Carbon dioxide (CO2) is arguably the most high-profile molecule of recent times. Although much of its bad press comes from environmental concerns associated with greenhouse gas emissions, there exists the possibility to harness this abundant resource for application to the synthesis and processing of useful materials. This article describes a selection of recent successes in using supercritical carbon dioxide (scCO2) as a solvent for polymerizations. Further, the uses of compressed CO2 as a processing tool in the fabrication of materials for applications such as coatings and biomaterials are discussed. Finally, the application of scCO2 to photolithography is demonstrated, with particular focus on CO2 as a processing solvent for the patterning of organic electronic devices.

A combined experimental/numerical approach was developed to determine the distribution of current density, temperature, and stress arising within the sample during spark plasma sintering (SPS) treatment of zirconium carbide (ZrCx) or oxycarbide (ZrCxOy). Stress distribution was calculated by using a numerical thermomechanical model, assuming that a slip without mechanical friction exists at the interfaces between the sample and the graphite elements. Heating up to 1950 °C at 100 °C min−1 and a constant applied pressure of 100 MPa were retained as process conditions. Simulated temperature distributions were found to be in excellent agreement with those measured experimentally. The numerical model confirms that, during the zirconium oxycarbide sintering, the temperature measured by the pyrometer on the die surface largely underestimates the actual temperature of the sample. This real temperature is in fact near the optimized sintering temperature for hot-pressed zirconium oxycarbide specimens. It is also shown that high stress gradients existing within the sample are much higher than the thermal ones. The amplitude of the stress gradients was found to be correlated with those of temperature even if they are also influenced by the macroscopic sample properties (coefficient of thermal expansion and elastic modulus). At high temperature, the radial and angular stresses, which are much higher than the vertical applied stress, provide the more significant contribution to the stress-related driving force for densification during the SPS treatment. The heat lost by radiation toward the wall chambers controlled both the thermal and stress gradients.

Thin films of Ga-doped ZnO (GZO) were prepared on glass and Al2O3 (0001) substrates by using RF magnetron sputtering at a substrate temperature of 350 °C, RF power of 175 W, and working pressure of 6 mTorr. The effect of film thickness and substrate type on the structural and electrical properties of the thin films was investigated. X-ray diffraction study showed that GZO thin films on glass substrates were grown as a polycrystalline hexagonal wurtzite phase with a c-axis preferred, out-of-plane orientation and random in-plane orientation. However, GZO thin films on Al2O3 (0001) substrates were epitaxially grown with an orientation relationship of . The structural images from scanning electron microscopy and atomic force microscopy showed that the GZO thin films on glass substrates had a rougher surface morphology than those on Al2O3 (0001) substrates. The electrical resistivity of 1000 nm-thick GZO thin films grown on glass and Al2O3 (0001) substrates was 3.04 × 10−4 Ωcm and 1.50 × 10−4 Ωcm, respectively. It was also found that the electrical resistivity difference between the films on the two substrates decreased from 9.48 × 10−4 Ωcm to 1.45 × 10−4 Ωcm with increasing the film thickness from 100 nm to 1000 nm.

The continuous improvement in luminous efficacy of “white” light-emitting-diode (LED) sources offers the potential of considerable energy savings in general lighting applications. Recent experiments at UCSB have demonstrated 117 lumens per watt (lm/W) in white LEDs, with further improvements expected in the near future. Considerable progress has also been achieved using nonpolar GaN, such as a-plane {1120} and m-plane {1100} GaN, or semipolar GaN substrates. Such devices avoid the deleterious effects of charge separation due to spontaneous and piezoelectric polarization inherent in most c-axis-oriented devices.

Single perovskite polycrystalline Pb(Mg1/3Nb2/3)O3–PbTiO3 (PMN-PT) thin films with PMN to PT ratios around the morphotropic phase boundary composition (070PMN-0.30PT, 0.65PMN-0.35PT, and 0.60PMN-0.40PT) have been prepared by chemical solution deposition (CSD). Air-stable and precipitate-free PMN and PT precursor sols were separately synthesized, and PMN-PT sols were obtained by the simple mixture in air of the former. The PMN-PT sols were deposited onto Pt-coated Si substrates and dried on a hot-plate. Crystallization of the films was carried out by rapid thermal processing (RTP) in oxygen, using different temperatures, soaking times, and heating rates. Single perovskite PMN-PT thin films were obtained at low temperatures (650 °C) with short soaking times (6s) and rapid heating rates (200 °C/s). The films show a columnar growth and a uniform thickness. Both the evolution of the perovskite distortion and the electrical properties with the PMN to PT ratio indicate the correct formation of the solid solution. The temperature and frequency dependences of the permittivity and the ferroelectric loops also indicate an increase of the relaxor characteristic of the films as compared with bulk materials. Piezoelectric coefficients were measured across the ferroelectric loop by optical interferometry, and an enhancement of piezoelectricity at the MPB composition was found. A piezoelectric d33 coefficient of ∼55 pC/N was measured in ∼300-nm-thick films of this composition with a saturation polarisation of Ps ∼25 μC/cm2.

In a previous paper, we have demonstrated that a microcrystalline copper film well bonded to a polymer substrate can be stretched beyond 50% without cracking. The film eventually fails through the coevolution of necking and debonding from the substrate. Here we report much lower strains to failure (approximately 10%) for polymer-supported nanocrystalline metal films, the microstructure of which is revealed to be unstable under mechanical loading. We find that strain localization and deformation-associated grain growth facilitate each other, resulting in an unstable deformation process. Film/substrate delamination can be found wherever strain localization occurs. Therefore, we propose that three concomitant mechanisms are responsible for the failure of a plastically deformable but microstructurally unstable thin metal film: strain localization at large grains, deformation-induced grain growth, and film debonding from the substrate.

The strain-induced austenite (γ) to martensite (α′) transformation in AISI 316L austenitic stainless steel, either in powders or bulk specimens, has been investigated. The phase transformation is accomplished using either ball-milling processes (in powders)—dynamic approach—or by uniaxial compression procedures (in bulk specimens)—quasi-static approach. Remarkably, an increase in the loading rate causes opposite effects in each case: (i) it increases the amount of transformed α′ in ball-milling procedures, but (ii) it decreases the amount of α′ in pressed samples. Both the microstructural changes (e.g., crystallite size refinement, microstrains, or type of stacking faults) in the parent γ phase and the role of the concomitant temperature rise during deformation seem to be responsible for these opposite trends. Furthermore, the results show the correlation between the γ → α′ phase transformation and the development of magnetism and enhanced hardness.

Fundamental knowledge on the oxidation behavior of pure indium, commonly used as a low-temperature, fluxless soldering material in micro-electro-mechanical system (MEMS) devices, is of importance as it influences the solder joint reliability. A thermodynamic model of the oxidation and reduction behavior of indium is developed by constructing an Ellingham diagram, and by using H2(g) reactions. Partial pressure (p) of H2O was shown to be the critical parameter in creating a reducing environment in the applicable solder reflow temperature range. Verification of the thermodynamic models was then carried out through heating and melting of indium in controlled glove box environments by adjusting p(H2)/p(H2O). The nanometer scale thickness of the oxide layer grown on indium was measured by a spectroscopic ellipsometer. The growth mechanism for oxidation in air below 220 °C follows Uhlig's logarithmic law where electron transport is the rate-controlling mechanism, implying that there is an incubation period for the onset of initial oxidation. Its activation energy was found to be 0.65 eV.

Bulk metallic glasses (BMGs) with high thermal stability and good corrosion resistance were synthesized in the (Cu0.6Hf0.25Ti0.15)100−x−yNiyNbx system by copper mold casting. The addition of Ni element causes an extension of a supercooled liquid region (ΔTx = Tx – Tg) from 60 K for Cu60Hf25Ti15 to 70 K for (Cu0.6Hf0.25Ti0.15)95Ni5. The simultaneous addition of Ni and Nb to the alloy is effective in improving synergistically the corrosion resistance in 1 N HCl, 3 mass% NaCl, and 1 N H2SO4 + 0.01 N NaCl solutions. The highly protective Hf-, Ti-, and Nb-enriched surface film is formed by the rapid initial preferential dissolution of Cu and Ni, which is responsible for the high corrosion resistance of the alloys in the solutions examined.

The glass formation in Fe-rich ternary Fe-B-Nd and quaternary (Fe,B,Nd)96Nb4 alloys has been studied and the best ternary and quaternary glass formers are located at Fe67B23Nd10 and (Fe68B25Nd7)Nb4 with critical diameters of 1 and 4 mm, respectively. For (Fe,B,Nd)96Nb4 alloys, the competing phases with glass were identified by monitoring the microstructure change. Fe14Nd2B was discovered to be one competing phase, which is the principle magnetic phase for Nd-Fe-B hard magnets. Composites with uniformly distributed Fe14Nd2B were formed for quaternary alloys with a diameter of 1.5 to 3 mm. Bulk hard magnets could be obtained by directly annealing the composites in a compositional area. A hard magnet with a coercivity of 1,100 kAm−1 and a maximum energy product, (BH)max, of 33 kJm–3 was obtained at (Fe67B23Nd10)96Nb4 by annealing. The combination of hard magnetic properties and the large critical sample size may make these alloys a commercially viable candidate for industrial applications.

Dense, crystalline mullite (3Al2O3ċ2SiO2) coatings have been deposited by chemical vapor deposition on Si-based substrates using the AlCl3–SiCl4–CO2–H2 system. A graded coating composition has been achieved in the coatings, with the Al/Si ratio being stoichiometric (∼3) at the coating/substrate interface, and increasing monotonically toward the outer coating surface. The highest reported Al-rich mullite has been deposited in the process. At high Al/Si ratios, the mullite structure breaks down and an aluminosilicate phase similar to the metastable δ* Al2O3 is nucleated. Experimental evidence is presented in this study that this phase has some Si-incorporation in it and has been called δ*(Si)Al2O3. Like the other known aluminosilicates, δ*(Si)Al2O3 converts to mullite on heating at elevated temperatures.

We present a blunt mechanism to explain the serrated flow behavior and slight “work hardening” at the beginning of yielding during the compression of metallic glass, which is in line with the piling-up of parallel shear bands on the fracture surface with a gradually increasing space from the edge of surface to inside. Meanwhile, two intrinsic parameters, i.e., strength intensity of blunt behavior, , and global work-hardening sensitivity exponent, , are introduced to characterize the blunt effect on the net increase in flow stress or work-hardening behavior of metallic glass.

Al-based high-aspect-ratio microscale structures (HARMS) are basic building blocks for all-Al microdevices. Bonding of Al-based HARMS is essential for device assembly. In this paper, bonding of Al-based HARMS to flat Al plates using Al-Ge thin film intermediate layers is investigated. The structure of sputter codeposited Al-Ge thin films was studied by high-resolution transmission electron microscopy as a function of the average film composition. The structure of the interface region between Al-based HARMS bonded to flat Al plates is studied by combining focused ion beam sectioning and scanning electron microscopy. An extended bonding interface region, ∼100 μm in width, is observed and suggested to result from liquidus/solidus reactions as well as diffusion of Ge in solid Al at the bonding temperature of 500 °C. The extended interface region is suggested to be beneficial to Al-Al bonding via Al-Ge intermediate layers.

Low solubility dopant-host systems are well suited to study secondary phase segregation-microstructure dependence. We discuss the effect of microstructure on secondary phase segregation in epitaxial/oriented ZnO thin films with Cr as an unfavorable dopant (Cr:ZnO). Since differences in thin film microstructure are a function of the substrate and its orientation, simultaneous chemical vapor depositions were carried out on single crystals of Si (100), c-axis oriented Al2O3 (c-ALO), and r-axis oriented Al2O3 (r-ALO) resulting in epitaxial film growth on r-ALO and c-axis oriented film growth on Si and c-ALO, with a difference in vertical grain boundary density. To enhance the analysis sensitivity to the microstructure difference, the thickness of Cr:ZnO films was maintained at ∼50 nm. High-resolution transmission electron microscopy (HRTEM) analysis indicates uniform stress distribution in Cr:ZnO grown on r-ALO. Surface sensitive x-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectroscopy (TOF-SIMS) techniques were utilized for analysis of the data. We observe that a higher grain boundary density and the presence of an amorphous layer at the interface for films grown on Si(100) single crystal led to interfacial Cr-based secondary phase segregation as opposed to lower grain boundary density and epitaxial films grown on c-ALO and r-ALO single crystals, respectively. We also discuss the effects of trace carbon solubility on the film microstructure/secondary phase segregation relationship.

Titanium nitride nanopowders were synthesized through a chemical reduction of titanium tetrachloride by sodium in liquid ammonia. The products of the reaction were the mixture of sodium chloride and titanium nitride nanopowders. The mixture was then separated by ammonia extraction. The nanopowders were heated under vacuum up to 1200 °C and were characterized by x-ray diffraction (XRD), transmission electron microscopy (TEM), Brunauer-Emmet-Teller (BET) surface area measurement, and chemical analysis. The results show that the product is nanocrystalline cubic phase TiN with Ti/N atomic ratio performed 1:1, and the surface area is from 20 to 50 m2 ·g−1 depending on the heating temperature. The particle sizes estimated by the TEM analysis correspond well with the results of the surface area measurements. The XRD pattern indicates that the crystal size grows with an increase in heating temperature.

To understand the mechanism of the coercivity enhancement by a trace addition of Cu in Nd-Fe-B sintered magnets, we investigated the microstructure difference between Cu-doped and Cu-free alloys using high resolution scanning electron microscopy (HRSEM), transmission electron microscopy (TEM), and laser assisted three dimensional atom probe (LA-3DAP). From a serial sectioning back scattered electron (BSE) images of the Nd-rich phase obtained by an integration of the focused ion beam (FIB) and HRSEM technique, it was found that Cu addition leads to a continuous formation of Nd-rich thin layers along the grain boundaries. 3DAP analysis has shown that a thin Cu-rich layer with a thickness of approximately 2 nm is present at the interface between the Nd2Fe14B and Nd-rich phase grains.

When light is absorbed in organic semiconductors, bound electron–hole pairs known as excitons are generated. The electrons and holes separate from each other at an interface between two semiconductors by electron transfer. It is advantageous to form well-ordered nanostructures so that all of the excitons can reach the interface between the two semiconductors and all of the charge carriers have a pathway to the appropriate electrode. This article discusses charge and exciton transport in organic semiconductors, as well as the opportunities for making highly efficient solar cells and for using carbon nanotubes to replace metal oxide electrodes.

The thermoelectric properties of Nb-doped Zn4Sb3 compounds, (Zn1–xNbx)4Sb3 (x = 0, 0.005, and 0.01), were investigated at temperatures ranging from 300 to 685 K. The results showed that by substituting Zn with Nb, the thermal conductivities of all the Nb-doped compounds were lower than that of the pristine β-Zn4Sb3. Among the compounds studied, the lightly substituted (Zn0.995Nb0.005)4Sb3 compound exhibited the best thermoelectric performance due to the improvement in both its electrical resistivity and thermal conductivity. Its figure of merit, ZT, was greater than the undoped Zn4Sb3 compound for the temperature range investigated. In particular, the ZT of (Zn0.995Nb0.005)4Sb3 reached a value of 1.1 at 680 K, which was 69% greater than that of the undoped Zn4Sb3 obtained in this study.