Ag crystallite density, and suggests that thin IGF decorated with nano-Ag colloids may not be sufficient for low resistance contact to lightly doped emitters.

Impact of excess phosphorus doping and Si crystalline defects on Ag crystallite nucleation and growth in silver screen‐printed Si solar cells

AbstractGood quality contacts between metal and silicon emitter are crucial for high crystalline solar cell efficiencies. We investigate the impact of defects originating from electrically inactive phosphorus on contact formation within silver thick film metallized silicon solar cells. For this purpose, emitters with varying sheet resistance, depth, and dead layer were metallized with silver pastes from different generations. Macroscopic contact resistivity measurements were compared with the microscopic contact configurations studied by scanning electron microscopy. The density of direct contacts between Ag crystallites grown into Si and the Ag finger bulk is essential for low contact resistivity. The presence of glass‐free regions needed for such direct contacts depends on the paste composition and on the surface texture, and does not vary with the Si emitter properties. Indeed, the decrease in contact resistivity correlates with increasing density of Ag crystallites embedded in the Si surface. Furthermore, the density of Si surface‐embedded Ag crystallites scales proportional to the electrically inactive P and is independent of the sheet resistance. Using the newest silver paste, the Ag crystallite density is independent of the emitter doping, but the Ag crystallite size increases as a function of the thickness of the dead layer. Transmission electron microscopy characterization of the excess P‐doped Si crystal lattice shows that significant strain and Si bond weakening may play a major role for both Ag crystallite nucleation and growth. Finally, we studied Si crystal defects by metallizing nanocracks, dislocations, and grain boundaries and found that Ag crystallite nucleation is defect‐property dependent. Copyright © 2013 John Wiley &amp; Sons, Ltd.

From the solvothermally treated poly(vinylidenefluoride) colloidal suspension to sticky hydrophobic coating

Solvothermally treating an as-prepared poly(vinylidenefluoride) (PVDF) colloidal suspension leads to a significant impact on the surface properties of the resulting topcoat on a pertinent prime coating. The coating, possessing a fibrous porous matrix, exhibits a water contact angle in the range of 115–136°. However, the coating possesses droplets sticking ability that can be attributed to the pseudo-hydrogen bonding effect of the polarized C–H bonds in each repeating unit of PVDF polymer chains. The hydrophobicity of the topcoat is affected by the formulation of colloidal suspension, which is carried out by introducing a solution of PVDF in dimethylforamide into an excess of methanol. The colloidal suspension formed is subjected to solvothermal treatment subsequently. By thermodynamics, the treatment enhances chain packing density and growth of crystallites inside the colloidal particles of PVDF in the methanol-dominant dispersion medium. Furthermore, the realized chain packing states are retained during the drying of coating through chain affixation role of a small number of poly(divinylbenzene) nodules generated in situ. As a result, a fibrous porous matrix composed of the PVDF submicron knots is attained. The coexistence of the polarized CH2 group and the fibrous porous structure prompts a sticky hydrophobic surface.

Metallic Seed Nanolayers for Enhanced Nucleation of Nanocrystalline Diamond Thin Films

The enhancement of the nucleation and subsequent growth of nanocrystalline diamond (NCD) films with a submicrometer thickness control on silicon substrates is demonstrated by using a sputter deposition of six different metallic (Cr, Mo, Nb, Ti, V and W) seed nanolayers. The effectiveness of altered surface morphology and surface chemistry is discussed. We show that the number density of nanodiamond particles embedded on the nanorough metallic surfaces after an ultrasonic seeding step together with the dynamic surface chemistry during hot-filament chemical vapor deposition of diamond determine the nucleation kinetics, microstructure and surface topography of the NCD films. Overall, the smoothest NCD layer (root-mean-square roughness 10 nm) was obtained with the highest seed density of diamond nanoparticles anchored to the metallic (W) surface. In particular, the rapid carbide-forming metals Mo, Nb and W showed the highest number density of diamond crystallites formed during the NCD nucleation stage, which ...

Studies of some physical properties of PrFe0.7Ni0.3O3 thin films after 200 MeV Ag15+ irradiation

PrFe0.7Ni0.3O3 thin films (thickness ~ 200 nm) were prepared by pulsed laser ablation technique on LaAlO3 substrate. These films were irradiated with 200 MeV Ag15+ ions at various fluencies, ranging from 1 × 1011 to 1 × 1012 ions/cm2. These irradiated thin films were characterized by using X-ray diffraction, dc conductivity, dc magnetization and atomic force microscopy. These films exhibit orthorhombic structure and retain it even after irradiations. The crystallite size (110–137 nm), micro strain (1.48 × 10−2–1.75 × 10−2 line−2 m−4) and dislocation density (79.7 × 1014–53.2 × 1014 line/m2) vary with ion fluencies. An enhancement in resistivity at certain fluence and then a decrease in its value (0.22175–0.21813 Ω cm) are seen. A drastic change in observed magnetism after ion irradiation is seen. With ion irradiation, an increase in surface roughness, due to the formation of hillocks and other factors, is observed. Destruction of magnetic domains after irradiation can also be visualized with magnetic force microscopy and is in close agreement with magnetization data. The impact on various physical properties in these thin films after irradiation indicates a distortion in the lattice structure and consequently on single-particle band width caused by stress-induced defects.

Structural and mechanical properties of Sr+2-doped bismuth manganite thick films

Bismuth strontium manganites Bi1 − xSrxMnO3 (0.20 ≤ x ≤ 0.50) belonging to the orthorhombic structural family were prepared in furnace using a solid-state reaction technique. Thick films of Bi(1 − x)SrxMnO3 were prepared by simple screen printing route. X-ray diffraction data suggest that the synthesized materials have an orthorhombic structure. For synthesized materials, texture coefficient (TC), dislocation density (ρD), density of crystallites per unit area (ψ), and mechanical properties are reported along with the influence of x on the structure and mechanical properties of BiMnO3 thick films.

Characterization of crocodile teeth: Correlation of composition, microstructure, and hardness

Structure and composition of teeth of the saltwater crocodile Crocodylus porosus were characterized by several high-resolution analytical techniques. X-ray diffraction in combination with elemental analysis and infrared spectroscopy showed that the mineral phase of the teeth is a carbonated calcium-deficient nanocrystalline hydroxyapatite in all three tooth-constituting tissues: Dentin, enamel, and cementum. The fluoride content in the three tissues is very low (<0.1 wt.%) and comparable to that in human teeth. The mineral content of dentin, enamel, and cementum as determined by thermogravimetry is 71.3, 80.5, and 66.8 wt.%, respectively. Synchrotron X-ray microtomography showed the internal structure and allowed to visualize the degree of mineralization in dentin, enamel, and cementum. Virtual sections through the tooth and scanning electron micrographs showed that the enamel layer is comparably thin (100-200 μm). The crystallites in the enamel are oriented perpendicularly to the tooth surface. At the dentin-enamel-junction, the packing density of crystallites decreases, and the crystallites do not display an ordered structure as in the enamel. The microhardness was 0.60±0.05 GPa for dentin, 3.15±0.15 GPa for enamel, 0.26±0.08 GPa for cementum close to the crown, and 0.31±0.04 GPa for cementum close to the root margin. This can be explained with the different degree of mineralization of the different tissue types and is comparable with human teeth.

Correlating Photocatalytic Performance with Microstructure of Mesoporous Titania Influenced by Employed Synthesis Conditions

Ordered mesoporous anatase films can be prepared at low temperature by evaporation-induced self-assembly of a microemulsion used to preform nanocrystals of titania. Here, we study the impact of storage time of the reaction solution on the structure and photocatalytic properties of such films. The formation of anatase crystallites was found to initiate and proceed during storage of the reaction solution prior to the preparation of the titania films as expected. However, in contrast to current understanding, we find that the main part of the anatase formation occurs during aging of the prepared films in a controlled relative humidity as a consequence of the rapidly increased concentration of precursor caused by the solvent evaporation during film preparation. Ordered mesoporous films were thus obtained for reaction solutions stored up to 48 h, and the crystallinity of the pore walls was found to increase with increased storage time. Interestingly, the anatase crystallite size was found to remain between 2 and 5 nm for all films prepared from reaction solutions stored up to 48 h showing that the increased crystallinity is due to an increased number density of crystallites. Films prepared from reaction solutions stored for longer times than 48 h were found to be mesoporous but with a disordered pore arrangement. These films contained crystallites with sizes up to 10 nm, apparently too large to arrange in a meso-ordered fashion in the liquid crystalline template. The photocatalytic activity of the films was evaluated for phenol degradation and found to be higher for films prepared from reaction solutions with longer storage times of the reaction solution ascribed to their larger degree of crystallinity and larger crystallite size. Interestingly, although the degree of mesoporosity is important in providing access to high specific surface area and facile transport of reactants and products to the catalyst surface, the degree of order of the mesopores was found to be of less importance for the photocatalytic performance. In addition, this work provides new generic insight into the formation mechanism of low-temperature surfactant-templated synthesis of ordered mesoporous and crystalline materials.

Effect of sulfur additive on density of localized states in nanostructures chalcogenide Se95−xSxZn5 thin films

This paper reports the measurement of space charge limited conduction (SCLC) on the fabricated thin films of Se95−xSxZn5 (0.2≤x≤10) in temperature range 313–353K for the first time. At high electric fields (E∼104V/cm), the current could be fitted into the theory of space charge limited conduction, in case of uniform distribution of localized states in mobility gap. The homogeneity and surface morphology of thin films were assessed by scanning electron microscopy. The crystalline nature of the thin films was confirmed by powder XRD and the crystallite size was calculated using Scherer's formula. The crystallite size and density of localized states were found to increase with the increase of sulfur concentration. DC conductivity and activation energy were calculated and found to decrease and increase respectively, with the increase of sulfur concentration.

Nucleation rate reduction through stress relief of thermally annealed hydrogenated amorphous silicon films

The effect of film stress on crystallite nucleation is investigated in 0.11 μm thick, thermally annealed hydrogenated amorphous silicon films. Using a recently developed optical method, the crystallite density is measured as the films are isochronally annealed at 600 °C, which enables the determination of the crystallite nucleation rate. This rate is significantly suppressed around scratches, cleaved film edges, and laser ablated areas, extending laterally as much as 100–150 μm from these regions where the film connectivity is disrupted. μ-Raman measurements of the transverse optical mode of Si demonstrate an accompanying reduction in tensile stress in the regions where nucleation is suppressed. The first measurements of nucleation rate in stress and in stress relieved areas in the same film are presented.

Electrochemical Growth and Characterization of Lead Sulphide Thin Films

Growth of lead sulphide thin films has been carried out electrochemically on indium doped tin oxide coated conducting glass substrates from an aqueous acidic bath containing Pb(CH3COO)2 and Na2S2O3. X-ray diffraction pattern showed that the deposited films possess cubic structure with most prominent reflection along (200) plane. The dependency of microstructural parameters such as crystallite size, strain and dislocation density with film thickness has been analyzed. Surface morphology and film composition have been analyzed using scanning electron microscopy and energy dispersive analysis by X-rays. Optical absorption analysis showed that the prepared films possess a direct band gap value of 0.37 eV.

Imaging and diffraction of protein crystallization using TEM

Structural biology relies on good-quality protein crystals in order for structure determination. Many factors affect the growth process of a protein crystal including the way it nucleates and the types of damage and contamination during its growth. Although the nucleation process and quality of a crystal is vital to structure determination, they are both under-studied areas of research. Our research begins to explore ways of measuring the quality of protein crystals, using TEM, thus overcoming the problems associated with viewing wet specimens in a vacuum. Our current understanding of nucleation is that it is a two-step mechanism involving the formation of nuclei from dense liquid clusters; however; it is still unclear whether nuclei first start as amorphous aggregates or as crystalline lattices. Potentially, electron diffraction may be capable of uncovering this process. Using TEM imaging and diffraction of lysozyme as a model protein crystal, we report the internal two-dimensional strain and the density of crystallites in a protein crystal, at a resolution never seen before. The TEM diffraction shows unique features of crystal mosaicity that can be directly correlated to TEM images.

Nano-environment effects on the luminescence properties of Eu3+-doped nanocrystalline SnO2 thin films

Nanocrystalline tin (IV) oxide thin films doped with Eu(3+) ions are synthesized using a simple spin-coating method followed by postannealing in an O(2) flow at 700 °C. Transmission electron microscopy and x-ray photoelectron spectroscopy studies illustrate the incorporation of Eu(3+) ions in the films with a high atomic percentage of 2.7%-7.7%, which is found to be linearly dependent on the initial concentration of Eu(3+) in the precursor solution. Glancing incidence x-ray diffraction results show that the crystalline grain sizes decrease with increasing the Eu(3+) concentration and decreasing the postannealing temperature with the emergence of the Eu(2)Sn(2)O(7) phase at high Eu(3+) concentrations (≥5.3 at.%). Luminescence spectra of these doped samples show the characteristic narrow-band magnetic dipole emission at 593 nm and electric dipole emission at 614 nm of the Eu(3+) ions, arising from UV absorption at the SnO(2) band-edge followed by energy transfer to the emission centers. Manipulating the crystallite size, composition, and defect density of the samples greatly affects the absorption edge, energy transfer, and therefore the emission spectra. These modifications in the environment of the Eu(3+) ions allow the emission to be tuned from pure orange characteristic Eu(3+) emission to the broadband emission corresponding to the combination of strong characteristic Eu(3+) emission with the intense defect emissions.