Carbon concentration dependent grain growth of Cu2ZnSnS4thin films

Organic solvents are commonly used in ink precursors of Cu2ZnSnS4 (CZTS) nanocrystals to make thin films for applications such as solar cells. However, the traces of carbon residual left behind by the organic solvents after high-temperature annealing is generally considered to restrict the growth of nanocrystals to form large grains. This work reported the first systematic study on the influence of carbon content of organic solvents on the grain growth of CZTS nanomaterial during high temperature sulfurization annealing. Solvents with carbon atom per molecule varying from 3 to 10 were used to made ink of CZTS nanocrystals for thin film deposition. It has been found that, after high temperature sulfurization annealing, a bilayer structure was formed in the CZTS film using organic solvent containing 3 carbon atoms per solvent molecule based on glycerol and 1,3-propanediol. The top layer consisted of closelypacked large grains and the bottom layer was made of as-synthesized nanoparticles. In contrast, the CZTS film made with the solvent molecule with more carbon atoms including 1,5-pentanediol (5 carbon atoms) and 1,7-heptanediol (7 carbon atoms) consisted of nanoparticles embedded with large crystals. It is believed that the carbon residues left behind by the organic solvents affected the necking of CZTS nanocrystals to form large grains through influencing the surface property of nanocrystals. Furthermore, it has also been observed that the solvent affected the thickness of MoS2 layer which was formed between CZTS and Mo substrate. A thinner MoS2 film (50 nm) was obtained with the slurry using carbon-rich terpineol as solvent whereas the thickest MoS2 (350 nm) was obtained with the film made from 1,3-propanediol based solvent. The evaluation of the photoactivity of the CZTS thin films has demonstrated that a higher photocurrent was generated with the film containing more large grains.

A Huge Effect of Weak dc Electrical Fields on Grain Growth in Zirconia

We show that the application of a modest dc electrical field, about 4 V/cm, can significantly reduce grain growth in yttria-stabilized polycrystalline zirconia. These measurements were made by annealing samples, for 10 h at 1300°C, with and without an electrical field. The finding adds a new dimension to the role of applied electrical fields in sintering and superplasticity, phenomena that are critical to the net-shape processing of ceramics. Grain-growth retardation will considerably enhance the rates of sintering and superplasticity, leading to significant energy efficiencies in the processing of ceramics.

Effect of recrystallization and grain growth on the mechanical properties of an extruded AZ21 Mg alloy

An experimental investigation into the effect of microstructural changes, which occur during post-extrusion annealing of a Mg based AZ21 alloy, on tensile and fatigue properties is conducted. Mechanical properties in the as-cast, as-extruded, and microstructural states that correspond to recovery, recrystallization and grain growth stages of annealing are compared. Results show that these microstructural changes do not alter the yield strength of the alloy markedly whereas significant differences were noted in the ultimate tensile strength as well as ductility. The initiation of abnormal grain growth (or secondary recrystallization) renders the tensile stress-strain response elastic perfectly plastic and results in a large drop in ductility, as high as similar to 60% during intermediate stages of abnormal grain growth, vis-A-vis the ductility of the as-extruded alloy. While the fatigue performance of all the wrought alloys is far superior to as expected, abnormal grain growth leads to a marked decrease in the endurance that of the as-cast alloy, limit. Possible microscopic origins of these are discussed. (C) 2009 Elsevier B.V. All rights reserved.

Grain Growth in ECAE Processed Pure Magnesium

Grain growth kinetics was studied for commercially pure magnesium subjected to equal channel angular extrusion (ECAE). The specimens were ECAE processed upto 4 passes at 523 K following all the three important routes, namely A, 13, and C. Texture and microstructures of the samples were studied using Electron Back Scattered Diffraction (EBSD) technique in a Field Emission Gun Scanning Electron Microscope (FEG-SEM). It was observed that the grain size significantly reduces after ECAE. ECAE process produces a slightly rotated B and C-2 fiber. Static annealing leads to normal grain growth with unimodal distribution of grains through out the temperature range. Average activation energy for grain growth in the temperature range studied is found to be less than the activation energy for lattice diffusion and grain boundary diffusion of magnesium. No significant change in texture during isochronal annealing for 1 hour i.e., the predominant deformation texture remains same.

Metastable extension of the fluorite phase field in Y2O3---ZrO2 and its effect on grain growth

Pure Y2O3 and Y2O3---ZrO2 solid solutions have been prepared by melt atomization and by pyrolysis of nitrate solutions. Extended solubility is readily achieved in both techniques for the entire composition range investigated: melts with 0–30% ZrO2 and precursors with 0–50% ZrO2. However, solidification of under cooled droplets yields almost exclusively single phase powders with the structure of cubic yttria (D53). In contrast, the pyrolysis route leads to a sequence of metastable microstructures beginning with a nanocrystalline disordered fluorite-based (C1) solid solution. Further heating leads to the evolution of much larger (micron size) flake crystals with a {001} texture, concurrent with partial ordering of the oxygen ions to the sites occupied in the D53 structure. The driving force for ordering and the rate of grain growth decrease with increasing ZrO2 addition. Abrupt heating to high temperatures or electron irradiation can induce ordering without substantial grain growth. There is no significant reduction in porosity during the recrystallization, which with the other observations suggests that grain growth is driven by the free energy available for the ordering transformation from fluorite to the yttria structure. This route offers opportunities for single crystal thin film development at relatively low processing temperatures.

Metastable extension of the fluorite phase field in Y2O3---ZrO2 and its effect on grain growth

Pure Y2O3 and Y2O3-ZrO2 solid solutions have been prepared by melt atomization and by pyrolysis of nitrate solutions. Extended solubility is readily achieved in both techniques for the entire composition range investigated: melts with 0-30% ZrO2 and precursors with 0-50% ZrO2. However, solidification of under cooled droplets yields almost exclusively single phase powders with the structure of cubic yttria (D5(3)). In contrast, the pyrolysis route leads to a sequence of metastable microstructures beginning with a nanocrystalline disordered fluorite-based (C1) solid solution. Further heating leads to the evolution of much larger (micron size) flake crystals with a {001} texture, concurrent with partial ordering of the oxygen ions to the sites occupied in the D5(3) structure. The driving force for ordering and the rate of grain growth decrease with increasing ZrO2 addition. Abrupt heating to high temperatures or electron irradiation can induce ordering without substantial grain growth. There is no significant reduction in porosity during the recrystallization, which with the other observations suggests that grain growth is driven by the free energy available for the ordering transformation from fluorite to the yttria structure. This route offers opportunities for single crystal thin film development at relatively low processing temperatures.

Deformation-induced thermally activated grain growth in nanocrystalline nickel

Grain growth during indentation at low temperatures has been taken to imply that grain growth is largely stress induced and athermal in nanometals. Indentation experiments on electrodeposited nano-Ni indicate clearly that the load required for grain growth decreases with an increase in temperature, suggesting strongly that concurrent grain growth is thermally activated. (C) 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Directional grain growth from anisotropic kinetic roughening of grain boundaries in sheared colloidal crystals

The fabrication of functional materials via grain growth engineering implicitly relies on altering the mobilities of grain boundaries (GBs) by applying external fields. Although computer simulations have alluded to kinetic roughening as a potential mechanism for modifying GB mobilities, its implications for grain growth have remained largely unexplored owing to difficulties in bridging the widely separated length and time scales. Here, by imaging GB particle dynamics as well as grain network evolution under shear, we present direct evidence for kinetic roughening of GBs and unravel its connection to grain growth in driven colloidal polycrystals. The capillary fluctuation method allows us to quantitatively extract shear-dependent effective mobilities. Remarkably, our experiments reveal that for sufficiently large strains, GBs with normals parallel to shear undergo preferential kinetic roughening, resulting in anisotropic enhancement of effective mobilities and hence directional grain growth. Single-particle level analysis shows that the mobility anisotropy emerges from strain-induced directional enhancement of activated particle hops normal to the GB plane. We expect our results to influence materials fabrication strategies for atomic and block copolymeric polycrystals as well.

Grain growth and grain boundary dynamics in colloidal polycrystals

Grain boundary dynamics and grain growth play a pivotal role in the fabrication of functional polycrystalline materials. However, not much is known about the delicate interplay between various microscopic processes that drive grain boundary motion which eventually culminates in the desired grain morphology. Colloidal systems are ideally suited to bridge the gap between the microscopic and macroscopic processes underlying grain growth, since their dynamics can be followed in real space and real time with single-particle resolution. The present review aims at highlighting contributions from colloid experiments that have led to a holistic understanding of grain growth in polycrystalline materials.

Deformation-induced grain growth and twinning in nanocrystalline palladium thin films

The microstructure and mechanical properties of nanocrystalline Pd films prepared by magnetron sputtering have been investigated as a function of strain. The films were deposited onto polyimide substrates and tested in tensile mode. In order to follow the deformation processes in the material, several samples were strained to defined straining states, up to a maximum engineering strain of 10%, and prepared for post-mortem analysis. The nanocrystalline structure was investigated by quantitative automated crystal orientation mapping (ACOM) in a transmission electron microscope (TEM), identifying grain growth and twinning/detwinning resulting from dislocation activity as two of the mechanisms contributing to the macroscopic deformation. Depending on the initial twin density, the samples behaved differently. For low initial twin densities, an increasing twin density was found during straining. On the other hand, starting from a higher twin density, the twins were depleted with increasing strain. The findings from ACOM-TEM were confirmed by results from molecular dynamics (MD) simulations and from conventional and in-situ synchrotron X-ray diffraction (CXRD, SXRD) experiments.

Exceptional resistance to grain growth in nanocrystalline CoCrFeNi high entropy alloy at high homologous temperatures

Nanocrystalline CoCrFeNi high entropy alloy, synthesized by mechanical alloying followed by spark plasma sintering, demonstrated extremely sluggish grain growth even at very high homologous temperature of 0.68 T-m (900 degrees C) for annealing duration of 600 h. Mechanically alloyed powder had carbon and oxygen as impurities, which in turn led to the formation of two-phase mixture of FCC and Cr-rich carbide with fine distribution of Cr-rich oxide during spark plasma sintering. Sluggish grain growth is attributed to the Zener pinning effect from the fine dispersion of oxide, mutual retardation of grain boundaries in the presence of two phases, and sluggish diffusivity because of cooperative diffusion of multi-principle elements. (C) 2015 Elsevier B.V. All rights reserved.

Grain growth in protoplanetary disks

The majority of young, low-mass stars are surrounded by optically thick accretion disks. These circumstellar disks provide large reservoirs of gas and dust that will eventually be transformed into planetary systems. Theory and observations suggest that the earliest stage toward planet formation in a protoplanetary disk is the growth of particles, from sub-micron-sized grains to centimeter- sized pebbles. Theory indicates that small interstellar grains are well coupled into the gas and are incorporated to the disk during the proto-stellar collapse. These dust particles settle toward the disk mid-plane and simultaneously grow through collisional coagulation in a very short timescale. Observationally, grain growth can be inferred by measuring the spectral energy distribution at long wavelengths, which traces the continuum dust emission spectrum and hence the dust opacity. Several observational studies have indicated that the dust component in protoplanetary disks has evolved as compared to interstellar medium dust particles, suggesting at least 4 orders of magnitude in particle- size growth. However, the limited angular resolution and poor sensitivity of previous observations has not allowed for further exploration of this astrophysical process.

As part of my thesis, I embarked in an observational program to search for evidence of radial variations in the dust properties across a protoplanetary disk, which may be indicative of grain growth. By making use of high angular resolution observations obtained with CARMA, VLA, and SMA, I searched for radial variations in the dust opacity inside protoplanetary disks. These observations span more than an order of magnitude in wavelength (from sub-millimeter to centimeter wavelengths) and attain spatial resolutions down to 20 AU. I characterized the radial distribution of the circumstellar material and constrained radial variations of the dust opacity spectral index, which may originate from particle growth in these circumstellar disks. Furthermore, I compared these observational constraints with simple physical models of grain evolution that include collisional coagulation, fragmentation, and the interaction of these grains with the gaseous disk (the radial drift problem). For the parameters explored, these observational constraints are in agreement with a population of grains limited in size by radial drift. Finally, I also discuss future endeavors with forthcoming ALMA observations.