Andreas Johannes

Ion beam irradiation of nanostructures: sputtering, dopant incorporation, and dynamic annealing

Nanostructured materials are today subject to intense research, as their mesoscopic properties will enable a variety of new applications in the future. They can be grown with specific properties under equilibrium conditions by a variety of different top-down and bottom-up synthesis techniques. Subsequent modification, including doping or alloying using the highly non-equilibrium process of ion irradiation, significantly expands the potpourri of functionality of what is today an important material class. Important and newly discovered effects must be considered compared to ion irradiation of bulk or thin film counterparts, as the ion range becomes comparable to the size of the nanotructure. Here, we will review recent high fluence irradiation studies reporting on non-linear incorporation of implanted species, enhanced sputtering yields, morphological changes induced by the high thermal impact, as well as strongly enhanced dynamic annealing for such confined nanostructures. Our review will also include the concurrent and recent progress in developing new simulation tools in order to describe and quantify those newly observed effects.

Enhanced sputtering and incorporation of Mn in implanted GaAs and ZnO nanowires

We simulated and experimentally investigated the sputter yield of ZnO and GaAs nanowires, which were implanted with energetic Mn ions at room temperature. The resulting thinning of the nanowires and the dopant concentration with increasing Mn ion fluency were measured by accurate scanning electron microscopy (SEM) and nano-X-Ray Fluorescence (nanoXRF) quantification, respectively. We observed a clear enhanced sputter yield for the irradiated nanowires compared to bulk, which is also corroborated by iradina simulations. These show a maximum if the ion range matches the nanowire diameter. As a consequence of the erosion thinning of the nanowire, the incorporation of the Mn dopants is also enhanced and increases non-linearly with increasing ion fluency.

Magnetic polarons and large negative magnetoresistance in GaAs nanowires implanted with Mn ions.

We report on low-temperature magnetotransport and SQUID measurements on heavily doped Mn-implanted GaAs nanowires. SQUID data recorded at low magnetic fields exhibit clear signs of the onset of a spin-glass phase with a transition temperature of about 16 K. Magnetotransport experiments reveal a corresponding peak in resistance at 16 K and a large negative magnetoresistance, reaching 40% at 1.6 K and 8 T. The negative magnetoresistance decreases at elevated temperatures and vanishes at about 100 K. We interpret our transport data in terms of spin-dependent hopping in a complex magnetic nanowire landscape of magnetic polarons, separated by intermediate regions of Mn impurity spins, forming a paramagnetic/spin-glass phase.

Improved Ga grading of sequentially produced Cu(In,Ga)Se2 solar cells studied by high resolution X-ray fluorescence

There is particular interest to investigate compositional inhomogeneity of Cu(In,Ga)Se2 solar cell absorbers. We introduce an approach in which focused ion beam prepared thin lamellas of complete solar cell devices are scanned with a highly focused synchrotron X-ray beam. Analyzing the resulting fluorescence radiation ensures high resolution compositional analysis combined with high spatial resolution. Thus, we are able to detect subtle variations of the Ga/(Ga + In) ratio down to 0.01 on a submicrometer scale. We observed that for sequentially processed solar cells a higher selenization temperature leads to absorbers with almost homogenous Ga/(Ga + In) ratio, which significantly improved the conversion efficiency.

Persistent ion beam induced conductivity in zinc oxide nanowires

We report persistently increased conduction in ZnO nanowires irradiated by ion beam with various ion energies and species. This effect is shown to be related to the already known persistent photo conduction in ZnO and dubbed persistent ion beam induced conduction. Both effects show similar excitation efficiency, decay rates, and chemical sensitivity. Persistent ion beam induced conduction will potentially allow countable (i.e., single dopant) implantation in ZnO nanostructures and other materials showing persistent photo conduction.

Shape manipulation of ion irradiated Ag nanoparticles embedded in lithium niobate

Spherical silver nanoparticles were prepared by means of ion beam synthesis in lithium niobate. The embedded nanoparticles were then irradiated with energetic (84)Kr and (197)Au ions, resulting in different electronic energy losses between 8.1 and 27.5 keV nm(-1) in the top layer of the samples. Due to the high electronic energy losses of the irradiating ions, molten ion tracks are formed inside the lithium niobate in which the elongated Ag nanoparticles are formed. This process is strongly dependent on the initial particle size and leads to a broad aspect ratio distribution. Extinction spectra of the samples feature the extinction maximum with shoulders on either side. While the maximum is caused by numerous remaining spherical nanoparticles, the shoulders can be attributed to elongated particles. The latter could be verified by COMSOL simulations. The extinction spectra are thus a superposition of the spectra of all individual particles.

Atomic-scale structure, cation distribution, and bandgap bowing in Cu(In,Ga)S2 and Cu(In,Ga)Se2

Mixed chalcopyrite semiconductors like Cu(In,Ga)S2 and Cu(In,Ga)Se2 are characterized by the coexistence of different local atomic arrangements around the S or Se anion. The resulting anion displacement strongly influences the material bandgap. We studied the atomic-scale structure of Cu(In,Ga)S2 as a function of composition using x-ray absorption spectroscopy and valence force field simulations. Applying a specially developed model for not fully random cation distributions, we find that structural relaxation of the anion with respect to In and Ga contributes significantly more to the bandgap bowing observed for Cu(In,Ga)S2 and Cu(In,Ga)Se2 than relaxation with respect to Cu and group-III atoms.

Corrigendum: Enhanced sputtering and incorporation of Mn in implanted GaAs and ZnO nanowires (2014 J. Phys. D: Appl. Phys. 47 394003)

Corrigendum : Enhanced sputtering and incorporation of Mn in implanted GaAs and ZnO nanowires (2014 J. Phys. D: Appl. Phys. 47 394003)

Anomalous Plastic Deformation and Sputtering of Ion Irradiated Silicon Nanowires.

Silicon nanowires of various diameters were irradiated with 100 keV and 300 keV Ar+ ions on a rotatable and heatable stage. Irradiation at elevated temperatures above 300 °C retains the geometry of the nanostructure and sputtering can be gauged accurately. The diameter dependence of the sputtering shows a maximum if the ion range matches the nanowire diameter, which is in good agreement with Monte Carlo simulations based on binary collisions. Nanowires irradiated at room temperature, however, amorphize and deform plastically. So far, plastic deformation has not been observed in bulk silicon at such low ion energies. The magnitude and direction of the deformation is independent of the ion-beam direction and cannot be explained with mass-transport in a binary collision cascade but only by collective movement of atoms in the collision cascade with the given boundary conditions of a high surface to volume ratio.

Shaping and compositional modification of zinc oxide nanowires under energetic manganese ion irradiation.

For ZnO nanowires of 150 to 200 nm diameter standing on a flat substrate, the development of the surface contour/morphology and the local elemental composition under 175 keV Mn irradiation has been investigated both experimentally and by means of three-dimensional dynamic Monte Carlo computer simulation. The simulation results reveal a complex interplay of sputter erosion, implant incorporation, resputtering and atomic mixing, which is discussed in detail. The sputter-induced thinning of the wire is in good quantitative agreement with the experimental results obtained from pre- and post-irradiation scanning electron microscopy. The experiments also confirm the predicted sharpening of the tip, neck formation at the bottom interface, and ultimately the detachment of the nanowires from the substrate at high ion fluence. Additional good agreement with experimental results from nano-x-ray fluorescence is also obtained for the continuously increasing Mn/Zn atomic ratio within the nanowires as a function of ion fluence. The simulation yields a great deal of additional information that has not been accessible in the experiments. From this, preferential sputtering of O compared with Zn is deduced. A significant contamination of the wires with substrate material arises from ion mixing at the wire/substrate interface, rather than from redeposition of sputtered substrate atoms. Surprising hollow profiles are observed. Their formation is attributed to a special mechanism of collisional transport which is characteristic of the irradiation of nanowires at a suitable combination of wire diameter and ion energy.