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We have used fluctuation electron microscopy (FEM) to measure the medium range order in the molecular packing of 40 nm thick indomethacin glass films. Vapor deposition of indomethacin can create glasses with extraordinary kinetic stability and high density. We find peaks in the FEM variance at diffraction vector magnitudes between 0.03 and 0.09 Å-1, corresponding to intermolecular packing distances of 1-3 nm. FEM experiments were performed with a 13 nm diameter electron probe, so these data are sensitive to medium-range order in intermolecular packing. The FEM variance from an indomethacin glass with normal stability cooled from the liquid is significantly smaller than the variance from the ultrastable glass, suggesting that ultrastable glass is more structurally heterogeneous at a 13 nm length scale. A dose of ∼7×105 e-/nm2 with a very low beam current of ∼ 2.5 pA at 200 kV was used to minimize electron beam damage to the sample, and the average electron diffraction from the sample is unchanged at total electron doses fourteen times larger than required for a FEM experiment. These preliminary results on medium-range order in molecular glasses suggest that we may be able to provide insight into the structural differences between the remarkable ultrastable thin films and ordinary glasses.
We have previously reported, based on fluctuation electron microscopy (FEM) data, that Zr50Cu45Al5 bulk metallic glass (BMG) contains significant icosahedral and crystal-like medium-range order. Here, we report similar finding for Zr54Cu38Al8 BMG, which is a poorer glass former. Like Zr50Cu45Al5, Zr54Cu38Al8 contains icosahedral and crystal-like structures. In the as-cast state, the crystal-like peak in the FEM data is stronger than icosahedral-like peak. After annealing at 0.83Tg (573 K), the icosahedral-like peak increases, but, unlike Zr50Cu45Al5, the crystal-like peak does not decrease. This tendency toward stronger, more thermally stable crystal-like order may be associated with the poorer glass forming ability of Zr54Cu38Al8.
By using aberration corrected scanning transmission electron microscopy we have found no small scale lateral In composition fluctuations exist in the In0.15Ga0.85N active region of a light emitting diode. Images were acquired at 2% of the electron dose known to create electron beam damage, so the acquired images reflect the intrinsic structure of the InGaN active region. Position averaged convergent beam electron diffraction reveals the local sample thickness where images were acquired is 4.8 nm, eliminating the possibility that the absence of composition variation was observed due to projection through a thick sample. In addition, 2-3 atomic layer steps were observed in the top surface of In0.08Ga0.92N layers and the In0.15Ga0.85N active layers, providing a possible mechanism for lateral carrier confinement.
Pure and Cu-doped quantum dots of ZnSe@ZnS were synthesized in aqueous phase using microwave irradiation at 140 °C. X-ray diffraction analyses suggested the development of a ZnSe-ZnS structure. UV-vis measurements evidenced that the presence of Cu species in quantum dots caused the blue shift of exciton peaks with respect to pure, i.e. non doped ones. Photoluminescence spectra of quantum dots synthesized at Zn/Cu mole ratios of 1/0.001 and 1/0.005 exhibited a very strong emission peak centered on ˜ 515 nm. On the contrary, a weak emission peak was observed at 412 nm in pure ZnSe@ZnS quantum dots. The observed emission at 515 nm was attributed to the internal doping of Cu species, which should have induced d-d transitions in the host lattice. Quenching of the luminescence at 515 nm was observed for nominal Cu concentrations above 0.005 mM.
Extended abstract of a paper presented at the Pre-Meeting Congress: Materials Research in an Aberration-Free Environment, at Microscopy and Microanalysis 2004 in Savannah, Georgia, USA, July 31 and August 1, 2004.
Traditional science classroom activities rely on topics and experiments that are distant from the forefront of scientific research. As a result, students view science as stagnant and far removed from real life. Through a National Science Foundation-funded Research Experiences for Teachers (RET) program, we at the University of Wisconsin-Madison (UW) Materials Research Science and Engineering Center (MRSEC) work with secondary teachers to transform cutting-edge research in nanoscale science and engineering into curriculum that is appropriate for middle- and high-school classrooms. This benefits everyone involved: teachers learn about innovative science and the process of research; UW MRSEC personnel learn about science education and the state of today's schools; and students get to test and engage with new curriculum about breakthrough research. This past summer our RET participants conducted research on and developed curriculum about “smart” papers with microencapsulation technology, fuel cells, nano biosensors and liquid crystals, glassy metals, and Wells models.
We have used fluctuation electron microscopy (FEM) to measure nanoscale mediumrange order in amorphous Al92Sm8. Samples of this amorphous alloy formed by rapid quenching (melt-spinning) show a high density of pure Al nanocrystals (>1020 m-3) after low temperature (< 250 °C) devitrification. In samples amorphized by deformation (cold-rolling), primary Al-crystallization does not occur. This difference in devitrification behavior suggests an underlying structural difference in the amorphous state. FEM is a quantitative microscopy technique for determining nanoscale medium-range order in amorphous materials. Our measurements show that amorphous alloys formed by melt-spinning and cold-rolling have significant structural differences, and that annealing melt-spun alloy under conditions previously shown to modify the devitrification thermodynamics also changes the medium-range structure.
Fluctuation microscopy is an electron microscopy technique sensitive to medium-range order (MRO) in disordered materials. It has been applied to study amorphous germanium and silicon, leading to the conclusion that these materials exhibit more MRO than the conventional continuous random network model for their structure.
As originally proposed by Treacy and Gibson, fluctuation microscopy utilizes mesoscopicresolution (1.5 nm) hollow-cone dark field (HCDF) imaging in a TEM. The normalized variance of such images,
is a measure of the magnitude of fluctuations in the diffracted intensity from mesoscopic volumes of the sample and is sensitive to MRO via the three- and four-body atom distribution functions. Studying V as a function of the diffraction vector magnitude k gives information about the degree of MRO and the internal structure of ordered regions. V as a function of the inverse resolution Q gives information about the characteristic MRO length scale.