Enhanced Luminescence of Yb3+ Ions Implanted to ZnO through the Selection of Optimal Implantation and Annealing Conditions.

Rare earth-doped zinc oxide (ZnO:RE) systems are attractive for future optoelectronic devices such as phosphors, displays, and LEDs with emission in the visible spectral range, working even in a radiation-intense environment. The technology of these systems is currently under development, opening up new fields of application due to the low-cost production. Ion implantation is a very promising technique to incorporate rare-earth dopants into ZnO. However, the ballistic nature of this process makes the use of annealing essential. The selection of implantation parameters, as well as post-implantation annealing, turns out to be non-trivial because they determine the luminous efficiency of the ZnO:RE system. This paper presents a comprehensive study of the optimal implantation and annealing conditions, ensuring the most efficient luminescence of RE3+ ions in the ZnO matrix. Deep and shallow implantations, implantations performed at high and room temperature with various fluencies, as well as a range of post-RT implantation annealing processes are tested: rapid thermal annealing (minute duration) under different temperatures, times, and atmospheres (O2, N2, and Ar), flash lamp annealing (millisecond duration) and pulse plasma annealing (microsecond duration). It is shown that the highest luminescence efficiency of RE3+ is obtained for the shallow implantation at RT with the optimal fluence of 1.0 × 1015 RE ions/cm2 followed by a 10 min annealing in oxygen at 800 °C, and the light emission from such a ZnO:RE system is so bright that can be observed with the naked eye.

Threshold Ion Energies for Creating Defects in 2D Materials from First-Principles Calculations: Chemical Interactions Are Important.

The characteristics of two-dimensional (2D) materials can be tuned by low-energy ion irradiation provided that the ion energy is correctly chosen. The optimum ion energy is related to Ethion, the minimum kinetic energy the ion should have to displace an atom from the material. Ethion can be assessed using the binary collision approximation (BCA) when the displacement threshold of the atom is known. However, for some ions the experimental data contradict the BCA results. Using density functional theory molecular dynamics (DFT-MD), we study the collisions of low-energy ions with graphene and hexagonal boron nitride and demonstrate that the BCA can strongly overestimate Ethion because energy transfer takes a finite time, and therefore, chemical interactions of the ion with the target are important. Finally, for all projectiles from H up to Ar, we calculate the values of Ethion required to displace an atom from graphene and h-BN, the archetypal 2D materials.

Nonlinear compositional and morphological evolution of ion irradiated GaSb prior to nanostructure formation.

Low-energy ion irradiation of III-V semiconductor surfaces can lead to the formation of regular hexagonal dot patterns at the surface. We present experimental and computational results for ion irradiation of GaSb surfaces which elucidate the nature of the coupled compositional and morphological pattern-formation mechanisms. We demonstrate by in-situ grazing-incidence small-angle x-ray scattering (GISAXS) and angle-resolved Auger electron spectroscopy (ARAES) that the emergence of an altered compositional depth profile is essential to induce morphological changes at the surface. This morphological evolution of the surface follows nucleation-and-growth kinetics. Furthermore, we show from massive-scale molecular dynamics (MD) simulations that the compositional depth profile evolution leads to thermodynamic phase separation, providing a lateral compositional instability that drives pattern formation. Additionally, high-fluence simulations elucidate the irradiation-induced mechanisms of compositional depth profile formation. Prompt ion effects drive formation of single-element "protoclusters", predominantly of Sb. Structural and energetic characterization of the simulation results indicate that Sb may be more mobile than Ga, providing a diffusional pathway for long-temporal-scale compositional evolution of the irradiated surface. Our findings motivate the development of new, comprehensive models which consider the total spatial and temporal complexity of multicomponent systems evolving under ion irradiation.

Revealing the formation dynamics of the electric double layer by means of in-situ Rutherford backscattering spectrometry.

We report on a new versatile experimental setup for in situ Rutherford backscattering spectrometry at solid-liquid interfaces which enables investigations of electric double layers directly and in a quantitative manner. A liquid cell with a three-electrode arrangement is mounted in front of the beam line, and a thin Si3N4 window (thickness down to 150 nm) separates the vacuum of the detector chamber from the electrolyte in the cell. By minimizing the contribution of the window to the measurement, a large variety of elements at the solid-liquid interface with sensitivities far below one monolayer can be monitored. The attachment of Ba onto the Si3N4 surface as a function of contact time and pH value of the electrolyte solution was chosen as an example system. From our measurement, we can not only follow the evolution of the double layer but also derive limits for the point of zero charge for the Si3N4 surface. Our findings of 5.7≤pHPZC≤6.2 are in good agreement with values found in the literature obtained by other techniques. Despite focusing on a specific system in this work, the presented setup allows for a large variety of in situ investigations at solid-liquid interfaces such as, but not limited to, tracing electrochemical reactions and monitoring segregation, adsorption, and dissolution and corrosion processes.

Realization of wafer-scale nanogratings with sub-50 nm period through vacancy epitaxy.

Gratings, one of the most important energy dispersive devices, are the fundamental building blocks for the majority of optical and optoelectronic systems. The grating period is the key parameter that limits the dispersion and resolution of the system. With the rapid development of large X-ray science facilities, gratings with periodicities below 50 nm are in urgent need for the development of ultrahigh-resolution X-ray spectroscopy. However, the wafer-scale fabrication of nanogratings through conventional patterning methods is difficult. Herein, we report a maskless and high-throughput method to generate wafer-scale, multilayer gratings with period in the sub-50 nm range. They are fabricated by a vacancy epitaxy process and coated with X-ray multilayers, which demonstrate extremely large angular dispersion at approximately 90 eV and 270 eV. The developed new method has great potential to produce ultrahigh line density multilayer gratings that can pave the way to cutting edge high-resolution spectroscopy and other X-ray applications.

Nanoscale modification of one-dimensional single-crystalline cuprous oxide.

In this work we report for the first time a method to modify the surface of Cu2O nanowires in a controllable way and physically weld them into a network form, which contributes to higher electrical conductivity as well as a strong water-repelling nature. We have used state-of-the-art theoretical calculations to support our experimental observations. We demonstrate how varying the irradiation fluence can modulate the surface and decorate the nanowire with a uniform distribution of Cu8O nanocrystals due to preferential sputtering. While several well studied joining techniques are available for carbon and metal-based nanowires, the same information for ceramic nanowires is scarce at present. The current study sheds light into this and a state-of-the-art 3D simulation technique predicts most of the modifications including surface modulation, oxygen depletion and welding. The welded network shows higher electrical conductivity than the unwelded assembly. With Cu2O being of p-type the current ion beam joining technique shows a novel path for fabricating p-i-n junctions or solar cell devices through bottom-up approach. Furthermore, we have explored the response of this network to moisture. Our calculation based on density functional theory predicts the hydrophilic nature of individual copper oxide nanowires both before and after irradiation. However, the network shows a strong water-repelling nature, which has been explained quantitatively using the Cassie-Baxter model.

Site-controlled formation of single Si nanocrystals in a buried SiO2 matrix using ion beam mixing.

For future nanoelectronic devices - such as room-temperature single electron transistors - the site-controlled formation of single Si nanocrystals (NCs) is a crucial prerequisite. Here, we report an approach to fabricate single Si NCs via medium-energy Si+ or Ne+ ion beam mixing of Si into a buried SiO2 layer followed by thermally activated phase separation. Binary collision approximation and kinetic Monte Carlo methods are conducted to gain atomistic insight into the influence of relevant experimental parameters on the Si NC formation process. Energy-filtered transmission electron microscopy is performed to obtain quantitative values on the Si NC size and distribution in dependence of the layer stack geometry, ion fluence and thermal budget. Employing a focused Ne+ beam from a helium ion microscope, we demonstrate site-controlled self-assembly of single Si NCs. Line irradiation with a fluence of 3000 Ne+/nm2 and a line width of 4 nm leads to the formation of a chain of Si NCs, and a single NC with 2.2 nm diameter is subsequently isolated and visualized in a few nanometer thin lamella prepared by a focused ion beam (FIB). The Si NC is centered between the SiO2 layers and perpendicular to the incident Ne+ beam.

A versatile ion beam spectrometer for studies of ion interaction with 2D materials.

We present an ultrahigh vacuum setup for ion spectroscopy of freestanding two-dimensional solid targets. An ion beam of different ion species (e.g., Xe with charge states from 1 to 44 and Ar with charge states from 1 to 18) and kinetic energies ranging from a few 10 eV to 400 keV is produced in an electron beam ion source. Ions are detected after their transmission through the 2D target with a position sensitive microchannel plate detector allowing the determination of the ion's exit charge state as well as the scattering angle with a resolution of approximately 0.04°. Furthermore, the spectrometer is mounted on a swiveling frame covering a scattering angle of ±8° with respect to the incoming beam direction. By utilizing a beam chopper, we measure the time-of-flight of the projectiles and determine the energy loss when passing a 2D target with an energy uncertainty of about 2%. Additional detectors are mounted close to the target to observe emitted secondary particles and are read-out in coincidence with the position and time information of the ion detector. A signal in these detectors can also be used as a start trigger for time-of-flight measurements, which then yield an energy resolution of 1% and an approximately 1000-fold larger duty cycle. First results on the interaction of slow Xe30+ ions with a freestanding single layer of graphene obtained with the new setup are compared to recently published data where charge exchange and energy were measured by means of an electrostatic analyzer.

Implanting Germanium into Graphene.

Incorporating heteroatoms into the graphene lattice may be used to tailor its electronic, mechanical and chemical properties, although directly observed substitutions have thus far been limited to incidental Si impurities and P, N and B dopants introduced using low-energy ion implantation. We present here the heaviest impurity to date, namely 74Ge+ ions implanted into monolayer graphene. Although sample contamination remains an issue, atomic resolution scanning transmission electron microscopy imaging and quantitative image simulations show that Ge can either directly substitute single atoms, bonding to three carbon neighbors in a buckled out-of-plane configuration, or occupy an in-plane position in a divacancy. First-principles molecular dynamics provides further atomistic insight into the implantation process, revealing a strong chemical effect that enables implantation below the graphene displacement threshold energy. Our results demonstrate that heavy atoms can be implanted into the graphene lattice, pointing a way toward advanced applications such as single-atom catalysis with graphene as the template.

Large-scale self-organized gold nanostructures with bidirectional plasmon resonances for SERS.

Efficient substrates for surface-enhanced Raman spectroscopy (SERS) are under constant development, since time-consuming and costly fabrication routines are often an issue for high-throughput spectroscopy applications. In this research, we use a two-step fabrication method to produce self-organized parallel-oriented plasmonic gold nanostructures. The fabrication routine is ready for wafer-scale production involving only low-energy ion beam irradiation and metal deposition. The optical spectroscopy features of the resulting structures show a successful bidirectional plasmonic response. The localized surface plasmon resonances (LSPRs) of each direction are independent from each other and can be tuned by the fabrication parameters. This ability to tune the LSPR characteristics allows the development of optimized plasmonic nanostructures to match different laser excitations and optical transitions for any arbitrary analyte. Moreover, in this study, we probe the polarization and wavelength dependence of such bidirectional plasmonic nanostructures by a complementary spectroscopic ellipsometry and Raman spectroscopy analysis. We observe a significant signal amplification by the SERS substrates and determine enhancement factors of over a thousand times. We also perform finite element method-based calculations of the electromagnetic enhancement for the SERS signal provided by the plasmonic nanostructures. The calculations are based on realistic models constructed using the same particle sizes and shapes experimentally determined by scanning electron microscopy. The spatial distribution of electric field enhancement shows some dispersion in the LSPR, which is a direct consequence of the semi-random distribution of hotspots. The signal enhancement is highly efficient, making our SERS substrates attractive candidates for high-throughput chemical sensing applications in which directionality, chemical stability, and large-scale fabrication are essential requirements.

Ultrafast electronic response of graphene to a strong and localized electric field.

The way conduction electrons respond to ultrafast external perturbations in low dimensional materials is at the core of the design of future devices for (opto)electronics, photodetection and spintronics. Highly charged ions provide a tool for probing the electronic response of solids to extremely strong electric fields localized down to nanometre-sized areas. With ion transmission times in the order of femtoseconds, we can directly probe the local electronic dynamics of an ultrathin foil on this timescale. Here we report on the ability of freestanding single layer graphene to provide tens of electrons for charge neutralization of a slow highly charged ion within a few femtoseconds. With values higher than 1012 A cm-2, the resulting local current density in graphene exceeds previously measured breakdown currents by three orders of magnitude. Surprisingly, the passing ion does not tear nanometre-sized holes into the single layer graphene. We use time-dependent density functional theory to gain insight into the multielectron dynamics.

Tuning the Fabrication of Nanostructures by Low-Energy Highly Charged Ions.

Slow highly charged ions have been utilized recently for the creation of monotype surface nanostructures (craters, calderas, or hillocks) in different materials. In the present study, we report on the ability of slow highly charged xenon ions (^{129}Xe^{Q+}) to form three different types of nanostructures on the LiF(100) surface. By increasing the charge state from Q=15 to Q=36, the shape of the impact induced nanostructures changes from craters to hillocks crossing an intermediate stage of caldera structures. A dimensional analysis of the nanostructures reveals an increase of the height up to 1.5 nm as a function of the potential energy of the incident ions. Based on the evolution of both the geometry and size of the created nanostructures, defect-mediated desorption and the development of a thermal spike are utilized as creation mechanisms of the nanostructures at low and high charge states, respectively.

Temperature-Dependent Charge Transport through Individually Contacted DNA Origami-Based Au Nanowires.

DNA origami nanostructures have been used extensively as scaffolds for numerous applications such as for organizing both organic and inorganic nanomaterials, studying single molecule reactions, and fabricating photonic devices. Yet, little has been done toward the integration of DNA origami nanostructures into nanoelectronic devices. Among other challenges, the technical difficulties in producing well-defined electrical contacts between macroscopic electrodes and individual DNA origami-based nanodevices represent a serious bottleneck that hinders the thorough characterization of such devices. Therefore, in this work, we have developed a method to electrically contact individual DNA origami-based metallic nanowires using electron beam lithography. We then characterize the charge transport of such nanowires in the temperature range from room temperature down to 4.2 K. The room temperature charge transport measurements exhibit ohmic behavior, whereas at lower temperatures, multiple charge transport mechanisms such as tunneling and thermally assisted transport start to dominate. Our results confirm that charge transport along metallized DNA origami nanostructures may deviate from pure metallic behavior due to several factors including partial metallization, seed inhomogeneities, impurities, and weak electronic coupling among AuNPs. Besides, this study further elucidates the importance of variable temperature measurements for determining the dominant charge transport mechanisms for conductive nanostructures made by self-assembly approaches.

Alignment of Gold Nanoparticle-Decorated DNA Origami Nanotubes: Substrate Prepatterning versus Molecular Combing.

DNA origami has become an established technique for designing well-defined nanostructures with any desired shape and for the controlled arrangement of functional nanostructures with few nanometer resolution. These unique features make DNA origami nanostructures promising candidates for use as scaffolds in nanoelectronics and nanophotonics device fabrication. Consequently, a number of studies have shown the precise organization of metallic nanoparticles on various DNA origami shapes. In this work, we fabricated large arrays of aligned DNA origami decorated with a high density of gold nanoparticles (AuNPs). To this end, we first demonstrate the high-yield assembly of high-density AuNP arrangements on DNA origami adsorbed to Si surfaces with few unbound background nanoparticles by carefully controlling the concentrations of MgCl2 and AuNPs in the hybridization buffer and the hybridization time. Then, we evaluate two methods, i.e., hybridization to prealigned DNA origami and molecular combing in a receding meniscus, with respect to their potential to yield large arrays of aligned AuNP-decorated DNA origami nanotubes. Because of the comparatively low MgCl2 concentration required for the efficient immobilization of the AuNPs, the prealigned DNA origami become mobile and displaced from their original positions, thereby decreasing the alignment yield. This increased mobility, on the other hand, makes the adsorbed origami susceptible to molecular combing, and a total alignment yield of 86% is obtained in this way.

Optical characterisation of plasmonic nanostructures on planar substrates using second-harmonic generation.

Off-normal, polarization dependent second-harmonic generation (SHG) measurements were performed ex situ on plasmonic nanostructures grown by self-assembly on nanopatterned templates. These exploratory studies of Ag nanoparticle (NP) arrays show that the sensitivity of SHG to the local fields, which are modified by the NP size, shape and distribution, makes it a promising fixed wavelength characterization technique that avoids the complexity of spectroscopic SHG. The off-normal geometry provides access to the out-of-plane SH response, which is typically an order-of-magnitude larger than the in-surface-plane response measured using normal incidence, for example in SHG microscopy. By choosing the plane of incidence orthogonal to the NP array direction, it was shown that the p-polarized SH response, as a function of input polarization, is very sensitive to NP morphology, with a change of 20% in the aspect ratio of the NPs producing a variation of a factor of 30 in the easily measureable ratio of the p-polarized SH field strength for s- and p-polarized input. The results show that such a fixed geometry could be used for the in situ characterization of anisotropic nanostructure morphology during growth by self-assembly, which could be particularly useful in situations where rotating the sample may be neither desirable nor easily accomplished.

Faceted nanostructure arrays with extreme regularity by self-assembly of vacancies.

Semiconductor quantum dots and wires are important building blocks for future electronic and optoelectronic devices. The common way of producing semiconductor nanostructures is by molecular beam epitaxy (MBE). In this additive growth process atoms are deposited onto crystalline surfaces and self-assemble into 3D structures. Here we present a subtractive process, in which surface vacancies are created by ion impacts. On terraces of crystalline surfaces their nucleation forms depressions which coarsen and finally lead to a self-organized 3D morphology. It is shown that this kind of spontaneous pattern formation is inherent to the ion induced erosion process on crystalline surfaces and is analogous to 3D growth by MBE. However, novel facets are found due to slightly different energetics and kinetics of ad-atoms and surface vacancies, especially at Ehrlich-Schwoebel step-edge barriers. Depending on the crystal orientation, three-fold, four-fold, six-fold symmetry, as well as extremely regular periodic nanogrooves can be produced on different orientations of group IV (Si, Ge) and III-V (GaAs, InAs) semiconductors.

Charge exchange and energy loss of slow highly charged ions in 1 nm thick carbon nanomembranes.

Experimental charge exchange and energy loss data for the transmission of slow highly charged Xe ions through ultrathin polymeric carbon membranes are presented. Surprisingly, two distinct exit charge state distributions accompanied by charge exchange dependent energy losses are observed. The energy loss for ions exhibiting large charge loss shows a quadratic dependency on the incident charge state indicating that equilibrium stopping force values do not apply in this case. Additional angle resolved transmission measurements point on a significant contribution of elastic energy loss. The observations show that regimes of different impact parameters can be separated and thus a particle's energy deposition in an ultrathin solid target may not be described in terms of an averaged energy loss per unit length.

Silicide induced ion beam patterning of Si(001).

Low energy ion beam pattern formation on Si with simultaneous co-deposition of Ag, Pd, Pb, Ir, Fe or C impurities was investigated by in situ scanning tunneling microscopy as well as ex situ atomic force microscopy, scanning electron microscopy, transmission electron microscopy and Rutherford backscattering spectrometry. The impurities were supplied by sputter deposition. Additional insight into the mechanism of pattern formation was obtained by more controlled supply through e-beam evaporation. For the situations investigated, the ability of the impurity to react with Si, i.e. to form a silicide, appears to be a necessary, but not a sufficient condition for pattern formation. Comparing the effects of impurities with similar mass and nuclear charge, the collision kinetics is shown to be not of primary importance for pattern formation. To understand the observed phenomena, it is necessary to assume a bi-directional coupling of composition and height fluctuations. This coupling gives rise to a sensitive dependence of the final morphology on the conditions of impurity supply. Because of this history dependence, the final morphology cannot be uniquely characterized by a steady state impurity concentration.

Printing nearly-discrete magnetic patterns using chemical disorder induced ferromagnetism.

Ferromagnetism in certain alloys consisting of magnetic and nonmagnetic species can be activated by the presence of chemical disorder. This phenomenon is linked to an increase in the number of nearest-neighbor magnetic atoms and local variations in the electronic band structure due to the existence of disorder sites. An approach to induce disorder is through exposure of the chemically ordered alloy to energetic ions; collision cascades formed by the ions knock atoms from their ordered sites and the concomitant vacancies are filled randomly via thermal diffusion of atoms at room temperature. The ordered structure thereby undergoes a transition into a metastable solid solution. Here we demonstrate the patterning of highly resolved magnetic structures by taking advantage of the large increase in the saturation magnetization of Fe60Al40 alloy triggered by subtle atomic displacements. The sigmoidal characteristic and sensitive dependence of the induced magnetization on the atomic displacements manifests a sub-50 nm patterning resolution. Patterning of magnetic regions in the form of stripes separated by ∼ 40 nm wide spacers was performed, wherein the magnet/spacer/magnet structure exhibits reprogrammable parallel (↑/spacer/↑) and antiparallel (↑/spacer/↓) magnetization configurations in zero field. Materials in which the magnetic behavior can be tuned via ion-induced phase transitions may allow the fabrication of novel spin-transport and memory devices using existing lateral patterning tools.

Topography-controlled alignment of DNA origami nanotubes on nanopatterned surfaces.

The controlled positioning of DNA nanostructures on technologically relevant surfaces represents a major goal along the route toward the full-scale integration of DNA-based materials into nanoelectronic and sensor devices. Previous attempts to arrange DNA nanostructures into defined arrays mostly relied on top-down lithographic patterning techniques combined with chemical surface functionalization. Here we combine two bottom-up techniques for nanostructure fabrication, i.e., self-organized nanopattern formation and DNA origami self-assembly, in order to demonstrate the electrostatic self-alignment of DNA nanotubes on topographically patterned silicon surfaces. Self-organized nanoscale ripple patterns with periodicities ranging from 20 nm to 50 nm are fabricated by low-energy ion irradiation and serve as substrates for DNA origami adsorption. Electrostatic interactions with the charged surface oxide during adsorption direct the DNA origami nanotubes to the ripple valleys and align them parallel to the ripples. By optimizing the pattern dimensions and the Debye length of the adsorption buffer, we obtain an alignment yield of ∼70%. Since this novel and versatile approach does not rely on any chemical functionalization of the surface or the DNA nanotubes, it can be applied to virtually any substrate material and any top-down or bottom-up nanopatterning technique. This technique thus may enable the wafer-scale fabrication of ordered arrays of functional DNA-based nanowires.