Liverios Lymperakis

Revealing the Design Principles of High‐Performance Biological Composites Using Ab initio and Multiscale Simulations: The Example of Lobster Cuticle

In the course of evolution nature developed materials based on organic–inorganic nanocomposites with complex, hierarchical organization from A u ngstroms to millimeters tailored via molecular self-assembly. [1–3] Such materials possess outstanding stiffness, toughness, and strength related to their low density, while the mechanical characteristics of their underlying constituents are rather modest. [2,4] This remarkable performance is a consequence of their hierarchical structure, the specific design at each level of organization, and the inherent strong heterogeneity [4] resulting in the accommodation of macroscopic loadings bydifferentdeformationmechanisms at differentlength scales. Therefore, to understand the macroscopic mechanical properties of the tissue, one should take into account its structure–property relations at all length scales down to the molecular level. To date, this key challenge has been only partly addressed due to severe obstacles in obtaining mechanical and structural data at the nanometer scale. The mechanical properties of important proteins and biominerals as well as some details about their exact structure are still unknown. A powerful tool to overcome these difficulties and to better understand the structure–property relationships in biomaterials is multiscale modeling encompassing all length scales. [3,5] Some progress in the development of multiscale structure–property relationships for mineralized tissues has been achieved by combined modeling and experimental approaches applied to bone, [4] nacre, [6] and fish skin armor. [7] However, these approaches do not explicitly integrate a molecular-level description and use continuum mechanics at the meso- and macroscale (e.g., finite element analysis) coupled with experimental data obtained, for example, by nanoindentation. A

Gallium adsorption on (0001) GaN surfaces

We study the adsorption behavior of Ga on ~0001! GaN surfaces combining experimental specular reflection high-energy electron diffraction with theoretical investigations in the framework of a kinetic model for adsorption and ab initio calculations of energy parameters. Based on the experimental results we find that for substrate temperatures and Ga fluxes typically used in molecular-beam epitaxy of GaN, finiteequilibrium Ga surface coverages can be obtained. The measurement of a Ga/GaN adsorption isotherm allows the quantification of the equilibrium Ga surface coverage as a function of the impinging Ga flux. In particular, we show that a large range of Ga fluxes exists, where 2.5 60.2 monolayers ~in terms of the GaN surface site density! of Ga are adsorbed on the GaN surface. We further demonstrate that the structure of this adsorbed Ga film is in good agreement with the laterally contracted Ga bilayer model predicted to be most stable for strongly Ga-rich surfaces @Northrup et al., Phys. Rev. B 61, 9932 ~2000!#. For lower Ga fluxes, a discontinuous transition to Ga monolayer equilibrium coverage is found, followed by a continuous decrease towards zero coverage; for higher Ga fluxes, Ga droplet formation is found, similar to what has been observed during Ga-rich GaN growth. The boundary fluxes limiting the region of 2.5 monolayers equilibrium Ga adsorption have been measured as a function of the GaN substrate temperature giving rise to a Ga/GaN adsorption phase diagram. The temperature dependence is discussed within an ab initio based growth model for adsorption taking into account the nucleation of Ga clusters. This model consistently explains recent contradictory results of the activation energy describing the critical Ga flux for the onset of Ga droplet formation during Ga-rich GaN growth @Heying et al., J. Appl. Phys. 88, 1855 ~2000!; Adelmann et al., J. Appl. Phys. 91, 9638 ~2002!.#.

Robustness and optimal use of design principles of arthropod exoskeletons studied by ab initio-based multiscale simulations

Recently, we proposed a hierarchical model for the elastic properties of mineralized lobster cuticle using (i) ab initio calculations for the chitin properties and (ii) hierarchical homogenization performed in a bottom-up order through all length scales. It has been found that the cuticle possesses nearly extremal, excellent mechanical properties in terms of stiffness that strongly depend on the overall mineral content and the specific microstructure of the mineral-protein matrix. In this study, we investigated how the overall cuticle properties changed when there are significant variations in the properties of the constituents (chitin, amorphous calcium carbonate (ACC), proteins), and the volume fractions of key structural elements such as chitin-protein fibers. It was found that the cuticle performance is very robust with respect to variations in the elastic properties of chitin and fiber proteins at a lower hierarchy level. At higher structural levels, variations of design parameters such as the volume fraction of the chitin-protein fibers have a significant influence on the cuticle performance. Furthermore, we observed that among the possible variations in the cuticle ingredients and volume fractions, the experimental data reflect an optimal use of the structural variations regarding the best possible performance for a given composition due to the smart hierarchical organization of the cuticle design.

Morphology and surface reconstructions of GaN(1100) surfaces

GaN is grown by plasma-assisted molecular-beam epitaxy on ZnO(1100) substrates. Well-oriented (1100) GaN surfaces are obtained, and (1101) oriented facets are also observed. On the GaN(1100) surfaces under Ga-rich conditions, a surface reconstruction with approximate symmetry of “4×5” is found. A model is proposed in which this reconstruction consists of ⩾2 monolayers of Ga terminating the GaN surface.

Ab initio study of thermodynamic, structural, and elastic properties of Mg-substituted crystalline calcite.

Arthropoda, which represent nearly 80% of all known animal species, are protected by an exoskeleton formed by their cuticle. The cuticle represents a hierarchically structured multifunctional biocomposite based on chitin and proteins. Some groups, such as Crustacea, reinforce the load-bearing parts of their cuticle with calcite. As the calcite sometimes contains Mg it was speculated that Mg may have a stiffening impact on the mechanical properties of the cuticle (Becker et al., Dalton Trans. (2005) 1814). Motivated by these facts, we present a theoretical parameter-free quantum-mechanical study of the phase stability and structural and elastic properties of Mg-substituted calcite crystals. The Mg-substitutions were chosen as examples of states that occur in complex chemical environments typical for biological systems in which calcite crystals contain impurities, the role of which is still the topic of debate. Density functional theory calculations of bulk (Ca,Mg)CO₃ were performed employing 30-atom supercells within the generalized gradient approximation as implemented in the Vienna Ab-initio Simulation Package. Based on the calculated thermodynamic results, low concentrations of Mg atoms are predicted to be stable in calcite crystals in agreement with experimental findings. Examining the structural characteristics, Mg additions nearly linearly reduce the volume of substituted crystals. The predicted elastic bulk modulus results reveal that the Mg substitution nearly linearly stiffens the calcite crystals. Due to the quite large size-mismatch of Mg and Ca atoms, Mg substitution results in local distortions such as off-planar tilting of the CO₃²⁻ group.

Polarity in GaN and ZnO: Theory, measurement, growth, and devices

The polar nature of the wurtzite crystalline structure of GaN and ZnO results in the existence of a spontaneous electric polarization within these materials and their associated alloys (Ga,Al,In)N and (Zn,Mg,Cd)O. The polarity has also important consequences on the stability of the different crystallographic surfaces, and this becomes especially important when considering epitaxial growth. Furthermore, the internal polarization fields may adversely affect the properties of optoelectronic devices but is also used as a potential advantage for advanced electronic devices. In this article, polarity-related issues in GaN and ZnO are reviewed, going from theoretical considerations to electronic and optoelectronic devices, through thin film, and nanostructure growth. The necessary theoretical background is first introduced and the stability of the cation and anion polarity surfaces is discussed. For assessing the polarity, one has to make use of specific characterization methods, which are described in detail. Subsequently, the nucleation and growth mechanisms of thin films and nanostructures, including nanowires, are presented, reviewing the specific growth conditions that allow controlling the polarity of such objects. Eventually, the demonstrated and/or expected effects of polarity on the properties and performances of optoelectronic and electronic devices are reported. The present review is intended to yield an in-depth view of some of the hot topics related to polarity in GaN and ZnO, a fast growing subject over the last decade.

Hidden surface states at non-polar GaN (101¯0) facets: Intrinsic pinning of nanowires

We investigate the electronic structure of the GaN(101¯0) prototype surface for GaN nanowire sidewalls. We find a paradoxical situation that a surface state at all k points in the bandgap cannot be probed by conventional scanning tunneling microscopy, due to a dispersion characterized by a steep minimum with low density of states (DOS) and an extremely flat maximum with high DOS. Based on an analysis of the decay behavior into the vacuum, we identify experimentally the surface state minimum 0.6 ± 0.2 eV below the bulk conduction band in the gap. Hence, GaN nanowires with clean (101¯0) sidewall facets are intrinsically pinned.

Ab Initio Based conformational study of the crystalline α‐chitin

The equilibrium structure including the network of hydrogen bonds of an α-chitin crystal is determined combining density-functional theory (DFT), self-consistent DFT-based tight-binding (SCC-DFTB), and empirical forcefield molecular dynamics (MD) simulations. Based on the equilibrium geometry several possible crystal conformations (local energy minima) have been identified and related to hydrogen bond patterns. Our results provide new insight and allow to resolve the contradicting α-chitin structural models proposed by various experiments.

Band offsets at zincblende-wurtzite GaAs nanowire sidewall surfaces

The band structure and the Fermi level pinning at clean and well-ordered sidewall surfaces of zincblende (ZB)-wurtzite (WZ) GaAs nanowires are investigated by scanning tunneling spectroscopy and density functional theory calculations. The WZ-ZB phase transition in GaAs nanowires introduces p-i junctions at the sidewall surfaces. This is caused by the presence of numerous steps, which induce a Fermi level pinning at different energies on the non-polar WZ and ZB sidewall facets.

Effect of edge threading dislocations on the electronic structure of InN

The open issue of the n-type conductivity and its correlation to threading dislocations (TDs) in InN is addressed through first principles calculations on the electronic properties of a-edge TDs. All possible dislocation core models are considered (4-, 5/7-, and 8-atom cores) and are found to modify the band structure of InN in a distinct manner. In particular, nitrogen and indium low coordinated atoms in the eight-atom core induce states near the valence band maximum and above the conduction band minimum, respectively. The formation of a nitrogen–nitrogen “wrong” bond is observed at the 5/7-atom core resulting in a state inside the band gap. The 4- and 5/7-atom cores induce occupied states resonant in the conduction band due to In–In strain induced interactions and wrong bonds, respectively. These occupied states designate TDs as a source of higher electron concentrations in InN and provide direct evidence that TDs contribute to its inherent n-type conductivity.