New avenues for residual stress analysis in ultrathin atomic layer deposited free-standing membranes through release of micro-cantilevers.

The fabrication of thinnest, yet undeformed membrane structures with nanometer resolution is a prerequisite for a variety of Microelectromechanical systems (MEMS). However, functionally relevant thin films are susceptible to growth-generated stress. To tune the performance and reach large aspect ratios, knowledge of the intrinsic material properties is indispensable. Here, we present a new method for stress evaluation through releasing defined micro-cantilever segments by focused ion beam (FIB) milling from a predefined free-standing membrane structure. Thereby, the cantilever segment is allowed to equilibrate to a stress-released state through measurable strain in the form of a resulting radius of curvature. This radius can be back-calculated to the residual stress state. The method was tested on a 20 nm and 50 nm thick tunnel-like ALD Image 1 membrane structure, revealing a significant amount of residual stress with 866 MPa and 6104 MPa, respectively. Complementary finite element analysis to estimate the stress distribution in the structure showed a 97% and 90% agreement in out-of-plane deflection for the 20 nm and 50 nm membranes, respectively. This work reveals the possibilities of releasing entire membrane segments from thin film membranes with a significant amount of residual stress and to use the resulting bending behavior for evaluating stress and strain by measuring their deformation.

Atomic-scale 3D imaging of individual dopant atoms in an oxide semiconductor.

The physical properties of semiconductors are controlled by chemical doping. In oxide semiconductors, small variations in the density of dopant atoms can completely change the local electric and magnetic responses caused by their strongly correlated electrons. In lightly doped systems, however, such variations are difficult to determine as quantitative 3D imaging of individual dopant atoms is a major challenge. We apply atom probe tomography to resolve the atomic sites that donors occupy in the small band gap semiconductor Er(Mn,Ti)O3 with a nominal Ti concentration of 0.04 at. %, map their 3D lattice positions, and quantify spatial variations. Our work enables atomic-level 3D studies of structure-property relations in lightly doped complex oxides, which is crucial to understand and control emergent dopant-driven quantum phenomena.

Atomic resolution imaging of beryl: an investigation of the nano-channel occupation.

Beryl in different varieties (emerald, aquamarine, heliodor etc.) displays a wide range of colours that have fascinated humans throughout history. Beryl is a hexagonal cyclo-silicate (ring-silicate) with channels going through the crystal along the c-axis. The channels are about 0.5 nm in diameter and can be occupied by water and alkali ions. Pure beryl (Be3 Al2 Si6 O18 ) is colourless (variety goshenite). The characteristic colours are believed to be mainly generated through substitutions with metal atoms in the lattice. Which atoms that are substituted is still debated it has been proposed that metal ions may also be enclosed in the channels and that this can also contribute to the crystal colouring. So far spectroscopy studies have not been able to fully answer this. Here we present the first experiments using atomic resolution scanning transmission electron microscope imaging (STEM) to investigate the channel occupation in beryl. We present images of a natural beryl crystal (variety heliodor) from the Bin Thuan Province in Vietnam. The channel occupation can be visualized. Based on the image contrast in combination with ex situ element analysis we suggest that some or all of the atoms that are visible in the channels are Fe ions.

Effect of V/III ratio on the structural and optical properties of self-catalysed GaAs nanowires.

The performance of GaAs nanowire (NW) devices depends critically on the presence of crystallographic defects in the NWs such as twinning planes and stacking faults, and considerable effort has been devoted to understanding and preventing the occurrence of these. For self-catalysed GaAs NWs grown by molecular beam epitaxy (MBE) in particular, there are in addition other types of defects that may be just as important for NW-based optoelectronic devices. These are the point defects such as the As vacancy and the Ga antisite occurring due to the inherently Ga-rich conditions of the self-catalysed growth. Here we demonstrate experimentally the effects of these point defects on the optical properties of GaAs/AlGaAs core-shell NWs grown by self-catalysed MBE. The present results enable insight into the role of the point defects both on their own and in conjunction with crystallographic planar defects.

In situ electronic probing of semiconducting nanowires in an electron microscope.

For the development of electronic nanoscale structures, feedback on its electronic properties is crucial, but challenging. Here, we present a comparison of various in situ methods for electronically probing single, p-doped GaAs nanowires inside a scanning electron microscope. The methods used include (i) directly probing individual as-grown nanowires with a sharp nano-manipulator, (ii) contacting dispersed nanowires with two metal contacts and (iii) contacting dispersed nanowires with four metal contacts. For the last two cases, we compare the results obtained using conventional ex situ litho-graphy contacting techniques and by in situ, direct-write electron beam induced deposition of a metal (Pt). The comparison shows that 2-probe measurements gives consistent results also with contacts made by electron beam induced deposition, but that for 4-probe, stray deposition can be a problem for shorter nanowires. This comparative study demonstrates that the preferred in situ method depends on the required throughput and reliability.

Position-controlled uniform GaAs nanowires on silicon using nanoimprint lithography.

We report on the epitaxial growth of large-area position-controlled self-catalyzed GaAs nanowires (NWs) directly on Si by molecular beam epitaxy (MBE). Nanohole patterns are defined in a SiO2 mask on 2 in. Si wafers using nanoimprint lithography (NIL) for the growth of positioned GaAs NWs. To optimize the yield of vertical NWs the MBE growth parameter space is tuned, including Ga predeposition time, Ga and As fluxes, growth temperature, and annealing treatment prior to NW growth. In addition, a non-negligible radial growth is observed with increasing growth time and is found to be independent of the As species (i.e., As2 or As4) and the growth temperatures studied. Cross-sectional transmission electron microscopy analysis of the GaAs NW/Si substrate heterointerface reveals an epitaxial growth where NW base fills the oxide hole opening and eventually extends over the oxide mask. These findings have important implications for NW-based device designs with axial and radial p-n junctions. Finally, NIL positioned GaAs/AlGaAs core-shell heterostructured NWs are grown on Si to study the optical properties of the NWs. Room-temperature photoluminescence spectroscopy of ensembles of as-grown core-shell NWs reveals uniform and high optical quality, as required for the subsequent device applications. The combination of NIL and MBE thereby demonstrates the successful heterogeneous integration of highly uniform GaAs NWs on Si, important for fabricating high throughput, large-area position-controlled NW arrays for various optoelectronic device applications.

Compositional characterization of GaAs/GaAsSb nanowires by quantitative HAADF-STEM.

The Sb concentration in axial GaAs(1-x)Sb(x) inserts of otherwise pure GaAs nanowires has been investigated with quantitative high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM). The Sb concentration was quantified by comparing the experimental image intensities normalized to the incident beam intensity with intensities simulated with a frozen lattice multislice approach. Including static atomic displacements in the simulations was found to be crucial for correct compositional analysis of GaAs(1-x)Sb(x). HAADF intensities of individual nanowires were analysed both across the nanowires, exploiting their hexagonal cross-sectional shape, and along the evenly thick central part of the nanowires. From the cross-sectional intensity profiles, a decrease in the Sb concentration towards the nanowire outer surfaces was found. The longitudinal intensity profiles revealed a gradual build-up of Sb in the insert. The decrease of the Sb concentration towards the upper interface was either gradual or abrupt, depending on the growth routine chosen. The compositional analysis with quantitative HAADF-STEM was verified by energy dispersive X-ray spectroscopy.

Controlling crystal phases in GaAs nanowires grown by Au-assisted molecular beam epitaxy.

Control of the crystal phases of GaAs nanowires (NWs) is essential to eliminate the formation of stacking faults which deteriorate the optical and electronic properties of the NWs. In addition, the ability to control the crystal phase of NWs provides an opportunity to engineer the band gap without changing the crystal material. We show that the crystal phase of GaAs NWs grown on GaAs(111)B substrates by molecular beam epitaxy using the Au-assisted vapor-liquid-solid growth mechanism can be tuned between wurtzite (WZ) and zinc blende (ZB) by changing the V/III flux ratio. As an example we demonstrate the realization of WZ GaAs NWs with a ZB GaAs insert that has been grown without changing the substrate temperature.

Correlated micro-photoluminescence and electron microscopy studies of the same individual heterostructured semiconductor nanowires.

To correlate optical properties to structural characteristics, we developed a robust strategy for characterizing the same individual heterostructured semiconductor nanowires (NWs) by alternating low temperature micro-photoluminescence (µ-PL), low voltage scanning (transmission) electron microscopy and conventional transmission electron microscopy. The NWs used in this work were wurtzite GaAs core with zinc blende GaAsSb axial insert and AlGaAs radial shell grown by molecular beam epitaxy. The series of experiments demonstrated that high energy (200 kV) electrons are detrimental for the optical properties, whereas medium energy (5-30 kV) electrons do not affect the PL response. Thus, such medium energy electrons can be used to select NWs for correlated optical-structural studies prior to µ-PL or in NW device processing. The correlation between the three main µ-PL bands and crystal phases of different compositions, present in this heterostructure, is demonstrated for selected NWs. The positions where a NW fractures during specimen preparation can considerably affect the PL spectra of the NW. The effects of crystal-phase variations and lattice defects on the optical properties are discussed. The established strategy can be applied to other nanosized electro-optical materials, and other characterization tools can be incorporated into this routine.

Wurtzite GaAs/AlGaAs core-shell nanowires grown by molecular beam epitaxy.

We report the growth of GaAs/AlGaAs core-shell nanowires (NWs) on GaAs(111)B substrates by Au-assisted molecular beam epitaxy. Electron microscopy shows the formation of a wurtzite AlGaAs shell structure both in the radial and the axial directions outside a wurtzite GaAs core. With higher Al content, a lower axial and a higher radial growth rate of the AlGaAs shell were observed. Room temperature and low temperature (4.4 K) micro-photoluminescence measurements show a much higher radiative efficiency from the GaAs core after the NW is overgrown with a radial AlGaAs shell.

Zinc blende GaAsSb nanowires grown by molecular beam epitaxy.

We report the growth of GaAsSb nanowires (NWs) on GaAs(111)B substrates by Au-assisted molecular beam epitaxy. The structural characteristics of the GaAsSb NWs have been investigated in detail. Their Sb mole fraction was found to be about 25%. Their crystal structure was found to be pure zinc blende (ZB), in contrast to the wurtzite structure observed in GaAs NWs grown under similar conditions. The ZB GaAsSb NWs exhibit rotational twins around their [111]B growth axis, with twin-free segments as long as 500 nm. The total volumes of GaAsSb segments with twinned and un-twinned orientations, respectively, were found to be equal by x-ray diffraction analysis of NW ensembles.