Дисертації з теми "Nanocrystalline copper"

Free-standing nanocrystalline copper-based composite and particle-free copper films were produced by direct- and pulse-current plating. Nanosize 50-nm Al2O3 or 5-nm diamond particles were codeposited into a copper matrix prepared on a rotating disk electrode (RDE). The electrolytes contained CuSO4.5H2O (0.25 M), H2SO4 (0.56 M or 1.5 M), 50-nm Al2O3 (12.5 g/L or 1.0 g/L) or 5-nm diamond (0.5 g/L) particles, and gelatine (0.1 g/L, 0.05 g/L, or 0.02 g/L). The deposition was carried out at room temperature. The RDE was rotated at 1800 rpm for high-alumina particle baths (12.5 g/L) and 1000 rpm for low-alumina particle (1.0 g/L), diamond particle (0.5 g/L), and particle-free baths. The free-standing composite and copper films were characterized by x-ray diffraction (XRD), scanning electron microscopy (SEM), micro hardness tester, and transmission electron microscopy (TEM). Grain size and crystal texture were obtained by XRD measurement. SEM gave information on surface morphology and composition of films. The hardness of nanocrystalline materials was measured by micro hardness tester. TEM was used to confirm the presence of nanocrystalline copper grains. The uncompensated potential became more cathodic with increasing current density in pulse-current plating. The current efficiency was in the range of 0.93 ¨C 1.09 for both direct- and pulse-current plating. Gelatine concentration, the presence of nanosize dispersoids, and pH have no significant effect on electrode potential and current efficiency. Grain size decreased with increasing current density for particle-free copper and most of the composite films by direct- and pulse-current plating. The microhardness of nanocrystalline materials was increased by decreasing grain size for most of the particle-free copper and composite films. The existence of high-angle grain boundaries in nanocrystalline films resulted in negative Hall-Petch slopes. The presence of low concentration of alumina or diamond particles had no effect on grain size and microhardness. The pH had no obvious influence on grain size, microhardness, and alumina content in composite films. Random crystal texture is observed for Cu-Al2O3 composite and particle-free copper films and the (111) preferred texture for Cu-diamond composite films. The (100) preferred substrate orientation had no effect on deposit texture. The current density for both direct- and pulse-current plating had no significant effect on material texture. The presence of particles has no significant influence on nanocrystalline texture. Surface morphology varied for films made under different bath conditions. High gelatine concentration resulted in low-particle impregnation. Films made using 0.1 g/L gelatine resulted in spherical particles with grain size of 64 nm and porous surface. Films made using 0.02 g/L gelatine resulted in smooth surface with smaller grains of 40 nm. Films with high-alumina particle embedding, for example sample 7/9-1, resulted in porous and dark surface. High-alumina particle concentration (12.5 g/L) with 0.02 g/L gelatine in the deposition baths resulted in high-alumina content (0.11 wt% - 2.76 wt%) in composite films. The higher current density (297 mA/cm2) resulted in the lower alumina particle (0.076 wt%) embedding rate for the same bath parameter setting. The presence of both Al and O was found in copper-alumina composites and C element (diamond) was detected in copper-diamond composite films by EDS.

Ultrafine grained (UFG) and nanocrystalline materials have attracted considerable interest because of their unique mechanical properties as compared with coarse grained conventional materials. The fabrication of relatively large amounts of these materials still remains a challenge, and a thorough understanding of the relationship between microstructure and mechanical properties is lacking. The objective of this study was to investigate the mechanical properties of UFG and nanocrystalline copper obtained respectively by a top down approach of severe plastic deformation of wrought copper and a bottom up approach of consolidation of copper nanoparticles using equal channel angular extrusion (ECAE). A critical assessment and correlation of the mechanical behavior of ECAE processed materials to the microstructure was established through the determination of the effect of strain level and strain path on the evolution of strength, ductility and yield anisotropy in UFG oxygen free high conductivity copper in correlation with grain size, grain morphology and texture. ECAE was shown to be a viable method to fabricate relatively large nanocrystalline consolidates with excellent mechanical properties. Tensile strengths as high as 790 MPa and fracture strain of 7 % were achieved for consolidated 130nm copper powder. The effects of extrusion route, number of passes and extrusion rate on consolidation performance were evaluated. The relatively large strain observed was attributed to the bimodal grain size distribution and accommodation by large grains. The formation of bimodal grain size distribution also explains the simultaneous increase in strength and ductility of ECAE processed wrought Cu with number of passes. Texture alone cannot explain the mechanical anisotropy in UFG wrought copper but we showed that grain morphology has a strong impact and competes with texture and grain refinement in controlling the resulting yield strength. Tension-compression asymmetry was observed in UFG wrought copper. This asymmetry is not always in favor of compression as reported in literature, and is also influenced by grain morphology through the interaction of dislocations with grain boundaries. Different prestrains in tension and compression should be experimented to have a better understanding of the encountered anisotropy in Bauschinger parameter in relation with the observed tension-compression asymmetry.

Thesis (S.B.)--Massachusetts Institute of Technology, Dept. of Mechanical Engineering, 2007.
Includes bibliographical references (p. 24).
In the well-known Hall-Petch behavior, yield and flow stresses in polycrystalline metals increase with a decrease in grain size. As grain size continues to decrease, mechanical strength peaks. As grain size further decreases, mechanical strength begins to decrease. As grain size approaches zero, the total structure is composed of an increasingly high percentage of grain boundaries, which exhibit the properties of an amorphous structure. Molecular dynamics simulations, with the goal of exploring this behavior, were performed on nanocrystalline and amorphous microstructures using the embedded atom potential developed by Mishin et al. A 0.2 shear strain was applied to each of the nanocrystalline and amorphous samples. From these simulations, we have observed the inverse Hall-Petch behavior of nanocrystalline structures. We have also shown that the amorphous structure as zero grain size is reasonable as the limiting case for the inverse Hall-Petch trends in nanocrystalline structures.
by David R. Gandy.
S.B.

Nanocrystalline materials have been under extensive study in the past two decades. The reduction in grain size induces many abnormal behaviors in the properties of nanocrystalline materials, that have been investigated systematically and quantitatively. As one of the most fundamental relations in materials science, the structure-property relation should still apply on materials of nano-scale grain sizes. The characterization of grain boundaries (GBs) and related entities remains a big obstacle to understanding the structure-property relation in nanocrystalline materials. It is challenging experimentally to determine the topological properties of polycrystalline materials due to the complex and disordered grain boundary network presented in the nanocrystalline materials. The constantly improving computing power enables us to study the structure-property relation in nanocrystalline materials via Monte Carlo and molecular dynamic simulations. In this study, we will first propose a geometrical construction method based on inverse Monte Carlo simulation to generate digital microstructures with desired topological properties such as grain size, interface area, triple junction length as well as their statistical distributions. The influences on the grain shapes by different topological properties are studied. Two empirical geometrical laws are examined including the Lewis rule and Aboav-Weaire law. Secondly, defect free nanocrystalline Copper (nc-Cu) samples are generated by filling atoms into the Voronoi structure and then relaxed by molecular dynamics simulations. Atoms in the relaxed nc-Cu samples are then characterized into grain atoms, GB interface atoms, GB triple junction atoms and vertex atoms using a newly proposed method. Atoms in each GB entity can also be identified. Next, the topological properties of nc-Cu samples before and after relaxation are calculated and compared, indicating that there exists a physical limit in the number of atoms to form a stable grain boundary interface and triple junction in nanocrystalline materials. In addition, we are able to obtain the statistical averages of geometrical and thermal properties of atoms across each GB interfaces, the so-called GB profiles, and study the grain size, misorientation and temperature effects on the microstructures in nanocrystalline materials. Finally, nc-Cu samples with different topological properties are deformed under simple shear using MD simulation in an attempt to study the structure-property relation in nanocrystalline materials.

Outstanding Thesis
Approved for public release; distribution is unlimited
This thesis presents research on the cold gas-dynamic spray processa relatively new technology that may be utilized to create metal coatings in the solid state. While the thermodynamics and fluid mechanics of the cold gas-dynamic spray process are well understood, the effects of feedstock powder microstructure and composition on the deposition process remain largely unknown. In particular, this thesis aims to shed light on these effects as they pertain to common face-centered cubic metals and their alloysnotably copper and brass. Deposition efficiency, coating thickness per pass, hardness, porosity and compositional variance were all characterized as functions of spraying pressure, spraying temperature and feedstock particle composition in each of the materials. This thesis presents evidence that while brass can be deposited using cold gas-dynamic spray, the resulting material does not possess a dense, uniform microstructure. In fact, deposits made with Cu-90/10 wt.% Zn brass have more than 400% more porosity than standard copper coatings, possess extensive microstructural cracking and wide compositional variance from grain to grain.

The synthesis via chemical solutions (aqueous) (SCS) wet route is a low-temperature and cost-effective growth technique of high crystalline quality oxide semiconductors films. Here we report on morphology, chemical composition, structure and ethanol sensing performances of a device prototype based on zincdoped copper oxide nanocrystallite layer. By thermal annealing in electrical furnace for 30 min at temperatures higher than 550 ˚C, as-deposited zinc doped Cu2O samples are converted to tenorite, ZnxCu1-xOy, (x=1.3wt%) that demonstrate higher ethanol response than sensor structures based on samples treated at 450 ˚C. In case of the specimens after post-growth treatment at 650 ˚C was found an ethanol gas response of about 79 % and 91 % to concentrations of 100 ppm and 500 ppm, respectively, at operating temperature of 400 ˚C in air.

Thesis (Ph. D.)--University of California, San Diego, 2008.
Title from first page of PDF file (viewed Jan. 9, 2009). Available via ProQuest Digital Dissertations. Vita. Includes bibliographical references (p. 179-188).

Nanocrystalline materials are being explored as potential off-chip interconnects materials for next generation microelectronics packaging. Mechanical behavior and deformation mechanisms in nanocrystalline copper and nickel have been explored. Nanostructured copper interconnections exhibit better fatigue life as compared to microcrystalline copper interconnects at a pitch of 100 and #956;m and lower. Nanocrystalline copper is quite stable upto 100 oC whereas nickel is stable even up to 400 oC. Grain boundary (GB) diffusion along with grain rotation and coalescence has been identified as the grain growth mechanism. Ultimate tensile and yield strength of nanocrystalline (nc) Cu and Ni are atleast 5 times higher than microcrystalline counterparts. Considerable amount of plastic deformation has been observed and the fracture is ductile in nature. Fracture surfaces show dimples much larger than grain size and stretching between dimples indicates localized plastic deformation. Activation energies for creep are close to GB diffusion activation energies indicating GB diffusion creep. Creep rupture at 45o to the loading axis and fracture surface shows lot of voiding and ductile kind of fracture. Grain rotation and coalescence along direction of maximum resolved shear stress plays an important role during creep. Grain refinement enhances the endurance limit and hence high cycle fatigue life. However, a deteriorating effect of grain refinement has been observed on low cycle fatigue life. This is because of the ease of crack initiation in nanomaterials. Persistent slip bands (PSBs) at an angle of 45o to loading axis are observed at higher strain ranges (> 1% for nc- Cu) with a width of about 50 nm. No relationship has been observed between PSBs and crack initiation. A non-recrystallization annealing treatment, 100 oC/ 2 hrs for nc- Cu and 250 oC/ 2 hrs for nc- Ni has been shown to improve the LCF life without lowering the strength much. Fatigue crack growth resistance is higher in nc- Cu and Ni compared to their microcrystalline counterparts. This is due to crack deflection at GBs leading to a tortuous crack path. Nanomaterials exhibit higher threshold stress intensity factors and effective threshold stress intensity is proportional to the elastic modulus of the material.

Silver (Ag) is a precious metal with a low stacking fault energy that is known to form copious nanoscale coherent twin boundaries during magnetron sputtering synthesis. Nanotwinned Ag metals are potentially attractive for creating new interface-dominated nanomaterials with unprecedented mechanical and physical properties. Grain-boundary segregation of solute elements has been found to increase the stability of interfaces and hardness of nanocrystalline metals. However, heavily alloying inevitably complicates the underlying deformation mechanisms due to the hardening effects of solutes, or a change of stacking fault energies in Ag caused by alloying. For the above reasons, we developed a microalloying (or doping) strategy by carefully selecting Cu as the primary impurity – a solute that is predicted to have no solid-solution strengthening effect in Ag when its content is below 3.0 wt.%. Neither will Cu affect the stacking fault energy of Ag at a concentration <1.0 wt.%. Moreover, Cu atoms are ~12% smaller than Ag ones, and Ag-Cu is an immiscible system, which facilitates the segregation of Cu into high-energy interface sites such as grain-boundaries and twin-boundary defects. In this thesis, large-scale hybrid Monte-Carlo and molecular dynamics simulations are used to study the unexplored mechanical behavior of Cu-segregated nanocrystalline nanotwinned Ag. First, the small-scale mechanics of solute Cu segregation and its effects on incipient plasticity mechanisms in nanotwinned Ag were studied. It was found that solute Cu atoms are segregated concurrently to grain boundaries and intrinsic twin-boundary kink-step defects. Low segregated Cu contents (< 1 at.%) are found to substantially increase twin-defect stability, leading to a pronounced rise in yield strength at 300 K. Second, atomistic simulations with a constant grain size of 45 nm and a wide range of twin boundary spacings were performed to investigate the Hall-Petch strength limit in nanocrystalline nanotwinned Ag containing either perfect or kinked twin boundaries. Three distinct strength regions were discovered as twin boundary decreases, delineated by normal Hall-Petch strengthening with a positive slope, the grain-boundary-dictated mechanism with near-zero Hall-Petch slope, and twin-boundary defect induced softening mechanism with a negative Hall-Petch slope. Third, by systematically studying smaller grain sizes, we find that the “strongest” size for pure nanotwinned Ag is achieved for a grain size of ~16 nm, below which softening occurs. The controlling plastic deformation mechanism changes from dislocation nucleation to grain boundary motion. This transition decreases to smaller grain sizes when Cu contents are segregated to the interfaces. Our simulations show that continuous Hall-Petch strengthening without softening, down to grain sizes as small as 6 nm, is reached when adding Cu atoms up to 12 at. %. For Cu contents ≥ 15 at. %, however, the predominant plastic deformation mechanism changes to shear-band induced softening. The present thesis provides new fundamental insights into solute segregation, and strengthening mechanisms mediated by grain boundaries and twin boundaries in face-centered cubic Ag metals, which is expected to motivate experimental studies on new nanotwinned metals with superior mechanical properties controlled by microalloying.

Nanocrystalline (NC) metals and alloys are known to possess superior mechanical properties, e.g., strength, hardness, and wear-resistance, as compared to conventional microcrystalline materials. NC metals are characterized by a mean grain size <100 nm; in this grain size regime, inelastic deformation can occur via a combination of interface-mediated mechanisms viz., grain boundary sliding/migration, and dislocation nucleation from grain boundary sources. Recent studies have suggested that these interface-mediated inelastic deformation mechanisms in fcc metals are influenced by non-glide stresses and interfacial free volume, unlike dislocation glide mechanisms that operate in microcrystalline fcc metals. Further, observations of tension-compression strength asymmetry in NC metals raise the possibility that yield and inelastic flow in these materials may not be adequately described by solely the deviatoric stress. Unfortunately, most literature concerning the mechanical testing of NC metals is limited to uniaxial deformation or nanoindentation techniques, and the multiaxial deformation behavior is often predicted assuming initially isotropic yield and subsequent flow normal to the yield surface. The primary objective of this thesis is to obtain a better understanding of the nature of inelasticity in NC metals by simulating multiaxial deformation at the atomistic resolution, and developing methods to interpret the results in ways that would be useful from a continuum constitutive modeling viewpoint. First, we have presented a novel, statistical mechanics-based approach to unambiguously resolve the elastic-plastic transition as an avalanche in the proliferation of mobile defects. This approach is applied to nanocrystalline Cu to explore the influence of pressure and multiaxial stress states on the inelastic deformation behavior. The results suggest that initial yield in nanocrystalline Cu under biaxial loading is only weakly anisotropic in the 5 nm grain size regime, and that plastic flow evolves in a direction normal to the von Mises yield surface. However, triaxial deformation simulations reveal a significant effect of the superimposed hydrostatic stress on yielding under shear. These results are analyzed in detail in order to assess the influence of pre-existing internal stresses and interfacial excess volume on the inelastic deformation behavior. Further, we have studied the effects of imposed hydrostatic pressure on the shear deformation behavior of Cu bicrystals containing symmetric tilt interfaces, as well as Cu nanocrystals of different grain sizes. Most interfaces exhibit an increase in shear strength with imposed compressive hydrostatic pressure. However, for some interfaces, this trend is reversed. Neither the sign nor the magnitude of the pressure-induced elevation in shear strength appears to correlate with interface structure or particular deformation mechanism(s). In Cu nanocrystals, we observe that imposed compressive pressure leads to strengthening under shear deformation, and the effect of imposed pressure on the shear strength becomes stronger with increase in grain size or temperature. Activation parameters for shear deformation have been computed for these nanocrystals, and computed values seem to agree with existing experimental and theoretical estimates. Finally, we have proposed some modifications to conventional isothermal molecular dynamics algorithms, in order to isolate dislocation nucleation events from interfacial sources, and thereby permit explicit computation of the activation parameters for such events.

碩士
國立高雄應用科技大學
機械與精密工程研究所
103
This study investigates the mechanical behavior of nano-scale monocrystalline and polycrystalline copper metal by computer aided. The indentation and tensile of nanocrystalline was simulated by molecular dynamics simulation theory with Fortran code. It is found that the grain-size effect, temperature effect and gradient effect can influence the stiffness and hardness with slip vector distribution, centrosymmetric parameters, shear strain distribution, and equivalent stress in nano-scale monocrystalline and polycrystalline copper metal. In the indentation test, we obtain better stiffness, hardness, and elastic recovery copper metal with monocrystalline than copper metal with polycrystalline. The Hall–Petch curve for the polycrystalline copper metal showed that the inverse value at small grain size (> 3.5 nm) due to grain rotate with high internal stress around the boundary. The kinetic energy would increase by temperature increase brought material defects and thus decrease the mechanical behavior. In the tensile test, we found blatant twin crystal interface with monocrytalline, which has different slip plane orientation and mechanical property by stretching lattice direction. We obtain better mechanical behavior with bigger grain size, and the necking harden was found at small grain size (< 2.0 nm). The soften situation that found at big grain size (>2.0 nm) will reduce by increase temperature.

Samples were prepared by high-energy implantation of Cu ions into a SiO_2 (5μm)/Si (substrate) matrix. Cu ions were implanted to a nominal dose of 1×10^16 - 3×10^17 /cm^2 at a sequential beam energy of 5000 - 800 keV and at a current density of ~5 μA/cm2. Implantation was carried out at LN2 temperature in a vacuum of < 10^-7 Torr. Nucleation and growth was induced by subsequential anneals in 5%H_2+95%N_2 (forming gas) for one hour at 500, 800, and 1100C. Determination of the nanocrystal structure and morphology within the silica film was accomplished by correlating results from X-Ray Diffraction (XRD), Rutherford Backscattering Spectroscopy (RBS), Transmission Electron Microscopy (TEM) and Extended X-ray Absorption Fine Structure (EXAFS). Results show that a mean dose of 1×10^16 /cm2 tends to form a significant fraction of Cu-O bonds at all annealing temperatures, except 1100C at which most Cu evaporates from the SiO_2 film. Oxides are also apparent in the as-implanted and 500C annealed sample of dose 3×10^16 /cm2. All higher anneals and doses readily formed Cu nanocrystals. In particular a dose of 3×10^17 /cm^2 showed similar EXAFS to that of a bulk Cu standard largely independent of temperature, while 1×10^17 cm^2 exhibited a crystalline size growth with increasing temperature. TEM displayed the nanocrystal size distribution, while XRD and in particular EXAFS data verified a mean nanocrystal size growth with dose as well as annealing temperature. The latter exemplified by an increase in co-ordination number. Further, EXAFS showed the bond length remained constant for all samples, except 1×10^16 /cm2 possibly due to oxides, at all annealing temperatures. The bond length was found to be distinctively longer than that for a bulk Cu standard.

碩士
國立臺灣大學
化學工程學研究所
91
In this study, we synthesize copper-titanium dioxide catalysts by loading on nanocrystalline titanium dioxide prepared by sol-gel process. The Cu-loading methods are impregnation and sol-gel method. Photocatalytic reactions of decomposition in alcohol solution to produce hydrogen were investigated. The results show that the former is better than the later. By TPR analysis it can be speculated that Cu adsorbs on the surface of titanium dioxide by chemical adsorption. Therefore, the different phototcatalytic activity of loading methods is resulted from Cu covered with titanium dioxide by using sol-gel method. From the experiments we find out that the initial producing rate of hydrogen with copper-titanium dioxide catalysts is much higher than with titanium dioxide. It proves that the loading of Cu really enhance the photocatalytic reactivity. The initial producing rate 3124 (μmole/hr) of hydrogen gives the most active powders, with the Cu loading amount of 1.2 wt% by using impregnation. Besides, in experiments we found that the activity of Cu-impregnating titanium dioxide is decayed due to long time exposure under the atmosphere. In this study, we also try to use the titanium oxide prepared by sol-gel method and commercial product Degussa P-25 as substrate respectively, and loaded copper onto surface via impregnation. The specific surface areas are 110 m2 / g and 43 m2 / g individually. The results show that the activity changes slowly very much to follow with the Cu loading amount growth if commercial powder with less specific surface was applied as substrate. The reason is that the less specific surface result in the loading of Cu is covered by one another, and influences on the photocatalytic performance. .

Copper is a widely used conductor in the manufacture of printed wiring boards (PWB). The trends in miniaturization of electronic devices create increasing challenges to all electronic industries. In particular PWB manufacturers face great challenges because the increasing demands in greater performance and device miniaturization pose enormous difficulties in manufacturing and product reliability. Nanocrystalline and ultrafine grain copper can potentially offer increased reliability and functionality of the PWB due to the increases in strength and achievable wiring density by reduction in grain size. The first part of this thesis is concerned with the synthesis and characterization of nanocrystalline and ultra-fine grain-sized copper for potential applications in the PWB industry. Nanocrystalline copper with different amounts of sulfur impurities (25- 230ppm) and grain sizes (31-49nm) were produced and their hardness, electrical resistivity and etchability were determined. To study the thermal stability of nanocrystalline copper, differential scanning calorimetry and isothermal heat treatments combined with electron microscopy techniques for microstructural analysis were used. Differential scanning calorimetry was chosen to continuously monitor the grain growth process in the temperature range from 40C to 400C. During isothermal annealing experiments samples were annealed at 23C, 100C and 300C to study various potential thermal issues for these materials in PWB applications such as the long-term room temperature thermal stability as well as for temperature excursions above the operation temperature and peak temperature exposure during the PWB manufacturing process. From all annealing experiments the various grain growth events and the overall stability of these materials were analyzed in terms of driving and dragging forces. Experimental evidence is presented which shows that the overall thermal stability, grain boundary character and texture evolution of copper is greatly related to changes in driving and dragging forces, which in turn, are strongly depended on parameters such as annealing temperature and time, total sulfur impurity content and the distribution of the impurities within the material. It was shown that a simple increase in the sulfur impurity level does not necessarily improve the thermal stability of nanocrystalline copper.

Thesis (M. Tech. degree in Chemistry) Tshwane University of Technology 2013.
Discusses the nanostructured platinum group catalysts provide an efficient route for the oxidative coupling of naphthols. The potential of a new catalytic reaction described in the patent literature has not yet been fully explored, although the reaction could provide an efficient new route to chromophoric systems containing conjugated aromatic rings.

碩士
國立臺灣科技大學
材料科學與工程系
104
Up to now, the mechanism to cause room temperature ferromagnetism in CeO2 doped with divalent cations is still controversial. In this study, CeO2 nanoparticles (NPs) doped with Cu2+ were prepared by precipitation method. The doping level was from 0 to 17 at%. Crystal structure, particle size and valency were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-rays absorption spectroscopy (XAS). Magnetism at room temperature was revealed by vibrating sample magnetometer (VSM) and magnetic circular dichroism (MCD). XAS spectra revealed that with increasing the Cu concentration, the mixed valence states and presence of Cu1+ and Ce3+ was observed when the doping level is lower than the critical point (10%). Moreover, the charge transfer effect between Cu and Ce was also perceived. Additionally, the Cu ion does not substitute for the Ce ion and would exist in interstitial site from Extended X-ray Absorption Fine Structure (EXAFS) calculation. As doping level is over 10%, nanosized CuO formed at the surface of CeO2 and decreased the Ce valent. M-H hysteresis curves for all NPs exhibit Room temperature ferromagnetism (RTFM) behavior. Significantly, magnetic moment was only identified on Ce M-edge XMCD spectra. It is proposed that the origin of RTFM and the existence of cross-coupling between the magnetic and electric interaction, termed as magnetoelectronic properties, can be described by Bound magnetic polaron (BMP).

碩士
國立虎尾科技大學
光電與材料科技研究所
93
The characteristics and performance of indium tin oxide (Indium Tin Oxide, ITO) as diffusion barrier between copper and silicon were studied by using the transmission electron microscope (TEM), scanning electron microscope (SEM), X-ray diffraction (XRD), energy dispersive spectroscopy (EDS), and sheet resistance measurement. The results revealed that the structure and thickness of indium tin oxide between copper and silicon is nanocrystalline and 10 nm, respectively and it can be effective to hinder diffusion between copper and silicon. The indium tin oxide thin film was found to be a good diffusion barrier against Cu at least up to 650°C. The failure temperature of ITO films diffusion barrier (10 nm) was about 700°C. Our results show that ITO film can be considered as diffusion barriers for Cu metallization. The failure mechanism of indium tin oxide diffusion barrier is that the agglomeration of copper thin film and then induced indium tin oxide thin film to agglomerate. In order to raise the failure temperature, the indium tin oxide of 20 nm was deposited on copper as a capping layer. The results show that the failure temperature was lifted 750℃ after adding a capping layer ITO on Cu film.

碩士
國立臺北科技大學
機電整合研究所
100
Electroplating is defined as an application process of electrodeposition. It has a wide range of industrial applications which require the functional and appearance improvements over the substrate surface. Electroplating has become an integral part of the manufacturing technology and process improvement has been a major task for the engineers and scientists. The supercritical phase is a special state of a substance between liquid and gas phases in certain heated and pressurized environments which exceed its critical point. Carbon dioxide, as a colorless and odorless inert gas in the ambient temperature and pressure, becomes supercritical phase in a pressure higher than 7.39 MPa and the temperature higher than 31.3 ?C. Its applications include the well-developed supercritical fluid extraction. Electrodeposited copper has good electrical conductivity, and is more easily prepared from acidic electroplating solution, such as the low-cost, easily controlled copper sulfate electrolyte. This study focused on the implementation of the electroplated copper plating in copper sulfate bath with the assistance of supercritical carbon dioxide. Comparison between conventional plating and the supercritical carbon dioxide assisted electroplating was performed with consideration in the effects of additives in the plating bath. In this study, the effectiveness of the proposed supercritical process successfully demonstrated the potential even without additives in the plating bath. The grain size of the coating was reduced and the hardness increased accordingly. However, the internal stress of the coating increased in supercritical plating. Fortunately, by raising the current density, the internal stress can be effectively reduced. The possible underlined mechanisms for the observed experimental results were also explored in this thesis.

碩士
國立成功大學
材料科學及工程學系碩博士班
96
In this study nano-twin coppers were synthesized by using a pulsed electrodeposition technique from an electrolyte of CuSO4, in which the current density and frequency were experiment parameters. Electron back-scattering diffractioin (EBSD) and XRD were carried on characterizing microstructure features of preferred orientation, grain size and boundary character. It was observed that the grain size decreases with increasing the current density and with decreasing the frequency. Increasing a current density leads to enhance a nucleation rate, resulting in a fine-grain microstructure. However, as a frequency increases, a disproportionation reation of cuprous ions and a dissolution reaction of copper adatoms into bulk solution, resulting in a coarse-grain microstructure. The average grain size of as-deposited coppers determined from XRD, EBSD and TEM are 82.9nm, 1.035μm and for 0.5μm to 1.0μm, respectively. The as-deposited Cu samples consisted of growth twins and irregular-shaped grains with a {110} preferred orientation. Scherrer’s equation is not able to determine a correct grain size of preferred orientation materials. The determination of grain size using XRD is limited due to the application of Scherrer’s equation. TEM images show a higher spatial resolution of microstructures than EBSD, but the observed area of EBSD could be several orders larger than that of TEM. This means that an orientation image map obtained from EBSD provides a higher accuracy in statistics than a microstructure from TEM.

Thin film nanostructures may be defined as assemblies, arrays, or randomly distributed nanoparticles, nanowires, or nanotubes, which together form a layer of materials supported on a substrate surface. Because such nanostructures are supported on a substrate surface, their potential applications cover a wide area in optical, magnetic, electrochemical, electromagnetic, and optoelectronic devices. The focus of the present thesis is the development of methodologies to grow certain thin film nanostructures of some transition metal oxides (TMOs), including copper oxides and LixCoO2, through CVD, sol-gel, and electromagnetic radiation-mediated approaches. The work towards this objective can be divided into three parts: first, the design, synthesis, and systematic identification of novel metalorganic precursors of copper (monometallic) and Li and Co (bimetallic); second, the growth of nanostructured oxides thin films using these precursors; and third, the application of electromagnetic radiation to control or tailor the growth of as grown nanostructures. The underlying growth mechanisms substantiated by appropriate evidence have been put forward, wherever found relevant and intriguing. It may be added that the principal objective of the work reported here has been to explore the several ideas noted above and examine possibilities, rather than to study any specific one of them in significant detail. It is hoped earnestly that this has been accomplished to a reasonable extent. Chapter 1 reviews briefly the reports available in the literature on three specific methods of growing thin films nanostructures, namely chemical vapour deposition, sol-gel processing and light-induced approach. The objective of this chapter has been to provide the background of the work done in the thesis, and is substantiated with a number of illustrative examples. Some of the fundamental concepts involved, viz., plasmons and excitons, have been defined with illustration wherever found relevant in the context of the work. Chapter 2 describes the various techniques used for synthesis and characterisation of the metalorganic complexes as well as of the thin films. This chapters covers mostly experimental details, with brief descriptions of the working principles of the analytical procedures adopted, namely, infrared spectroscopy, mass spectroscopy, elemental analysis, and thermal analysis for characterisation of the metalorganic complexes. This is followed by a similarly brief account of techniques employed to characterize the thin films prepared in this work, viz., glancing incidence X-ray diffraction (GIXRD), field-emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), electrostatic force microscopy (EFM), transmission electron microscopy (TEM), glancing incidence infra-red spectroscopy (GIIR) and, UV-visible spectroscopy. The metalorganic chemical vapour deposition (MOCVD) systems built in house and used for growth of films are described in detail. The topics in the different sections of the chapter are accompanied by pertinent diagrams. Chapter 3 deals with the design, synthesis and characterisation of novel polynuclear complexes of copper and cobalt. Keeping in mind the various advantages such as low toxicity, ease of synthesis, non-pyrophoricity, and low temperature volatility, of environmentally benign complexes based on biologically compatible such as triethanolamine, diethanolamine, the objective has been to synthesize complexes containing triethanolamine and diethanolamine of transition metals such as cobalt and copper, and to investigate their applicability in MOCVD processes as a novel class of precursors. With the notion of ‘better’ and efficient design of precursors, an attempt has been made, through a semi-empirical modeling, to understand the correlation between volatility and various intrinsic molecular parameters such as lattice energy, vibrational-rotational energy, and internal symmetry. Chapter 4 discusses the growth of nanoporous Cu4O3-C composite films through the MOCVD process employing Cu4(deaH)(dea)(oAc)5.(CH3)2CO as the precursor. The various characteristic aspects of as-grown films, such as their crystallinity, morphology, and composition have been covered elaborately in various sections of this chapter. The chapter describes the efficient guiding and confining of light exploiting the photonic band gap of these nanoporous films, which indicates the potential usefulness of these and similar films as optical waveguides. A model described in the literature on absorbing photonic crystals, wherein a periodically modulated absorption entails an inevitable spatial modulation of dispersion, i.e., of the index contrast to open a photonic band gap, has been used to calculate the indices of refraction of one of these nanoporous films. The chapter also reports briefly the preliminary electrochemical investigations carried out on a typical film, examining the notion of its application as the anode in a Li-ion rechargeable battery. Chapter 5 describes the synthesis of nanocrystalline LixCoO2 films by the sol-gel method. Reports available in literature indicate that the various phases of LixCoO2 are extremely sensitive to processing temperature, making it difficult to control dimensionality of a given phase using temperature as one of process parameters. We have investigated the possibility of using incoherent light to tailor the particle size/shape of this material. The as-grown and irradiated films were characterised by X-ray diffraction, and by microscopic and spectroscopic techniques.Optical spectroscopy was carried out in order to gain insight into the physico-chemical mechanism involved in such structural and morphological transformation. Chapter 6 deals with the synthesis of self-assembled nanostructures from the pre-synthesized nanocrystals building blocks, through optical means of exciton formation and dissociation. It has been demonstrated that, upon prolonged exposure to (incoherent) ultraviolet-visible radiation, LixCoO2 nanocrystals self-assemble into acicular architectures, through intermediate excitation of excitons. Furthermore, it has been shown that such self-assembly occurs in nanocrystals, which are initially anchored to the substrate surface such as that of fused quartz. This new type of process for the self-assembly of nanocrystals, which is driven by light has been investigated by available microscopic and spectroscopic techniques. Chapter 7 describes the stabilisation of chemically reactive metallic lithium in a carbonaceous nanostructure, viz., a carbon nanotube, achieved through the MOCVD process involving a lithium-alkyl moiety. This moiety is formed in situ during deposition through partial decomposition of a metalorganic precursor synthesized in house, which contains both lithium and cobalt. It is surmised that the stabilization of metallic Li in the nanostructure in situ occurs through the partial decomposition of the metalorganic precursor. Quantitative X-ray photoelectron spectroscopy carried out on such a film reveals that as much as 33.4% metallic lithium is trapped in carbon. Lastly, Chapter 8 briefly highlights the outlook for further investigations suggested by the work undertaken for this thesis. Novel precursors derived from biologically compatible ligands can open up possibility of growing new type of micro/nano-structures, and of unusual phases in the CVD grown films. Furthermore, it is proposed that the novel method of growth and alignment of nanocrystals through irradiation with incoherent light, employed for the specific material LixCoO2, may be employed for various other metallic and semiconducting materials.

Ceramics and polymer-ceramic composites associated with high dielectric constants are of both scientific and industrial interest as these could be used in devices such as capacitors, resonators and filters. High dielectric constant facilitates smaller capacitive components, thus offering the opportunity to miniaturize the electronic devices. Hence there is a continued interest on high dielectric constant materials over a wide range of temperatures. Recently, CaCu3Ti4O12 (CCTO) ceramic which has centro-symmetric body centered cubic structure has attracted considerable attention due to its large dielectric constant (ε ~104-105) which is nearly independent of frequency (upto 10 MHz) and low thermal coefficient of permittivity (TCK) over 100-600K temperature range. Apart from the high dielectric ceramics, high dielectric polymer-ceramic composites have also become promising materials for capacitor applications. By combining the advantages of high dielectric ceramics and low leakage behaviour of polymers, one can fabricate new hybrid materials with high dielectric constants, and high breakdown field to achieve high volume efficiency and energy storage density for capacitor applications. The CCTO polycrystalline powders were generally prepared by the conventional solid-solid reaction route with CaCO3, TiO2 and CuO as the starting materials. This method of preparation often requires high temperatures and longer durations. To overcome these difficulties, in the present investigations, an attempt has been made to synthesize CCTO by adopting microwave assisted heating technique and wet chemical synthesis routes. Also the CCTO crystallites (size varying from nano to micrometers) incorporated in the Polyvinyliden fluoride (PVDF) and Polyaniline (PANI) matrix and several composites with high dielectric constants were fabricated and investigated. Further, the high dielectric constant glasses in the system (100-x)TeO2-xCaCu3Ti4O12, (x=0.5 to 3) were fabricated by the conventional melt-quenching technique and their structural and dielectric properties were studied. The results obtained pertaining to these aforementioned investigations are classified as follows. Chapter 1 is intended to give basic information pertaining to the dielectrics and various mechanisms associated with high dielectric constants. Brief exposure to the high dielectric constant materials is also given. The structural aspects of CCTO, various synthetic routes adopted for the synthesis and the origin of the dielectric anomaly in CCTO are elaborated. In addition, basic information about the high dielectric polymer-ceramic composites and glasses are provided. In chapter 2 the various experimental techniques that were employed to synthesize and characterize the materials under investigation were discussed. Chapter 3 reports the synthesis and characterization of CaCu3Ti4O12, (CCTO) powders by microwave assisted heating at 2.45 GHz, 1.1kW. The processing and sintering were carried out at different temperatures for varied durations. The optimum calcination temperature using microwave heating was found to be 950oC for 20 minutes to obtain cubic CCTO powders. This is found to be fast and energy efficient as compared to that of the conventional methods. The structure, morphology and dielectric properties of the CCTO ceramic processed by microwave assisted heating were studied via X-ray diffraction, Scanning electron microscopy (SEM) and impedance analyser. These studies revealed that, the microwave sintered (MS) samples were less porous than that of the conventional ones. Relative density of about 95% was achieved for the MS pellets (1000oC/60min) while for the conventional sintered (CS) pellets (1100oC/2h) it was only 91%. The dielectric constants for the microwave sintered (1000oC/60min) ceramics were found to vary from 11000 to 6950 in the 100 Hz to 100 kHz frequency range. The presence of larger grains (6-10μm) in the MS samples contributed to the higher dielectric constants. Chapter 4 deals with the synthesis of complex oxalate precursor, CaCu3(TiO)4(C2O4)8 • 9H2O, by the wet chemical route. The various trials and the different reaction schemes involved for the preparation of complex oxalate precursor were highlighted. The oxalate precipitate thus obtained was characterized by the wet chemical analyses, X-ray diffraction, FTIR absorption and TG/DTA analyses. The complex oxalate precursor, CaCu3(TiO)4(C2O4 )8.9H2O was subjected to thermal oxidative decomposition and the products of thermal decomposition were investigated employing XRD,TGA, DTA and FTIR techniques. Nanocrystallites of CaCu3Ti4O12 with the size varying from 30-200 nm were obtained at a temperature as low as 680oC. The nanocrystallites of CaCu3Ti4O12 were characterized using Electron Spin Resonance (ESR) and optical reflectance techniques. The selected area electron diffraction (SAED) pattern with the zone axis [012] and spot pattern in electron diffraction (ED) indicate their single-crystalline nature. The optical reflectance and ESR spectra indicate that the Cu (II) coordination changes from distorted octahedra to nearly flattened tetrahedra (squashed) to square planar geometry with increasing heat treatment temperature. The powders derived from the oxalate precursor have excellent sinterability resulting in high density ceramics which exhibited giant dielectric constants upto 40,000 (1 kHz) at 25oC, accompanied by low dielectric loss < 0.07. The effect of calcium content on the dielectric properties of CaxCu3Ti4O12 (x=0.90, 0.97, 1.0, 1.1 and 1.15) derived from the oxalate route was described in Chapter 5. The structural, morphological and dielectric properties of the ceramics were studied using X-ray diffraction, Scanning Electron Microscope along with Energy Dispersive X-ray Analysis (EDX), and Impedance analyzer. The X-ray diffraction patterns obtained for the x= 0.97, 1.0 and 1.1 ceramics could be indexed to a body– centered cubic perovskite related structure associated with the space group Im3. The microstructural studies revealed that the grains are surrounded by exfoliated sheets of Cu-rich phase. The microstructure that is evolved for the Ca0.97 ceramic more or less resembles that of the Ca1.0 ceramic, but the density of such exfoliated sheets of cu-rich phase is lesser for the Ca0.97 ceramic and none for Ca1.1 ceramic. The sintered pellet (x=0.97) was ground and thinned to the required thickness (~ 20nm) and analyzed using Transmission Electron Microscopy (TEM). The current-voltage (I-V) characteristics of the ceramics exhibited non-linear behaviour. The dielectric properties of these suggest that the sample corresponding to the composition x=0.97, has a reduced dielectric loss while retaining its high dielectric constant. Chapter 6 illustrates the results concerning the fabrication and characterization of nanocrystal composites of Polyaniline (PANI) and CaCu3Ti4O12 (CCTO). These were prepared using a simple procedure involving in-situ polymerization of aniline in dil. HCl. The PANI and the PANI-CCTO composites were subjected to X-ray diffraction, Fourier Transform Infrared (FTIR), Thermo gravimetric, Scanning Electron Microscopic (SEM) and Transmission electron microscopic analyses. The FTIR spectra recorded for the composites was similar to that of pure PANI unlike in the case of X-ray diffraction wherein the characteristics of both PANI and CCTO were reflected. The TGA in essence indicated the composites to have better thermal stability than that of pure PANI. The composite corresponding to 50%CCTO-50%PANI exhibited higher dielectric constant (4.6x106 @100Hz). The presence of the nano crystallites of CCTO embedded in the nanofibers of PANI matrix was established by TEM. The AC conductivity increased slightly upto 2kHz as the CCTO content increased in the PANI which was attributed to the polarization of the charge carriers. The value of dielectric constant obtained was higher than that of the other PANI based composites reported in the literature. Chapter 7 deals with the fabrication and characterization of diphasic Poly(vinylidene fluoride) (PVDF)-CCTO composite. The CCTO crystallites (size varying from nano to micrometers) incorporated in the Polyvinylidene fluoride (PVDF) and composites with varying CCTO content were fabricated. The structural, morphological and dielectric properties of the composites were studied using X-ray diffraction, Thermal analysis, Scanning Electron Microscope (SEM), Transmission Electron Microscopic (TEM) and Impedance analyzer. The room temperature dielectric constant as high as 95 at 100Hz has been realized for the composite with 0.55 Vol.fraction of CCTO (micro sized crystallites), which has increased to about 190 at 150oC. Whereas, the PVDF/CCTO nanocrystal composite with 0.13Vol.fraction of CCTO has exhibited higher room temperature dielectric constant (90 at 100Hz). The PVDF/CCTO nanocrystal composite was further investigated for the breakdown strength and electric modulus. The breakdown strength plotted against the dielectric constant evidenced an inverse relationship of breakdown voltage with the dielectric constant. The relaxation processes associated with these composites were attributed to the interfacial polarization or Maxwell-Wagner-Sillars (MWS) effect. Various theoretical models were employed to rationalize the dielectric behavior of these composites. The fabrication and characterization details of optically clear colored glasses in the system (100-x)TeO2-xCaCu3Ti4O12, (x=0.5 to 3 mol%) are reported in Chapter 8. The color varies from olive green to brown as the CaCu3Ti4O12 (CCTO) content increased in TeO2 matrix. The X-ray powder diffraction and differential scanning calorimetric analyses that were carried out on the as-quenched samples confirmed their amorphous and glassy nature respectively. The optical transmittance of the glasses exhibited typical band-pass filter characteristics. The dielectric constant and loss in the 100 Hz-1MHz frequency range were monitored as a function of temperature (323K673K). The dielectric constant and the loss increased as the CCTO content increased in TeO2 at all the frequencies and temperatures under study. Further, the dielectric constant and the loss were found to be frequency independent in the 323-473 K temperature range. The value obtained for the loss at 1MHz was 0.0019 which was typical of low loss materials, and exhibited near constant loss (NCL) contribution to the ac conductivity in the 100Hz-1MHz frequency range. The electrical relaxation was rationalized using the electrical modulus formalism. These glasses are found to be more stable (a feature which may be of considerable interest) as substrates for high frequency circuit elements in conventional semiconductor industries. Thesis ends with summary and conclusions, though each chapter is provided with conclusions and complete list of references.

Microtrusses are hybrid materials composed of a three-dimensional array of struts capable of efficiently transmitting an externally applied load. The strut connectivity of microtrusses enables them to behave in a stretch-dominated fashion, allowing higher specific strength and stiffness values to be reached than conventional metal foams. While much attention has been given to the optimization of microtruss architectures, little attention has been given to the strengthening mechanisms inside the materials that make up this architecture. This thesis examines strengthening mechanisms in aluminum alloy and copper alloy microtruss systems with and without a reinforcing structural coating. C11000 microtrusses were stretch-bend fabricated for the first time; varying internal truss angles were selected in order to study the accumulating effects of plastic deformation and it was found that the mechanical performance was significantly enhanced in the presence of work hardening with the peak strength increasing by a factor of three. The C11000 microtrusses could also be significantly reinforced with sleeves of electrodeposited nanocrystalline Ni-53wt%Fe. It was found that the strength increase from work hardening and electrodeposition were additive over the range of structures considered. The AA2024 system allowed the contribution of work hardening, precipitation hardening, and hard anodizing to be considered as interacting strengthening mechanisms. Because of the lower formability of AA2024 compared to C11000, several different perforation geometries in the starting sheet were considered in order to more effectively distribute the plastic strain during stretch-bend fabrication. A T8 condition was selected over a T6 condition because it was shown that the plastic deformation induced during the final step was sufficient to enhance precipitation kinetics allowing higher strengths to be reached, while at the same time eliminating one annealing treatment. When hard anodizing treatments were conducted on O-temper and T8 temper AA2024 truss cores, the strength increase was different for different architectures, but was nearly the same for the two parent material tempers. Finally, the question of how much microtruss strengthening can be obtained for a given amount of parent metal strengthening was addressed by examining the interaction of material and geometric parameters in a model system.