Grain growth, oxygen stoichiometry, and phase stability of nanostructurally stabilized cubic zirconia ͑NSZ͒ are investigated under 2 MeV Au-ion bombardment at 160 and 400 K to doses up to 35 displacements per atom ͑dpa͒. The NSZ films are produced by ion-beam-assisted deposition technique at room temperature with an average grain size of 7.7 nm. The grain size increases with irradiation dose to ϳ30 nm at ϳ35 dpa. Slower grain growth is observed under 400 K irradiations, as compared to 160 K irradiations, indicating that the grain growth is not thermally activated and irradiation-induced grain growth is the dominating mechanism. While the cubic structure is retained and no new phases are identified after the high-dose irradiations, oxygen reduction in the irradiated NSZ films is detected. The ratio of O to Zr decreases from ϳ2.0 for the as-deposited films to ϳ1.65 after irradiation to ϳ35 dpa. The loss of oxygen suggests a significant increase in oxygen vacancies in nanocrystalline zirconia under ion irradiation. The oxygen deficiency may be essential in stabilizing the cubic phase to larger grain sizes.
Patterned micro- and nanostructured surfaces have received increasing attention because of their ability to tune the hydrophobicity and hydrophilicity of their surfaces. However, the mechanical properties of these studied surfaces are not sufficiently robust for load-bearing applications. Here we report transparent nanocrystalline ZrO 2 films possessing combined properties of hardness and complete wetting behavior, which are expected to benefit tribology, wear reduction, and biomedical applications where ultrahydrophilic surfaces are required. This ultrahydrophilic behavior may be explained by the Wenzel model.
Exceptional size-dependent electronic-ionic conductivity of nanostructured ceria can significantly alter materials properties in chemical, physical, electronic and optical applications. Using energetic ions, we have demonstrated effective modification of interface volume and grain size in nanocrystalline ceria from a few nm up to ∼25 nm, which is the critical region for controlling size-dependent material property. The grain size increases and follows an exponential law as a function of ion fluence that increases with temperature, while the cubic phase is stable under the irradiation. The unique self-healing response of radiation damage at grain boundaries is utilized to control the grain size at the nanoscale. Structural modification by energetic ions is proposed to achieve desirable electronic-ionic conductivity.
Efficient Er-related photo-, cathodo-, and electroluminescence at 1539 nm was detected from Er and O co-implanted n-type GaN on sapphire substrates. Several combinations of Er and O implants and postimplant annealing conditions were studied. The Er doses were in the range (0.01-5)ϫ10 15 ions/cm 2 and O doses (0.1-1)ϫ10 16 ions/cm 2 . GaN films implanted with 2ϫ10 15 Er 2ϩ /cm 2 at 350 keV and co-implanted with 10 16 O ϩ /cm 2 at 80 keV yielded the strongest photoluminescence intensity at 1539 nm. The annealing condition yielding the strongest Er-related photoluminescence intensity was a single anneal at 800°C ͑45 min͒ or at 900°C ͑30 min͒ in flowing NH 3 . The optimum O:Er ratio was found to be between 5:1 and 10:1. Co-implanting the GaN:Er films with F was also found to optically activate the Er, with slightly ͑20%͒ less photoluminescence intensity at 1539 nm compared to equivalent GaN:Er,O films. The Er-related luminescence lifetime at 1539 nm was found to depend on the excitation mechanism. Luminescence lifetimes as long as 2.95Ϯ0.15 ms were measured at 77 K under direct excitation with an InGaAs laser diode at 983 nm. At room temperature the luminescence lifetimes were 2.35Ϯ0.12, 2.15Ϯ0.11, and 1.74Ϯ0.08 ms using below-band-gap excitation, above-band-gap excitation, and impact excitation ͑reverse biased light emitting diode͒, respectively. The cross sections for Er in GaN were estimated to be 4.8ϫ10 Ϫ21 cm 2 for direct optical excitation at 983 nm and 4.8ϫ10 Ϫ16 cm 2 for impact excitation. The cross-section values are believed to be within a factor of 2-4.
Nanostructurally stabilized zirconium oxide (NSZ) hard transparent films were produced without chemical stabilizers by the ion beam assisted deposition technique (IBAD). A transmission electron microscopy study of the samples produced below 150 °C revealed that these films are composed of zirconium oxide (ZrO2) nanocrystallites of diameters 7.5 ± 2.3 nm. X-ray and selected-area electron diffraction studies suggested that the as-deposited films are consistent with cubic phase ZrO2. Rutherford backscattering spectroscopy (RBS) indicated the formation of stoichiometric ZrO2. The phase identity of these optically transparent NSZ films was in agreement with cubic ZrO2, as indicated by the matching elastic modulus values from the calculated results for pure cubic zirconium oxide and results of nanoindentation measurements. Upon annealing in air for 1 h, these NSZ films were found to retain most of their room temperature deposited cubic phase x-ray diffraction signature up to 850 °C. Size effect and vacancy stabilization mechanisms and the IBAD technique are discussed to explain the present results.
Room temperature operation of erbium and oxygen coimplanted GaN m-i-n (metal–insulator–n-type) diodes is demonstrated. Erbium related electroluminescence at λ=1.54 μm was detected under reverse bias after a postimplant anneal at 800°C for 45 min in flowing NH3. The integrated light emission intensity showed a linear dependence on applied reverse drive current.
Using a nonlocal electrostatic approach that incorporates the short-range structure of the contacting media, we evaluated the electrostatic contribution to the energy of the complex formation of two model proteins. In this study, we have demonstrated that the existence of an ordered interfacial water layer at the protein-solvent interface reduces the charging energy of the proteins in the aqueous solvent, and consequently increases the electrostatic contribution to the protein binding (change in free energy upon the complex formation of two proteins). This is in contrast with the finding of the continuum electrostatic model, which suggests that electrostatic interactions are not strong enough to compensate for the unfavorable desolvation effects.
Grain growth of nanocrystalline materials is generally thermally activated, but can also be driven by irradiation at much lower temperature. In nanocrystalline ceria and zirconia, energetic ions deposit their energy to both atomic nuclei and electrons. Our experimental results have shown that irradiation-induced grain growth is dependent on the total energy deposited, where electronic energy loss and elastic collisions between atomic nuclei both contribute to the production of disorder and grain growth. Our atomistic simulations reveal that a high density of disorder near grain boundaries leads to locally rapid grain movement. The additive effect from both electronic excitation and atomic collision cascades on grain growth demonstrated in this work opens up new possibilities for controlling grain sizes to improve functionality of nanocrystalline materials.
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