Enhanced Photoconductivity at Dislocations in SrTiO3.

Dislocations are 1D crystallographic line defects and are usually seen as detrimental to the functional properties of classic semiconductors. It is shown here that this not necessarily accounts for oxide semiconductors in which dislocations are capable of boosting the photoconductivity. Strontium titanate single crystals are controllably deformed to generate a high density of ordered dislocations of two slip systems possessing different mesoscopic arrangements. For both slip systems, nanoscale conductive atomic force microscope investigations reveal a strong enhancement of the photoconductivity around the dislocation cores. Macroscopic in-plane measurements indicate that the two dislocation systems result in different global photoconductivity behavior despite the similar local enhancement. Depending on the arrangement, the global photoresponse can be increased by orders of magnitude. Additionally, indications for a bulk photovoltaic effect enabled by dislocation-surrounding strain fields are observed for the first time. This proves that dislocations in oxide semiconductors can be of large interest for tailoring photoelectric functionalities. Direct evidence that electronic transport is confined to the dislocation core points to a new emerging research field.

Dislocation-toughened ceramics.

Functional and structural ceramics have become irreplaceable in countless high-tech applications. However, their inherent brittleness tremendously limits the application range and, despite extensive research efforts, particularly short cracks are hard to combat. While local plasticity carried by mobile dislocations allows desirable toughness in metals, high bond strength is widely believed to hinder dislocation-based toughening of ceramics. Here, we demonstrate the possibility to induce and engineer a dislocation microstructure in ceramics that improves the crack tip toughness even though such toughening does not occur naturally after conventional processing. With modern microscopy and simulation techniques, we reveal key ingredients for successful engineering of dislocation-based toughness at ambient temperature. For many ceramics a dislocation-based plastic zone is not impossible due to some intrinsic property (e.g. bond strength) but limited by an engineerable quantity, i.e. the dislocation density. The impact of dislocation density is demonstrated in a surface near region and suggested to be transferrable to bulk ceramics. Unexpected potential in improving mechanical performance of ceramics could be realized with novel synthesis strategies.

Photoindentation: A New Route to Understanding Dislocation Behavior in Light.

It was recently found that extremely large plasticity is exhibited in bulk compression of single-crystal ZnS in complete darkness. Such effects are believed to be caused by the interactions between dislocations and photoexcited electrons and/or holes. However, methods for evaluating dislocation behavior in such semiconductors with small dimensions under a particular light condition had not been well established. Here, we propose the "photoindentation" technique to solve this issue by combining nanoscale indentation tests with a fully controlled lighting system. The quantitative data analyses based on this photoindentation approach successfully demonstrate that the first pop-in stress indicating dislocation nucleation near the surface of ZnS clearly increases by light irradiation. Additionally, the room-temperature indentation creep tests show a drastic reduction of the dislocation mobility under light. Our approach demonstrates great potential in understanding the light effects on dislocation nucleation and mobility at the nanoscale, as most advanced technology-related semiconductors are limited in dimensions.

Conceptual Framework for Dislocation-Modified Conductivity in Oxide Ceramics Deconvoluting Mesoscopic Structure, Core, and Space Charge Exemplified for SrTiO3.

The introduction of dislocations is a recently proposed strategy to tailor the functional and especially the electrical properties of ceramics. While several works confirm a clear impact of dislocations on electrical conductivity, some studies raise concern in particular when expanding to dislocation arrangements beyond a geometrically tractable bicrystal interface. Moreover, the lack of a complete classification on pertinent dislocation characteristics complicates a systematic discussion and hampers the design of dislocation-modified electrical conductivity. We proceed by mechanically introducing dislocations with three different mesoscopic structures into the model material single-crystal SrTiO3 and extensively characterizing them from both a mechanical as well as an electrical perspective. As a final result, a deconvolution of mesoscopic structure, core structure, and space charge enables us to obtain the complete picture of the effect of dislocations on functional properties, focusing here on electric properties.

Extraordinary plasticity of an inorganic semiconductor in darkness.

Inorganic semiconductors generally tend to fail in a brittle manner. Here, we report that extraordinary "plasticity" can take place in an inorganic semiconductor if the deformation is carried out "in complete darkness." Room-temperature deformation tests of zinc sulfide (ZnS) were performed under varying light conditions. ZnS crystals immediately fractured when they deformed under light irradiation. In contrast, it was found that ZnS crystals can be plastically deformed up to a deformation strain of εt = 45% in complete darkness. In addition, the optical bandgap of the deformed ZnS crystals was distinctly decreased after deformation. These results suggest that dislocations in ZnS become mobile in complete darkness and that multiplied dislocations can affect the optical bandgap over the whole crystal. Inorganic semiconductors are not necessarily intrinsically brittle.

Direct Observation of Impurity Segregation at Dislocation Cores in an Ionic Crystal.

Dislocations, one-dimensional lattice defects, are known to strongly interact with impurity atoms in a crystal. This interaction is generally explained on the basis of the long-range strain field of the dislocation. In ionic crystals, the impurity-dislocation interactions must be influenced by the electrostatic effect in addition to the strain effect. However, such interactions have not been verified yet. Here, we show a direct evidence of the electrostatic impurity-dislocation interaction in α-Al2O3 by visualizing the dopant atom distributions at dislocation cores using atomic-resolution scanning transmission electron microscopy (STEM). It was found that the dopant segregation behaviors strongly depend on the kind of elements, and their valence states are considered to be a critical factor. The observed segregation behaviors cannot be explained by the elastic interactions only, but can be successfully understood if the electrostatic interactions are taken into account. The present findings will lead to the precise and quantitative understanding of impurity induced dislocation properties in many materials and devices.

Adsorption sites of single noble metal atoms on the rutile TiO2 (1 1 0) surface influenced by different surface oxygen vacancies.

Atomic adsorption of Au and Pt on the rutile (1 1 0) surface was investigated by atomic-resolution aberration-corrected scanning transmission electron microscopy (STEM) measurements combined with density functional theory calculations. Au single atoms were deposited on the surface in a vacuum condition, and the observed results were compared with Pt single atoms on the same surface prepared by the same experimental manner. It was found that Au single atoms are stably adsorbed only at the bridging oxygen vacancy sites, which is quite different from Pt single atoms exhibiting the most frequently observed adsorption at the basal oxygen vacancy sites. Such a difference in oxygen-vacancy effect between Au and Pt can be explained by electronic structures of the surface vacancies as well as characters of outermost atomic orbitals of Au and Pt.

Strong correlation in 1D oxygen-ion conduction of apatite-type lanthanum silicate.

Oxygen-ion conduction in apatite-type lanthanum silicate, La9.33+0.67x (SiO4)6O2+x (x = 1), has theoretically been analyzed in a first-principles manner followed by the nudged elastic band method and the kinetic Monte Carlo method. Unlike the conventional cooperative interstitialcy mechanism along the single O4 columns, diffusing interstitial oxygen ions are frequently blocked by adjacent interstitial oxygen ions (Oint ions), leading to the strongly-correlated diffusivity and conductivity of oxygen ions in the case of chemical compositions with large x values. The getting-out mechanism from the O4 column is of importance in the long-range conduction, which temporarily transfers a part of Oint ions out of the columns to relax the blocking effect. The getting-out mechanism plays a key role also in the conduction perpendicular to the c axis (in the ab plane).

First-principles calculations of divalent substitution of Ca(2+) in tricalcium phosphates.

First-principles calculations were carried out to reveal local atomic arrangements and thermodynamic stability of substitutional divalent cations of Mg(2+), Zn(2+), Sr(2+) and Ba(2+) in tricalcium phosphates (TCPs). There are two modifications of α-TCP and ß-TCP, and a number of inequivalent Ca sites are present in the crystal structures. It was found that each divalent cation has energetically preferential Ca sites for substitution. For instance, Mg(2+) and Zn(2+) favor the substitution at the Ca-5 site of ß-TCP while Sr(2+) and Ba(2+) tend to occupy Ca-3 and Ca-4 in the ß-type crystal structure. The calculated site preference of these cations was in reasonable agreement with available experimental data. Moreover, it was found that these cations have negative formation energies at specific Ca sites especially in ß-TCP, indicating the stabilization of the ß phase.

The effect of chemical potential on the thermodynamic stability of carbonate ions in hydroxyapatite.

First-principles calculations were performed for CO3(2-) ions in hydroxyapatite in order to investigate the atomic structures and thermodynamic stability of CO3(2-) and its related defects. Two different chemical equilibrium conditions in high-temperature and aqueous-solution environments were considered, and atomic and ionic chemical potentials for the individual chemical equilibrium conditions were evaluated to calculate defect formation energies. It was found that A-type CO3(2-) (substituting OH(-)) is energetically more favorable than B-type CO3(2-) (substituting PO4(3-)) in the high-temperature environment, whereas B-type is preferred to A-type in the aqueous solution environment. This result successfully reproduces experimentally observed trends. In the formation of A-type and B-type CO3(2-), OH(-) vacancies or protons (interstitial or substitutional) act as charge-compensating defects.

Periodic nanowire array at the crystal interface.

A dislocation in a crystalline material has dangling bonds at its core and a strong strain field in its vicinity. Consequently, the dislocation attracts solute atoms and forms a so-called Cottrell atmosphere along the dislocation. A crystalline dislocation can be used as a template to produce nanowires by selectively doping foreign atoms along the dislocation. However, control of the configuration, spacing, and density of the formed periodic nanowire array has heretofore been extremely difficult. Here we show a method for fabricating ordered, electrically conductive nanowire arrays using periodic dislocations at crystal interfaces. As a demonstration, we fabricated arrays of titanium nanowires arranged at intervals of either 13 or 90 nm and then confirmed by scanning probe microscopy that they exhibit electrical conductivity inside an insulating aluminum oxide. Significantly, we were able to precisely control nanowire periodicity by the choice of crystal orientation and/or crystal planes at the crystal interface. This simple method for the fabrication of periodic nanowire arrays of highly controlled density should be widely applicable to electrical, magnetic, and optical devices.

Conducting nanowires in insulating ceramics.

Low-dimensional structures, such as microclusters, quantum dots and one- or two-dimensional (1D or 2D) quantum wires, are of scientific and technological interest due to their unusual physical properties, which are quite different from those in the bulk. Here we present a successful method for fabricating conducting nanowire bundles inside an insulating ceramic single crystal by using unidirectional dislocations. A high density of dislocations (10(9) cm(-2)) was introduced by activating a primary slip system in sapphire (alpha-Al2O3 single crystal) using a two-stage deformation technique. Plate specimens cut out from the deformed sapphire were then annealed to straighten the dislocations. Finally, the plates on which metallic Ti was evaporated were heat-treated to diffuse Ti atoms inside sapphire. As a result of this process, Ti atoms segregated along the unidirectional dislocations within about 5 nm diameter, forming unidirectional Ti-enriched nanowires, which exhibit excellent electrical conductivity. This simple technique could potentially to be applied to any crystal, and may give special properties to commonly used materials.