Nadezda V. Tarakina

Atomic-scale confinement of resonant optical fields.

In the presence of matter, there is no fundamental limit preventing confinement of visible light even down to atomic scales. Achieving such confinement and the corresponding resonant intensity enhancement inevitably requires simultaneous control over atomic-scale details of material structures and over the optical modes that such structures support. By means of self-assembly we have obtained side-by-side aligned gold nanorod dimers with robust atomically defined gaps reaching below 0.5 nm. The existence of atomically confined light fields in these gaps is demonstrated by observing extreme Coulomb splitting of corresponding symmetric and antisymmetric dimer eigenmodes of more than 800 meV in white-light scattering experiments. Our results open new perspectives for atomically resolved spectroscopic imaging, deeply nonlinear optics, ultrasensing, cavity optomechanics, as well as for the realization of novel quantum-optical devices.

Molecular beam epitaxy of high structural quality Bi2Se3 on lattice matched InP(111) substrates

Epitaxial layers of the topological insulator Bi2Se3 have been grown by molecular beam epitaxy on laterally lattice-matched InP(111)B substrates. High resolution X-ray diffraction shows a significant improvement of Bi2Se3 crystal quality compared to layers deposited on other substrates. The measured full width at half maximum of the rocking curve is Δω=13 arc sec, and the (ω−2θ) scans exhibit clear layer thickness fringes. Atomic force microscope images show triangular twin domains with sizes increasing with layer thickness. The structural quality of the domains is confirmed on the microscopic level by transmission electron microscopy.

High energy density in silver niobate ceramics

Solid-state dielectric energy storage is the most attractive and feasible way to store and release high power energy compared to chemical batteries and electrochemical super-capacitors. However, the low energy density (ca. 1 J cm−3) of commercial dielectric capacitors has limited their development. Dielectric materials showing field induced reversible phase transitions have great potential to break the energy storage density bottleneck. In this work, dense AgNbO3 ceramic samples were prepared successfully using solid state methods. Ferroelectric measurements at different temperatures reveal evidence of two kinds of polar regions. One of these is stable up to 70 °C, while the other remains stable up to 170 °C. The associated transition temperatures are supported by second harmonic generation measurements on poled samples and are correlated with the occurrence of two sharp dielectric responses. The average unit cell volume is seen to increase with increasing DC field and has been interpreted in terms of increasing levels of structural disorder in the system. At a high electric field the structure becomes ferroelectric with high polarization. This field induced transition exhibits a recoverable energy density of 2.1 J cm−3, which represents one of the highest known values for lead-free bulk ceramics.

Intracellularly Biodegradable Polyelectrolyte/Silica Composite Microcapsules as Carriers for Small Molecules.

Microcapsules that can be efficiently loaded with small molecules and effectively released at the target area through the degradation of the capsule shells hold great potential for treating diseases. Traditional biodegradable polyelectrolyte (PE) capsules can be degraded by cells and eliminated from the body but fail to encapsulate drugs with small molecular weight. Here, we report a poly-l-arginine hydrochloride (PARG)/dextran sulfate sodium salt (DEXS)/silica (SiO2) composite capsule that can be destructed in cells and of which the in situ formed inorganic SiO2 enables loading of small model molecules, Rhodamine B (Rh-B). The composite capsules were fabricated based on the layer-by-layer (LbL) technique and the hydrolysis of tetraethoxysilane (TEOS). Capsules composed of nondegradable PEs and SiO2, polyllamine hydrochloride (PAH)/poly(sodium 4-styrenesulfonate) (PSS)/silica (the control sample), were prepared and briefly compared with the degradable composite capsules. An intracellular degradation study of both types of composite capsules revealed that PARG/DEXS/silica capsules were degraded into fragments and lead to the release of model molecules in a relatively short time (2 h), while the structure of PAH/PSS/silica capsules remained intact even after 3 days incubation with B50 cells. Such results indicated that the polymer components played a significant role in the degradability of the SiO2. Specifically, PAH/PSS scaffolds blocked the degradation of SiO2. For PARG/DEXS/silica capsules, we proposed the effects of both hydrolytic degradation of amorphous silica and enzymatic degradation of PARG/DEXS polymers as a cell degradation mechanism. All the results demonstrated a new type of functional composite microcapsule with low permeability, good biocompatibility, and biodegradability for potential medical applications.

Room-temperature near-infrared silicon carbide nanocrystalline emitters based on optically aligned spin defects

Bulk silicon carbide (SiC) is a very promising material system for bio-applications and quantum sensing. However, its optical activity lies beyond the near infrared spectral window for in-vivo imaging and fiber communications due to a large forbidden energy gap. Here, we report the fabrication of SiC nanocrystals and isolation of different nanocrystal fractions ranged from 600 nm down to 60 nm in size. The structural analysis reveals further fragmentation of the smallest nanocrystals into ca. 10-nm-size clusters of high crystalline quality, separated by amorphization areas. We use neutron irradiation to create silicon vacancies, demonstrating near infrared photoluminescence. Finally, we detect, for the first time, room-temperature spin resonances of these silicon vacancies hosted in SiC nanocrystals. This opens intriguing perspectives to use them not only as in-vivo luminescent markers, but also as magnetic field and temperature sensors, allowing for monitoring various physical, chemical and biological processes.

Bifunctional ultraviolet/ultrasound responsive composite TiO2/polyelectrolyte microcapsules

Designing and fabricating multifunctional microcapsules are of considerable interest in both academic and industrial research aspects. This work reports an innovative approach to fabricate composite capsules with high UV and ultrasound responsive functionalities that can be used as external triggers for controlled release, yet with enhanced mechanical strength that can make them survive in a harsh environment. Needle-like TiO2 nanoparticles (NPs) were produced in situ into layer-by-layer (LbL) polyelectrolyte (PE) shells through the hydrolysis of titanium butoxide (TIBO). These rigid TiO2 NPs yielded the formed capsules with excellent mechanical strength, showing a free standing structure. A possible mechanism is proposed for the special morphology formation of the TiO2 NPs and their reinforcing effects. Synergistically, their response to UV and ultrasound was visualized via SEM, with the results showing an irreversible shell rapture upon exposure to either UV or ultrasound irradiation. As expected, the release studies revealed that the dextran release from the TiO2/PE capsules was both UV-dependent and ultrasound-dependent. Besides, the biocompatibility of the capsules with the incorporation of amorphous TiO2 NPs was confirmed by an MTT assay experiment. All these pieces of evidence suggested a considerable potential medicinal application of TiO2/PE capsules for controlled drug delivery.

AlGaInAs quantum dot solar cells: tailoring quantum dots for intermediate band formation

We report on the realization of quantum dot (QD) solar cells comprising a spectrally large absorption range. The QD absorption band is designed by integrating quaternary AlGaInAs QDs with varying aluminum contents in combination with conventional InAs/GaAs QDs in the intrinsic region of an AlGaAs p-i-n structure. By adjusting the material composition in the different QD layers, we can cover a spectral range from 680 to 1150 nm by QD absorption. Based on our results we discuss a newly proposed solar cell design employable to facilitate intermediate band absorption for an increased efficiency.

Enhanced Photocatalytic Activity of Heterostructured Ferroelectric BaTiO3/α-Fe2O3 and the Significance of Interface Morphology Control.

We have used a ferroelectric BaTiO3 substrate with a hematite (α-Fe2O3) nanostructured surface to form a heterogeneous BaTiO3/α-Fe2O3 photocatalyst. In this study we show that varying the mass ratio of α-Fe2O3 on BaTiO3 has a significant influence on photoinduced decolorization of rhodamine B under simulated sunlight. The highest photocatalytic activity was obtained for BaTiO3-Fe2O3-0.001M, with the lowest mass ratio of α-Fe2O3 in our study. This catalyst exhibited a 2-fold increase in performance compared to pure BaTiO3 and a 5-fold increase when compared to the higher-surface-area pure α-Fe2O3. The increases in performance become more marked upon scaling for the lower surface area of the heterostructured catalyst. Performance enhancement is associated with improved charge-carrier separation at the interface between the ferroelectric surface, which exhibits ferroelectric polarization, and the hematite. Increasing the mass ratio of hematite increases the thickness of this layer, lowers the number of triple-point locations, and results in reduced performance enhancement. We show that the reduced performance is due to a lack of light penetrating into BaTiO3 and to relationships between the depolarization field from the ferroelectric and carriers in the hematite. Our findings demonstrate that it is possible to use the built-in electric field of a ferroelectric material to promote charge-carrier separation and boost photocatalytic efficiency.

Gamma radiation induces hydrogen absorption by copper in water

One of the most intricate issues of nuclear power is the long-term safety of repositories for radioactive waste. These repositories can have an impact on future generations for a period of time orders of magnitude longer than any known civilization. Several countries have considered copper as an outer corrosion barrier for canisters containing spent nuclear fuel. Among the many processes that must be considered in the safety assessments, radiation induced processes constitute a key-component. Here we show that copper metal immersed in water uptakes considerable amounts of hydrogen when exposed to γ-radiation. Additionally we show that the amount of hydrogen absorbed by copper depends on the total dose of radiation. At a dose of 69 kGy the uptake of hydrogen by metallic copper is 7 orders of magnitude higher than when the absorption is driven by H2(g) at a pressure of 1 atm in a non-irradiated dry system. Moreover, irradiation of copper in water causes corrosion of the metal and the formation of a variety of surface cavities, nanoparticle deposits, and islands of needle-shaped crystals. Hence, radiation enhanced uptake of hydrogen by spent nuclear fuel encapsulating materials should be taken into account in the safety assessments of nuclear waste repositories.

Defect Crystal Structure of Low Temperature Modifications of Li2MO3 (M=Ti, Sn) and Related Hydroxides

Crystal structures of Li2MO3 (M=Sn, Ti) and TiO(OH)2 have been studied in detail and refined using X-ray powder diffraction data. All compounds posses a high concentration of defects in the structure. The crystal structures of the Li2MO3 salts obtained at 700°C reveal stacking faults of LiM2 metal layers, which leads to the appearance of short-range order in three possible space groups: C2/c, C2/m, P3112. The possibility to stabilize this imperfect state increases the mobility of the Li+ ions in the Li2TiO3 structure and allows the complete exchange of lithium by hydrogen in acid water solutions with formation of TiO(OH)2. The crystal structure of TiO(OH)2 belongs to the layered double hydroxide structure type with the 3R1 sequence of oxygen layers and can be described as a stacking of charge-neutral metal oxyhydroxide slabs [(OH)2OTi2O(OH)2].