Biotic and Abiotic Interactions in Freshwater Mesocosms Determine Fate and Toxicity of CuO Nanoparticles.

Transformation, dissolution, and sorption of copper oxide nanoparticles (CuO-NP) play an important role in freshwater ecosystems. We present the first mesocosm experiment on the fate of CuO-NP and the dynamics of the zooplankton community over a period of 12 months. Increasingly low (0.08-0.28 mg Cu L-1) and high (0.99-2.99 mg Cu L-1) concentrations of CuO-NP and CuSO4 (0.10-0.34 mg Cu L-1) were tested in a multiple dosing scenario. At the high applied concentration (CuO-NP_H) CuO-NP aggregated and sank onto the sediment layer, where we recovered 63% of Cu applied. For the low concentration (CuO-NP_L) only 41% of applied copper could be recovered in the sediment. In the water column, the percentage of initially applied Cu recovered was on average 3-fold higher for CuO-NP_L than for CuO-NP_H. Zooplankton abundance was substantially compromised in the treatments CuSO4 (p < 0.001) and CuO-NP_L (p < 0.001). Community analysis indicated that Cladocera were most affected (bk = -0.49), followed by Nematocera (bk = -0.32). The abundance of Cladocera over time and of Dixidae in summer was significantly reduced in the treatment CuO-NP_L (p < 0.001; p < 0.05) compared to the Control. Our results indicate a higher potential for negative impacts on the freshwater community when lower concentrations of CuO-NP (<0.1 mg Cu L-1) enter the ecosystem.

Ion compositions in artificial media control the impact of humic acid on colloidal behaviour, dissolution and speciation of CuO-NP.

The toxicity of copper oxide nanoparticles (CuO-NP) strongly depends on their interactions with the surrounding environment, impacting their dissolution and colloidal stability. This behaviour is studied quite extensively for simplified electrolytes, but information on the behaviour of CuO-NP in more complex artificial media are lacking. In our study, we analysed the colloidal behaviour and considered the speciation of CuO-NP in pure water and three artificial media of different complexity which are used in ecotoxicology. Measurements were done over 7 days in the absence and presence of humic acid (HA) as a model organic molecule. In pure water, the addition of HA lowered the zeta potential from +11 to -41 mV, while in all artificial media, it stayed constantly at about -20 mV. The hydrodynamic diameter of CuO-NP remained unaffected by HA in pure water and seawater, while in porewater and especially in freshwater, HA suppressed strong agglomeration. In pure water, HA strongly increased dissolution to the highest observed value (3% of total Cu), while HA reduced dissolution in all artificial media. Speciation calculations revealed that cations from the media competed with Cu from the NP surface for complexing sites of the HA. This competition may have caused the reduced dissolution in the presence of ions. Furthermore, speciation calculations also suggest that ion composition drove agglomeration behaviour rather than ion concentration: agglomeration was high when divalent cations where the major interaction partner and dominant in relative terms. HA may have reduced the relative dominance and thus altered the agglomeration, aligning it in all media. Summarizing, ion composition and the presence of HA strongly drive the dissolution and agglomeration of CuO-NP in artificial media, consequently, analysing complexation can help to predict environmental behaviour and toxicity.

Efficient Nitrogen Doping of Single-Layer Graphene Accompanied by Negligible Defect Generation for Integration into Hybrid Semiconductor Heterostructures.

While doping enables application-specific tailoring of graphene properties, it can also produce high defect densities that degrade the beneficial features. In this work, we report efficient nitrogen doping of ∼11 atom % without virtually inducing new structural defects in the initial, large-area, low defect, and transferred single-layer graphene. To shed light on this remarkable high-doping-low-disorder relationship, a unique experimental strategy consisting of analyzing the changes in doping, strain, and defect density after each important step during the doping procedure was employed. Complementary micro-Raman mapping, X-ray photoelectron spectroscopy, and optical microscopy revealed that effective cleaning of the graphene surface assists efficient nitrogen incorporation accompanied by mild compressive strain resulting in negligible defect formation in the doped graphene lattice. These original results are achieved by separating the growth of graphene from its doping. Moreover, the high doping level occurred simultaneously with the epitaxial growth of n-GaN micro- and nanorods on top of graphene, leading to the flow of higher currents through the graphene/n-GaN rod interface. Our approach can be extended toward integrating graphene into other technologically relevant hybrid semiconductor heterostructures and obtaining an ohmic contact at their interfaces by adjusting the doping level in graphene.

Vertically Oriented Growth of GaN Nanorods on Si Using Graphene as an Atomically Thin Buffer Layer.

The monolithic integration of wurtzite GaN on Si via metal-organic vapor phase epitaxy is strongly hampered by lattice and thermal mismatch as well as meltback etching. This study presents single-layer graphene as an atomically thin buffer layer for c-axis-oriented growth of vertically aligned GaN nanorods mediated by nanometer-sized AlGaN nucleation islands. Nanostructures of similar morphology are demonstrated on graphene-covered Si(111) as well as Si(100). High crystal and optical quality of the nanorods are evidenced through scanning transmission electron microscopy, micro-Raman, and cathodoluminescence measurements supported by finite-difference time-domain simulations. Current-voltage characteristics revealed high vertical conduction of the as-grown GaN nanorods through the Si substrates. These findings are substantial to advance the integration of GaN-based devices on any substrates of choice that sustains the GaN growth temperatures, thereby permitting novel designs of GaN-based heterojunction device concepts.

Ultrafast Dynamics of Lasing Semiconductor Nanowires.

Semiconductor nanowire lasers operate at ultrafast timescales; here we report their temporal dynamics, including laser onset time and pulse width, using a double-pump approach. Wide bandgap gallium nitride (GaN), zinc oxide (ZnO), and cadmium sulfide (CdS) nanowires reveal laser onset times of a few picoseconds, driven by carrier thermalization within the optically excited semiconductor. Strong carrier-phonon coupling in ZnO leads to the fastest laser onset time of ∼1 ps in comparison to CdS and GaN exhibiting values of ∼2.5 and ∼3.5 ps, respectively. These values are constant between nanowires of different sizes implying independence from any optical influences. However, we demonstrate that the lasing onset times vary with excitation wavelength relative to the semiconductor band gap. Meanwhile, the laser pulse widths are dependent on the optical system. While the fastest ultrashort pulses are attained using the thinnest possible nanowires, a sudden change in pulse width from ∼5 to ∼15 ps occurs at a critical nanowire diameter. We attribute this to the transition from single to multimode waveguiding, as it is accompanied by a change in laser polarization.

Composition mapping in InGaN by scanning transmission electron microscopy.

We suggest a method for chemical mapping that is based on scanning transmission electron microscopy (STEM) imaging with a high-angle annular dark field (HAADF) detector. The analysis method uses a comparison of intensity normalized with respect to the incident electron beam with intensity calculated employing the frozen lattice approximation. This procedure is validated with an In(0.07)Ga(0.93)N layer with homogeneous In concentration, where the STEM results were compared with energy filtered imaging, strain state analysis and energy dispersive X-ray analysis. Good agreement was obtained, if the frozen lattice simulations took into account static atomic displacements, caused by the different covalent radii of In and Ga atoms. Using a sample with higher In concentration and series of 32 images taken within 42 min scan time, we did not find any indication for formation of In rich regions due to electron beam irradiation, which is reported in literature to occur for the parallel illumination mode. Image simulation of an In(0.15)Ga(0.85)N layer that was elastically relaxed with empirical Stillinger-Weber potentials did not reveal significant impact of lattice plane bending on STEM images as well as on the evaluated In concentration profiles for specimen thicknesses of 5, 15 and 50 nm. Image simulation of an abrupt interface between GaN and In(0.15)Ga(0.85)N for specimen thicknesses up to 200 nm showed that artificial blurring of interfaces is significantly smaller than expected from a simple geometrical model that is based on the beam convergence only. As an application of the method, we give evidence for the existence of In rich regions in an InGaN layer which shows signatures of quantum dot emission in microphotoluminescence spectroscopy experiments.