Dieter Isheim

Colossal injection of catalyst atoms into silicon nanowires

The incorporation of impurities during the growth of nanowires from the vapour phase alters their basic properties substantially, and this process is critical in an extended range of emerging nanometre-scale technologies. In particular, achieving precise control of the behaviour of group III and group V dopants has been a crucial step in the development of silicon (Si) nanowire-based devices. Recently it has been demonstrated that the use of aluminium (Al) as a growth catalyst, instead of the usual gold, also yields an effective p-type doping, thereby enabling a novel and efficient route to functionalizing Si nanowires. Besides the technological implications, this self-doping implies the detachment of Al from the catalyst and its injection into the growing nanowire, involving atomic-scale processes that are crucial for the fundamental understanding of the catalytic assembly of nanowires. Here we present an atomic-level, quantitative study of this phenomenon of catalyst dissolution by three-dimensional atom-by-atom mapping of individual Al-catalysed Si nanowires using highly focused ultraviolet-laser-assisted atom-probe tomography. Although the observed incorporation of the catalyst atoms into nanowires exceeds by orders of magnitude the equilibrium solid solubility and solid-solution concentrations in known non-equilibrium processes, the Al impurities are found to be homogeneously distributed in the nanowire and do not form precipitates or clusters. As well as the anticipated effect on the electrical properties, this kinetics-driven colossal injection also has direct implications for nanowire morphology. We discuss the observed strong deviation from equilibrium using a model of solute trapping at step edges, and identify the key growth parameters behind this phenomenon on the basis of a kinetic model of step-flow growth of nanowires. The control of this phenomenon provides opportunities to create a new class of nanoscale devices by precisely tailoring the shape and composition of metal-catalysed nanowires.

Atom-probe tomographic study of interfaces of Cu2ZnSnS4 photovoltaic cells

The heterophase interfaces between the CdS buffer layer and the Cu2ZnSnS4 (CZTS) absorption layers are one of the main factors affecting photovoltaic performance of CZTS cells. We have studied the compositional distributions at heterophase interfaces in CZTS cells using three-dimensional atom-probe tomography. The results demonstrate: (a) diffusion of Cd into the CZTS layer; (b) segregation of Zn at the CdS/CZTS interface; and (c) a change of oxygen and hydrogen concentrations in the CdS layer depending on the heat treatment. Annealing at 573 K after deposition of CdS improves the photovoltaic properties of CZTS cells probably because of the formation of a heterophase epitaxial junction at the CdS/CZTS interface. Conversely, segregation of Zn at the CdS/CZTS interface after annealing at a higher temperature deteriorates the photovoltaic properties.

Nanoscale studies of the chemistry of a René N6 superalloy

Atom-probe field-ion microscopy (APFIM) is used to study partitioning of the alloying elements between the γ (FCC) and γ′ (L12) phases and their segregation behavior at γ/γ′ interfaces of a René N6 nickel-based superalloy. The atomic-scale resolution and real space reconstruction capability for elemental chemical mapping makes three-dimensional atom-probe microscopy especially suitable for subnanoscale investigations of complex multicomponent superalloys. Concentration profiles of this alloy, obtained from an atom probe analysis, reveal the partitioning behavior of the alloying elements in René N6. As anticipated, the matrix strengtheners, such as Mo and W, are partitioned to the γ (FCC) matrix, while Re segregates at the γ/γ′ interfaces; the Gibbsian interfacial excess of Re is determined by both one-dimensional (2.32 atoms nm−2) and three-dimensional atom-probe microscopies (3.92 atoms nm−2) and the values obtained are in reasonable agreement.

Heterogeneous silicon mesostructures for lipid-supported bioelectric interfaces

Silicon-based materials have widespread application as biophysical tools and biomedical devices. Here we introduce a biocompatible and degradable mesostructured form of silicon with multiscale structural and chemical heterogeneities. The material was synthesized using mesoporous silica as a template through a chemical-vapor-deposition process. It has an amorphous atomic structure, an ordered nanowire-based framework, and random submicrometre voids, and shows an average Young’s modulus that is 2–3 orders of magnitude smaller than that of single crystalline silicon. In addition, we used the heterogeneous silicon mesostructures to design a lipid-bilayer-supported bioelectric interface that is remotely controlled and temporally transient, and that permits non-genetic and subcellular optical modulation of the electrophysiology dynamics in single dorsal root ganglia neurons. Our findings suggest that the biomimetic expansion of silicon into heterogeneous and deformable forms can open up opportunities in extracellular biomaterial or bioelectric systems.

Development of a Refractory High Entropy Superalloy

Microstructure, phase composition and mechanical properties of a refractory high entropy superalloy, AlMo0.5NbTa0.5TiZr, are reported in this work. The alloy consists of a nano-scale mixture of two phases produced by the decomposition from a high temperature body-centered cubic (BCC) phase. The first phase is present in the form of cuboidal-shaped nano-precipitates aligned in rows along -type directions, has a disordered BCC crystal structure with the lattice parameter a1 = 326.9 ± 0.5 pm and is rich in Mo, Nb and Ta. The second phase is present in the form of channels between the cuboidal nano-precipitates, has an ordered B2 crystal structure with the lattice parameter a2 = 330.4 ± 0.5 pm and is rich in Al, Ti and Zr. Both phases are coherent and have the same crystallographic orientation within the former grains. The formation of this modulated nano-phase structure is discussed in the framework of nucleation-and-growth and spinodal decomposition mechanisms. The yield strength of this refractory high entropy superalloy is superior to the yield strength of Ni-based superalloys in the temperature range of 20 °C to 1200 °C.

Ultraviolet-laser atom-probe tomographic three-dimensional atom-by-atom mapping of isotopically modulated Si nanoscopic layers

Using ultraviolet-laser assisted local-electrode atom-probe (UV-LEAP) tomography, we obtain three-dimensional (3D) atom-by-atom images of isotopically modulated S28i and S30i ultrathin layers having thicknesses in the range of 5–30 nm. The 3D images display interfaces between the different monoisotopic layers with an interfacial width of ∼1.7 nm, thus demonstrating a significant improvement over isotope mapping achievable using secondary-ion mass-spectrometry or even visible laser-assisted atom-probe tomography. This sharpness is attributed to reduced thermal effects resulting from using a highly focused UV laser beam. Our findings demonstrate that UV-LEAP tomography provides the high accuracy needed to characterize, at the subnanometer scale, the emerging isotopically programmed nanomaterials.

Atomic resolution mapping of interfacial intermixing and segregation in InAs/GaSb superlattices: A correlative study

We combine quantitative analyses of Z-contrast images with composition analyses employing atom probe tomography (APT) correlatively to provide a quantitative measurement of atomic scale interfacial intermixing in an InAs/GaSb superlattice (SL). Contributions from GaSb and InAs in the Z-contrast images are separated using an improved image processing technique. Correlation with high resolution APT composition analyses permits an examination of interfacial segregation of both cations and anions and their incorporation in the short period InAs/GaSb SL. Results revealed short, intermediate, and long-range intermixing of In, Ga, and Sb during molecular beam epitaxial growth and their distribution in the SL.

Phonon Engineering in Isotopically Disordered Silicon Nanowires

The introduction of stable isotopes in the fabrication of semiconductor nanowires provides an additional degree of freedom to manipulate their basic properties, design an entirely new class of devices, and highlight subtle but important nanoscale and quantum phenomena. With this perspective, we report on phonon engineering in metal-catalyzed silicon nanowires with tailor-made isotopic compositions grown using isotopically enriched silane precursors (28)SiH4, (29)SiH4, and (30)SiH4 with purity better than 99.9%. More specifically, isotopically mixed nanowires (28)Si(x)(30)Si(1-x) with a composition close to the highest mass disorder (x ∼ 0.5) were investigated. The effect of mass disorder on the phonon behavior was elucidated and compared to that in isotopically pure (29)Si nanowires having a similar reduced mass. We found that the disorder-induced enhancement in phonon scattering in isotopically mixed nanowires is unexpectedly much more significant than in bulk crystals of close isotopic compositions. This effect is explained by a nonuniform distribution of (28)Si and (30)Si isotopes in the grown isotopically mixed nanowires with local compositions ranging from x = ∼0.25 to 0.70. Moreover, we also observed that upon heating, phonons in (28)Si(x)(30)Si(1-x) nanowires behave remarkably differently from those in (29)Si nanowires suggesting a reduced thermal conductivity induced by mass disorder. Using Raman nanothermometry, we found that the thermal conductivity of isotopically mixed (28)Si(x)(30)Si(1-x) nanowires is ∼30% lower than that of isotopically pure (29)Si nanowires in agreement with theoretical predictions.

Direct measurement of two-dimensional and three-dimensional interprecipitate distance distributions from atom-probe tomographic reconstructions

Edge-to-edge interprecipitate distance distributions are critical for predicting precipitation strengthening of alloys and other physical phenomena. A method to calculate this three-dimensional distance and the two-dimensional interplanar distance from atom-probe tomographic data is presented. It is applied to nanometer-sized Cu-rich precipitates in an Fe-1.7at.% Cu alloy. Experimental interprecipitate distance distributions are discussed.

C12/C13-ratio determination in nanodiamonds by atom-probe tomography

The astrophysical origins of ∼ 3 nm-diameter meteoritic nanodiamonds can be inferred from the ratio of C12/C13. It is essential to achieve high spatial and mass resolving power and minimize all sources of signal loss in order to obtain statistically significant measurements. We conducted atom-probe tomography on meteoritic nanodiamonds embedded between layers of Pt. We describe sample preparation, atom-probe tomography analysis, 3D reconstruction, and bias correction. We present new data from meteoritic nanodiamonds and terrestrial standards and discuss methods to correct isotopic measurements made with the atom-probe tomograph.