This manuscript describes, defines, and discusses the process of cold sintering, which can consolidate a broad set of inorganic powders between room temperature and 300 °C using a standard uniaxial press and die. This temperature range is well below that needed for appreciable bulk diffusion, indicating immediately the distinction from the well-known and thermally driven analogue, allowing for an unconventional method for densifying these inorganic powders. Sections of this report highlight the general background and history of cold sintering, the current set of known compositions that exhibit compatibility with this process, the basic experimental techniques, the current understanding of physical mechanisms necessary for densification, and finally opportunities and challenges to expand the method more generically to other systems. The newness of this approach and the potential for revolutionary impact on traditional methods of powder-based processing warrants this discussion despite a nascent understanding of the operative mechanisms.

The refractory nature of BaTiO3 leads to limited densification and grain growth for films processed at low temperatures and a modest nonlinear dielectric response due to a marked sensitivity to physical scale and material quality. Adding liquid-forming sintering aids, common in bulk ceramics, to thin films enhances mass transport, leading to enhanced grain growth at lower temperatures. This work explores the effectiveness of a sputtered CuO buffer layer with BaO–B2O3 (BBO) fluxes to engineer the microstructure of BaTiO3 films. Grain size and homogeneity increase in the presence of even a ∼1 nm CuO layer. In general, grain size increases from 75 to 370 nm with an addition of 2.2% BBO and 8 nm CuO. Room temperature capacitance in fluxed films increases by a factor of 5 over pure films, and ferroelectric phase transitions are clearly observable in dielectric measurements. CuO–BBO proves effective on (0001) Al2O3 and (100) MgO substrates, although all microstructures are notably finer for the latter.

A low-temperature thin-film processing method for BaTiO3 is studied to understand microstructure development in the presence of a liquid-forming phase. The addition of a eutectic barium borate flux is found to prevent nucleation of BaTiO3 during pulsed-laser deposition on sapphire substrates at 400 °C. Subsequent thermal annealing above the flux's eutectic temperature dramatically enhances the film's microstructural development and crystallinity. A secondary reaction phase of barium aluminate is identified at the substrate interface in both unfluxed and fluxed films, although it is more pronounced in the fluxed films. This barium aluminate phase in conjunction with the liquid flux serves to nucleate {111} twins in the barium titanate, which subsequently lead to enhanced grain growth. The resulting large-grained and dense thin films result in markedly improved dielectric properties.

Epitaxially oriented silicon nanowires (SiNWs) were grown on (111) Si substrates by the vapor–liquid–solid technique in an atmospheric-pressure chemical vapor deposition (APCVD) system using Au as the catalyst and SiCl4 as the source gas. The dependencies of SiNW growth rate on the growth temperature and SiCl4 partial pressure (PSiCl4) were investigated, and the experimental results were compared with calculated supersaturation curves for Si obtained from a gas phase equilibrium model of the SiCl4–H2 system. The SiNW growth rate was found to be weakly dependent on temperature but strongly dependent on the PSiCl4, exhibiting a maximum value qualitatively similar to that predicted from the equilibrium model. The results indicate that SiNW growth from SiCl4 is limited by gas phase chemistry and transport of reactant species to the growth surface under APCVD conditions. The experimental results are discussed within the context of a gas phase mass transport model that takes into account changes in equilibrium partial pressure due to curvature-related Gibbs–Thomson effects.

We present a novel synthesis technique to grow bulk quantities of semiconductor nanowires at temperatures less than 500 °C. Gallium is used as the liquid medium in a mechanism similar to vapor-liquid-solid (VLS). We demonstrated this low temperature technique with silicon and carbon nanowires. Gallium exhibits extremely low solubility for several elemental semiconductors. This property enables nucleation and growth of nanometer scale wires from large sized gallium droplets (>1 μm) eliminating the need for creation of quantum sized metal droplets.

Multiple silicon nanowires were synthesized using large gallium pools and microwave plasma. Results showed that nanowires growing out of different sized large gallium drops show little variation in diameters, suggesting that our non-traditional technique can be used to synthesize bulk amounts of monodispersed nanowires out of thin films of molten gallium.

We report for the first time, bulk synthesis of single crystalline silicon nanowires using molten gallium pools and an activated vapor phase containing silane. The resulting silicon nanowires were single crystalline with <100> growth direction. Nanowires contained an unexpectedly thin, non-uniform oxide sheath determined using high-resolution Transmission Electron Microscopy (TEM). Nanowires were tens of nanometers in diameter and tens to hundreds of microns long. The use of activated gas phase chemistry containing solute of interest over molten metal pools of low-solubility eutectics such as gallium offer a viable route to generate nanowire systems containing abrupt compositional hetero-interfaces.

Solute segregation to grain boundaries is a fundamental phenomenon in polycrystalline metal-oxide electroceramics that has enormous implications for the macroscopic dielectric behavior of the materials. This paper presents a systematic study of solute segregation in a model dielectric, titanium dioxide. We investigate the relative role of the electrostatic versus strain energy driving forces for segregation by studying yttrium-doped specimens. Through analytical transmission electron microscopy studies, we quantitatively determine the segregation behavior of the material. The measured Gibbsian interfacial excesses are compared to thermodynamic predictions.

In a recent publication we have described the synthesis of multiwalled carbon nanotubes (MWNTs) by the reaction of a hydrocarbon vapor over a dispersed iron catalyst that is deposited in situ on quartz substrates. Our system configuration involves entraining a mixture of xylene and ferrocene into an inert gas stream. Decomposition of the ferrocene at temperatures in the range 625-775 °C, and at atmospheric pressure, produces a coating of iron nanoparticles on the quartz surfaces, and these metal sites function as catalysts for the formation and growth of MWNTs. In this study, we report the influence of operating conditions on MWNT purity and yield. These parameters include the feed injection temperature, furnace temperature, hydrocarbon partial pressure, reaction time, space velocity, and iron to carbon ratio in the feed. We observed that the quality of the MWNTs dependc sensitively on the growth parameters and a window for the operating conditions is identified for the growth of high purity aligned MWNTs. Characterization of the MWNTs by electron microscopy has shown that there is a relationship between metal particle size and MWNT diameter.

Silicon-germanium (Si1−x Ge x :H) thin films have been prepared by plasma enhanced chemical vapor deposition of SiH4 and GeH4 and measured during growth using real time spectroscopic ellipsometry. A two-layer virtual interface analysis has been applied to study the structural evolution of Si:H films prepared in multistep processes utilizing alternating intermediate and low H2-dilution material layers, which have been designed to produce predominately amorphous films with a controlled distribution of microcrystalline particles. The compositional evolution of alloy-graded a-Si1−x Ge x :H has been studied as well using similar methods. In each case, depth profiles of microcrystalline content, f μc , or Ge content, x, have been extracted. Additionally, real time spectroscopic ellipsometry has been used to monitor post-deposition exposure of a-Si:H, a-Si1−xGex:H, and a-Ge:H films to a hydrogen plasma in situ in order to determine sub-surface amorphous film modification similar to that which would occur when a highly H2-diluted layer is deposited on a layer prepared with lower dilution. These analyses provide guidance for enhanced performance of Si:H based solar cells, through controlled bandgap grading using compositionally graded amorphous binary alloys (a-Si1−xGe x :H) or the incorporation of controlled fractions of microcrystallites into bulk amorphous i-layer materials, and by providing a fundamental understanding of the modification of component layers during the deposition of subsequent layers in multilayer stacks.