Atomic structure of 'W'-type quantum well heterostructures investigated by aberration-corrected STEM.

The atomic structure of (GaIn)As/Ga(AsSb)/(GaIn)As-'W'-type quantum well heterostructures ('W'-QWHs) is investigated by scanning transmission electron microscopy (STEM). These structures were grown by metal organic vapour phase epitaxy and are built for type-II laser systems in the infrared wavelength regime. For two samples grown at 525°C and 550°C, intensity profiles are extracted from the STEM images for each sublattice separately. These intensity profiles are compared to the one obtained from an image simulation of an ideal 'W'-QWH that is modelled in close agreement with the experiment. From the intensity profiles, the width of the different quantum wells (QWs) can be determined. Additionally, characteristics connected to the growth of the structures, such as segregation coefficients and material homogeneity, are calculated. Finally, composition profiles are derived from the STEM intensity profiles to a first approximation. For these composition profiles, the expected photoluminescence (PL) is computed based using the semiconductor luminescence equations. The PL spectra are then compared to experimental measurements for both samples.

Local sample thickness determination via scanning transmission electron microscopy defocus series.

The usable aperture sizes in (scanning) transmission electron microscopy ((S)TEM) have significantly increased in the past decade due to the introduction of aberration correction. In parallel with the consequent increase of convergence angle the depth of focus has decreased severely and optical sectioning in the STEM became feasible. Here we apply STEM defocus series to derive the local sample thickness of a TEM sample. To this end experimental as well as simulated defocus series of thin Si foils were acquired. The systematic blurring of high resolution high angle annular dark field images is quantified by evaluating the standard deviation of the image intensity for each image of a defocus series. The derived dependencies exhibit a pronounced maximum at the optimum defocus and drop to a background value for higher or lower values. The full width half maximum (FWHM) of the curve is equal to the sample thickness above a minimum thickness given by the size of the used aperture and the chromatic aberration of the microscope. The thicknesses obtained from experimental defocus series applying the proposed method are in good agreement with the values derived from other established methods. The key advantages of this method compared to others are its high spatial resolution and that it does not involve any time consuming simulations.

Structure determination in a new type of amorphous molecular solids with different nonlinear optical properties: a comparative structural analysis.

The microscopic structures of two amorphous molecular solids with extremely nonlinear optical properties have been studied. They consist of organotetrel chalcogenide clusters with the chemical formula [(RSn)4S6]. The basic molecular building blocks are adamantane-like {Sn4S6} cores with organic ligands R attached to the Sn atoms. While the material equipped with R=naphthyl generates frequency doubling upon irradiation with a simple infrared laser diode, the material decorated with R=phenyl responds by emitting brilliant white light. The structural differences were investigated using x-ray scattering and extended x-ray absorption fine structure combined with molecular Reverse Monte Carlo. Transmission electron microscopy and scanning precession electron diffraction were used to examine structural differences from mesoscopic down to microscopic scales. Characteristic differences were found on all scales. While close core-to-core distances between {Sn4S6} cluster cores and molecular distortions are found in the white light emitting material, undistorted molecules and significantly larger core distances characterize the material showing frequency doubling. Here however, results of scanning precession electron diffraction reveal the formation of nanocrystalline structures in the amorphous matrix, which we identify as cause for the suppression of white light emission.

Quantitative composition determination by ADF-STEM at a low-angular regime: a combination of EFSTEM and 4DSTEM.

High-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) is a valuable method for composition determination of nanomaterials. However, light elements do not scatter efficiently into the scattering angles employed for HAADF-STEM which hinders the composition determination of material systems containing light elements by HAADF-STEM. This makes the usage of lower scattering angles favourable. Moreover, static atomic displacements (SADs) caused by the small covalent radius of the substituting light elements in semiconductor alloys increase the scattering intensity at low angles. Nevertheless, at low angles, a quantitative match between complementary image simulations and experiments is not straight forward, since e.g. inelastic scattering and correlated phonon movement is often neglected in simulations. In this study, we establish a method to quantify material systems containing light elements at low angles by resolving the remaining sources of discrepancy. An outstanding agreement between simulations and experiments is achieved by using a combination of an in-column energy filter and a fast pixelated detector. By applying this method to GaNxAs1-x quantum wells, a good agreement of the TEM results with results from high-resolution x-ray diffraction is obtained. The method developed enables the nanoscale analysis of functional materials containing light elements, especially in the presence of SADs.

Optimization of imaging conditions for composition determination by annular dark field STEM.

Quantitative scanning transmission electron microscopy (STEM) allows composition determination for nanomaterials at an atomic scale. To improve the accuracy of the results obtained, optimized imaging parameters should be chosen for annular dark field imaging. In a simulation study, we investigate the influence of imaging parameters on the accuracy of the composition determination with the example of ternary III-V semiconductors. It is shown that inner and outer detector angles and semi-convergence angle can be optimized, also in dependence on specimen thickness. Both, a minimum sampling of the image and a minimum electron dose are required. These findings are applied experimentally by using a fast pixelated detector to allow free choice of detector angles.

Characterization of solar cells by photocurrent spectroscopy and current-voltage characteristics with high spatial resolution.

Spatially resolved photocurrent-spectroscopy and spatially resolved current-voltage characteristics are introduced as new methods to characterize solar cells. A combination of these two methods is shown to localize and characterize deficiencies and structural damages in processed solar cells with high spatial resolution. The local external and internal quantum efficiencies as well as the local characteristic parameters of the p-n junction like the short circuit current, the saturation current, the ideality factor, and the optically induced shunt resistance can be determined quantitatively. Both, a slab of a damaged and an undamaged (GaIn)(NAs) concentrator solar cell, are used as test structures. Upon these test structures domains with a high concentration of impurities in the crystal structure and structural imperfections in the upper contact region are identified and analyzed. Additional numerical simulations prove the reliability and show limits of the methods.

Simultaneous determination of local thickness and composition for ternary III-V semiconductors by aberration-corrected STEM.

Scanning transmission electron microscopy (STEM) is a suitable method for the quantitative characterization of nanomaterials. For an absolute composition determination on an atomic scale, the thickness of the specimen has to be known locally with high accuracy. Here, we propose a method to determine both thickness and composition of ternary III-V semiconductors locally from one STEM image as shown for the example material systems Ga(AsBi) and (GaIn)As. In a simulation study, the feasibility of the method is proven and the influence of specimen thickness and detector angles used is investigated. An application to an experimental STEM image of a Ga(AsBi) quantum well grown by metal organic vapour phase epitaxy yields an excellent agreement with composition results from high resolution X-ray diffraction.

Composition determination for quaternary III-V semiconductors by aberration-corrected STEM.

Quantitative scanning transmission electron microscopy (STEM) is a powerful tool for the characterization of nano-materials. Absolute composition determination for ternary III-V semiconductors by direct comparison of experiment and simulation is well established. Here, we show a method to determine the composition of quaternary III-V semiconductors with two elements on each sub lattice from the intensities of one STEM image. As an example, this is applied to (GaIn)(AsBi). The feasibility of the method is shown in a simulation study that also explores the influence of detector angles and specimen thickness. Additionally, the method is applied to an experimental STEM image of a (GaIn)(AsBi) quantum well grown by metal organic vapour phase epitaxy. The obtained concentrations are in good agreement with X-ray diffraction and photoluminescence results.

Three-dimensional structure of antiphase domains in GaP on Si(0 0 1).

Antiphase domains are three-dimensional crystal defects commonly arising at the interface of III-V semiconductors and Si. While control over their formation has been achieved, the geometry of the antiphase domain itself that is separated from the mainphase of the crystal by the so-called antiphase boundary, has not yet been fully understood. In this work, we first investigate the interface between GaP and Si itself by cross-sectional scanning tunneling microscopy (XSTM) to reveal possible intermixing within an 8 monolayers wide region. Furthermore, we present an extensive analysis combining transmission electron microscopy and XSTM to elucidate the shape of antiphase domains in GaP. To create a true-to-scale, three-dimensional model of an antiphase domain, firstly, plan-view transmission electron microscopy images are drawn on. Subsequently, the progression of many antiphase boundaries through the GaP crystal as viewed from the (1 1 0) and (1 [Formula: see text] 0) cleavage planes is analyzed all the way down to the atomic level by means of XSTM. This enables a detailed analysis of the shape and physical dimensions of the antiphase domains. A typical measured extension in growth directions is found to be a maximum of 60 nm and the maximum measured extension of the base plane in [[Formula: see text] 1 0] and [1 1 0] directions is about 160 nm and 50 nm, respectively. They appear as pyramids with anisotropic base planes whose side facets kink many times.

Composition determination of semiconductor alloys towards atomic accuracy by HAADF-STEM.

This paper presents a comprehensive investigation of an extended method to determine composition of materials by scanning transmission electron microscopy (STEM) high angle annular darkfield (HAADF) images and using complementary multislice simulations. The main point is to understand the theoretical capabilities of the algorithm and address the intrinsic limitations of using STEM HAADF intensities for composition determination. A special focus is the potential of the method regarding single-atom accuracy. All-important experimental parameters are included into the multislice simulations to ensure the best possible fit between simulation and experiment. To demonstrate the capabilities of the extended method, results for three different technical important semiconductor samples are presented. Overall the method shows a high lateral resolution combined with a high accuracy towards single-atom accuracy.

Thermally Introduced Bismuth Clustering in Ga(P,Bi) Layers under Group V Stabilised Conditions Investigated by Atomic Resolution In Situ (S)TEM.

We report the formation of Bi clusters in Ga(P1-x,Bix) layers during an in situ (scanning) transmission electron microscopy ((S)TEM) annealing investigation. The non-destructive temperature regime in dependence on the tertiarybutylphosphine (TBP) pressure in the in situ cell was investigated to ensure that the results are not distorted by any destructive behaviour of the crystal during the thermal treatment. The following annealing series of the Ga(P92.6Bi7.4) and Ga(P96.4Bi3.6) layers reveals that the threshold temperature at which the Bi clustering takes place is 600 °C in the Ga(P92.6Bi7.4) layer. Further thermal treatments up to 750 °C show a relationship between the Bi fraction in the Ga(P1-x,Bix) layer and the initial temperature at which the Bi clustering takes place. Finally, we investigate one Bi cluster at atomic resolution conditions. In these conditions, we found that the Bi cluster crystallized in a rhombohedral phase, aligning with its {101} planes parallel to the Ga(P,Bi) {202} planes.

Second-harmonic generation as a probe for structural and electronic properties of buried GaP/Si(0 0 1) interfaces.

Optical second-harmonic generation is demonstrated to be a sensitive probe of the buried interface between the lattice-matched semiconductors gallium phosphide and silicon with (0 0 1) orientation. Ex situ rotational anisotropy measurements on GaP/Si heterostructures show a strong isotropic component of the second-harmonic response not present for pure Si(0 0 1) or GaP(0 0 1). The strength of the overlaying anisotropic response directly correlates with the quality of the interface as determined by atomically resolved scanning transmission electron microscopy. Systematic comparison of samples fabricated under different growth conditions in metal-organic vapor phase epitaxy reveals that the anisotropy for different polarization combinations can be used as a selective fingerprint for the occurrence of anti-phase domains and twins. This all-optical technique can be applied as an in situ and non-invasive monitor even during growth.

An experimental approach for real time mass spectrometric CVD gas phase investigations.

This is a report on the first setup of a recently developed, extremely sensitive and very fast 3D quadrupole ion trap mass spectrometer inline in a metalorganic vapour phase epitaxy (MOVPE) system. This setup was developed ultimately for the decomposition- and the interaction analysis of various established as well as novel metalorganic sources for MOVPE deposition of III/V semiconductors. To make in-situ gas phase and growth interaction analysis on a new level of sensitivity possible without disturbing the MOVPE growth process itself, an optimized experimental connection of the mass spectrometer to the MOVPE system is required. This work reports on the realization of such an experimental setup and provides first proof of concept for decomposition analysis. In addition, a comparison to previous studies and gas-phase analysis at MOVPE systems will be given in this work.

Towards the liquid phase exfoliation of bismuth iodide.

Liquid phase exfoliation (LPE) of layered compounds towards few- or monolayers has been established as one of the prime methods in the growing field of 2D material research. Here, we present first steps towards an effective LPE of bismuth(iii) iodide, a semiconductor with potential as a photovoltaic absorber material. We highlight guidelines in the choice of exfoliating solvent, which differ significantly from those used with transition metal dichalcogenides or graphene. We also present first evidence of successful few-layer formation from spectroscopic, electron microscopy and electron diffraction investigations.

Tuning the magnetic properties of GaAs:Mn/MnAs hybrids via the MnAs cluster shape.

We report a systematic study of ferromagnetic resonance in granular GaAs:Mn/MnAs hybrids grown on GaAs(001) substrates by metal-organic vapour-phase epitaxy. The ferromagnetic resonance of the MnAs clusters can be resolved at all temperatures below T(c). An additional broad absorption is observed below 60 K and is ascribed to localized charge carriers of the GaAs:Mn matrix. The anisotropy of the MnAs ferromagnetic resonance field originates from the magneto-crystalline field and demagnetization effects of the ferromagnetic MnAs clusters embedded in the GaAs:Mn matrix. Its temperature dependence basically scales with magnetization. Comparison of the observed angular dependence of the resonance field with model calculations yields the preferential orientation and shape of the clusters formed in hybrid layers of different thickness (150-1000 nm) grown otherwise at the same growth conditions. The hexagonal axes of the MnAs clusters are oriented along the four cubic GaAs space diagonals. Thin layers contain lens-shaped MnAs clusters close to the surface, whereas thick layers also contain spherical clusters in the bulk of the layer. The magnetic properties of the hexagonal MnAs clusters can be tuned by a controlled variation of the cluster shape.

The low ionic strength crystal structure of horse cytochrome c at 2.1 A resolution and comparison with its high ionic strength counterpart.

BACKGROUND: Cytochrome c is an integral part of the mitochondrial respiratory chain. It is confined to the intermembrane space of mitochondria, and has the function of transferring electrons between its redox partners. Solution studies of cytochrome c indicate that the conformation of the molecule is sensitive to the ionic strength of the medium. RESULTS: The crystal structures of cytochromes c from several species have been solved at extremely high ionic strengths of near-saturated solutions of ammonium sulfate. Here we present the first crystal structure of ferricytochrome c at low ionic strength refined at 2.1 A resolution. In general, the structure has the same features as those determined earlier. However, there are some differences in both backbone and side-chain conformations in several areas. These areas coincide with those observed by NMR and resonance Raman spectroscopy to be sensitive to ionic strength. CONCLUSIONS: Neither ionic strength nor crystal-packing interactions have much influence on the conformation of horse cytochrome c. Nevertheless, some differences in the side-chain conformations at high and low ionic strengths may be important for understanding how the protein functions. Close examination of the gamma-turn (residues 27-29) conserved in cytochromes c leads us to propose the 'negative classical' gamma-turn to describe this unusual feature.

2.5 A structure of aspartate carbamoyltransferase complexed with the bisubstrate analog N-(phosphonacetyl)-L-aspartate.

In an X-ray diffraction study using the method of multiple isomorphous replacement, the structure of aspartate carbamoyltransferase (EC 2.1.3.2) complexed with the bisubstrate analog N-(phosphonacetyl)-L-aspartate (PALA) has been solved to 2.5 A. Ten rounds of model building and 123 cycles of restrained reciprocal space refinement have resulted in a model containing 94.4% of the theoretical atoms of the protein-inhibitor complex with an R-factor of 0.231. The fit of the model to the density is excellent, except for occasional side-chains and two sections of the regulatory chains that may be disordered. The electron density for the PALA molecule is readily identifiable for both catalytic (c) chains of the asymmetric unit and bonding interactions with several important residues including Ser52, Arg54, Thr55, Ser80, Lys84, Arg105, His134, Arg165, Arg229 and Gln231 are apparent. The carboxylate groups of the PALA molecule are in a nearly cis conformation. Gross quaternary changes between the T and R forms are noted and in agreement with earlier work from this laboratory. Namely, in the new structure the catalytic trimers move apart by 12 A along the 3-fold axis of the enzyme and relocate by 10 degrees relative to each other, adopting a more eclipsed position. The regulatory (r) chains in the new structure reorient about their 2-fold axis by 15 degrees. Large tertiary changes that include domain migration and rearrangement are also present between these two forms. In the R form both domains of the catalytic chain relocate closer to each other in order to bind to the inhibitor. The polar domain seems to bind primarily to the carbamoyl phosphate moiety of PALA, and the equatorial domain binds primarily to the L-aspartate moiety. Other changes in tertiary structure bring the 80s loop (from an adjacent catalytic chain) and the 240s loop into a position to interact with the PALA molecule. Changes have been searched for in all interface regions of the enzyme. While the C1-C4 and C1-R4 regions have been completely altered, most of the other interchain interfaces are similar in the T and R forms. The intrachain interfaces, between domains of the same catalytic chains, have undergone some reorganization as these domains move closer to each other when the inhibitor is bound. This new structure allows a reinterpretation of genetic and chemical modification studies done to date.(ABSTRACT TRUNCATED AT 400 WORDS)

Quantitative characterization of the interface roughness of (GaIn)As quantum wells by high resolution STEM.

The physical properties of semiconductor quantum wells (QW), like (GaIn)As/GaAs, are significantly influenced by the interface morphology. In the present work, high angle annular dark field imaging in (scanning) transmission electron microscopy ((S)TEM), in combination with contrast simulation, is used to address this question at atomic resolution. The (GaIn)As QWs were grown with metal organic vapor phase epitaxy on GaAs (001) substrates under different, precisely controlled conditions. In order to be able to compare different samples, a carefully applied method to gain reliable results from high resolution STEM micrographs was used. The thickness gradient of the TEM samples, caused by sample preparation, was compensated by the intensity of group V atomic columns, where no alloying takes place. After that, the In concentration map was plotted for the investigated regions based on the intensity of the group III atomic columns. The composition maps show that the Indium distribution across the quantum well is not homogeneous. The growth temperature of the QW can greatly influence the composition fluctuation and the interface morphology, with higher growth temperature resulting in larger composition fluctuations in the QWs and slightly wider interfaces, i.e. larger In-segregation. Growth interruptions are shown to significantly homogenize the elemental depth profile especially along the (GaIn)As/GaAs interface and hence have a positive effect on interface smoothness.

A test case for structure-based functional assignment: the 1.2 A crystal structure of the yjgF gene product from Escherichia coli.

The YER057c/YIL051c/YjgF protein family is a set of 24 full-length homologs, each approximately 130 residues in length, and each with no known function or relationship to proteins of known structure. To determine the function of this family, the structure of one member--the YjgF protein from Escherichia coli--was solved and refined at a resolution of 1.2 A. The YjgF molecule is a homotrimer with exact threefold symmetry. Its tertiary and quaternary structures are related to that of Bacillus subtilis chorismate mutase, although their active sites are completely different. The YjgF protein has an active site curiously similar to protein tyrosine phosphatases, including a covalently modified cysteine, but it is unlikely to be functionally related. The lessons learned from this attempt to deduce function from structure may be useful to future projects in structural genomics.

Crystal structure of viral serpin crmA provides insights into its mechanism of cysteine proteinase inhibition.

CrmA is an unusual viral serpin that inhibits both cysteine and serine proteinases involved in the regulation of host inflammatory and apoptosis processes. It differs from other members of the serpin superfamily by having a reactive center loop that is one residue shorter, and by its apparent inability to form SDS-stable covalent complexes with cysteine proteinases. To obtain insight into the inhibitory mechanism of crmA, we determined the crystal structure of reactive center loop-cleaved crmA to 2.9 A resolution. The structure, which is the first of a viral serpin, suggests that crmA can inhibit cysteine proteinases by a mechanism analogous to that used by other serpins against serine proteinases. However, one striking difference from other serpins, which may be significant for in vivo function, is an additional highly charged antiparallel strand for b sheet A, whose sequence and length are unique to crmA.