G. Hesser

Infrared Emitting and Photoconducting Colloidal Silver Chalcogenide Nanocrystal Quantum Dots from a Silylamide-Promoted Synthesis

Here, we present a hot injection synthesis of colloidal Ag chalcogenide nanocrystals (Ag(2)Se, Ag(2)Te, and Ag(2)S) that resulted in exceptionally small nanocrystal sizes in the range between 2 and 4 nm. Ag chalcogenide nanocrystals exhibit band gap energies within the near-infrared spectral region, making these materials promising as environmentally benign alternatives to established infrared active nanocrystals containing toxic metals such as Hg, Cd, and Pb. We present Ag(2)Se nanocrystals in detail, giving size-tunable luminescence with quantum yields above 1.7%. The luminescence, with a decay time on the order of 130 ns, was shown to improve due to the growth of a monolayer thick ZnSe shell. Photoconductivity with a quantum efficiency of 27% was achieved by blending the Ag(2)Se nanocrystals with a soluble fullerene derivative. The co-injection of lithium silylamide was found to be crucial to the synthesis of Ag chalcogenide nanocrystals, which drastically increased their nucleation rate even at relatively low growth temperatures. Because the same observation was made for the nucleation of Cd chalcogenide nanocrystals, we conclude that the addition of lithium silylamide might generally promote wet-chemical synthesis of metal chalcogenide nanocrystals, including in as-yet unexplored materials.

Mechanisms for room temperature direct wafer bonding

Reducing the temperature needed for high strength bonding which was and is driven by the need to reduce effects of coefficient of thermal expansion mismatch, reduce thermal budgets, and increase throughput has led to the development of plasma treatment procedures capable of bonding Si wafers below 300 °C with a bond strength equivalent to Si bulk. Despite being widely used, the physical and chemical mechanisms enabling low temperature wafer bonding have remained poorly understood. We developed an understanding of the beneficial surface modifications by plasma and a model based on short range low temperature diffusion through bonding experiments combined with results from spectroscopic ellipsometry, depth resolving Auger electron spectroscopy, and transmission electron microscopy measurements. We also present experimental results showing that even at room temperature reasonable bond strength can be achieved. We conclude that the gap closing mechanism is therefore a process which balances the lowering of the total energy by minimizing the sum of the free surface energy (maximizing the contact area between the surfaces) and strain energy in the oxide at the bond interface.

Size control and midinfrared emission of epitaxial PbTe∕CdTe quantum dot precipitates grown by molecular beam epitaxy

Epitaxial quantum dots with symmetric and highly facetted shapes are fabricated by thermal annealing of two-dimensional (2D) PbTe epilayers embedded in a CdTe matrix. By varying the thickness of the initial 2D layers, the dot size can be effectively controlled between 5 and 25nm, and areal densities as high as 3×1011cm−2 can be achieved. The size control allows the tuning of the quantum dot luminescence over a wide spectral range between 2.2 and 3.7μm. As a result, ultrabroadband emission from a multilayered quantum dot stack is demonstrated, which is a precondition for the development of superluminescent diodes operating in the near infrared and midinfrared.

Stranski-Krastanow growth of tensile strained Si islands on Ge (001)

Stranski-Krastanow island growth is demonstrated for tensile strained silicon epilayers on Ge (001) substrates over a wide range of growth temperatures. Small, Si-rich islands show sidewall faces near {1,1,10}, whereas larger islands are {113}-terminated truncated pyramids with an aspect ratio near 0.1. In contrast to compressively strained Ge on Si, we find for Si on Ge a significantly thicker wetting layer of >8 ML and coexistence of islands and dislocations.

An orphan dermaseptin from frog skin reversibly assembles to amyloid‐like aggregates in a pH‐dependent fashion

Dermaseptin PD‐3‐7 (aDrs) from frog skin contains three aspartic acid residues resulting in a negative net charge at neutral pH, as opposed to numerous other dermaseptins which are cationic helical antimicrobial peptides. Still, this peptide can be fitted into an amphipathic α helix by an Edmundson wheel projection. However, folding to the proposed helix was induced to only a low extent by zwitterionic vesicles or even detergents. Furthermore, no evidence of antibacterial or cytotoxic activity from soluble aDrs could be obtained. The peptide has an inherent propensity to an extended conformation in aqueous solution and self‐assembles into amyloid fibrils in a reversible pH‐controlled fashion, which was studied in some detail; above pH 5, the amyloid fibrils disassemble in a cooperative manner. This is probably caused by deprotonation of both side chain and terminal carboxyl groups, which results in intermolecular electrostatic repulsion. At neutral pH, this process proceeds instantaneously to the soluble form. Within the transition interval (pH 5–6.5), however, ‘backward’ granular aggregates, 10–500 nm in size, are formed. Such metastable amorphous aggregates, which are quickly released from an amyloid depot by a shift in pH, can mediate a strong cytotoxic effect. This activity does not involve lysis or interference with the cellular redox status, but apparently acts via an as yet unidentified mechanism. In this study, we present a new member of an emerging class of self‐assembling frog skin peptides with extraordinary self‐aggregation properties, which may potentially be relevant for biological processes.

Hydroxyapatite nanoparticles as novel low-refractive index additives for the long-term UV-photoprotection of transparent composite materials

Hydroxyapatite (HA) nanoparticles are introduced as a novel type of low-refractive-index additives for the formation of transparent polymer powder coatings. The beneficial effects of nano-HA for the long-term UV-photoprotection of polyester composite materials under accelerated weathering conditions are demonstrated in this work. These results are of considerable interest for the development of new hybrid organic–inorganic systems to be used as coating materials for outdoor applications such as transparent UV-resistant protection layers stabilized with functional nanoparticles based on cheap and biocompatible compounds.

Quantum dots with coherent interfaces between rocksalt-PbTe and zincblende-CdTea)

The formation of PbTe quantum dots (QDs) in a crystalline CdTe host matrix is demonstrated by the annealing of a coherent, heteroepitaxial PbTe layer clad between CdTe layers. The resulting QDs have a centrosymmetric shape and they exhibit intense room-temperature mid-infrared photoluminescence due to an electron-hole pair recombination in the narrow-gap PbTe. The intense luminescence approves the high quality of the QD interfaces, between the sixfold coordinated rocksalt structure of PbTe and the fourfold coordinated zincblende structure of CdTe. To gain further insight into the structural interface properties, we compare quantitatively multislice simulations of HRTEM images with first-principles total-energy calculations in the repeated-slab approximation. The most drastic effect occurs at the electrostatically neutral (110) interface, where we find a lateral spatial offset between the two crystal halves due to rebonding across the interface. For the two polar (001) interfaces, significantly different l...

Para-sexiphenyl-CdSe/ZnS nanocrystal hybrid light emitting diodes

CdSe/ZnS core/shell nanocrystals (NCs) are integrated into para-sexiphenyl (p-6P) based hybrid light emitting diodes, to obtain green and red emission in addition to blue emission originated from p-6P. For the active region of the devices, ultrathin layers of p-6P and NCs are deposited by hot wall epitaxy and spin casting, respectively, resulting in current-voltage characteristics with small leakage currents and low onset voltages. The achieved electroluminescence exhibits narrow emission line widths and thus high color purity, as required for color display applications.

Confining metal-halide perovskites in nanoporous thin films

In situ perovskite nanocrystal formation within nanoporous thin films allows emission color tuning in optoelectronic devices. Controlling the size and shape of semiconducting nanocrystals advances nanoelectronics and photonics. Quantum-confined, inexpensive, solution-derived metal halide perovskites offer narrowband, color-pure emitters as integral parts of next-generation displays and optoelectronic devices. We use nanoporous silicon and alumina thin films as templates for the growth of perovskite nanocrystallites directly within device-relevant architectures without the use of colloidal stabilization. We find significantly blue-shifted photoluminescence emission by reducing the pore size; normally infrared-emitting materials become visibly red, and green-emitting materials become cyan and blue. Confining perovskite nanocrystals within porous oxide thin films drastically increases photoluminescence stability because the templates auspiciously serve as encapsulation. We quantify the template-induced size of the perovskite crystals in nanoporous silicon with microfocus high-energy x-ray depth profiling in transmission geometry, verifying the growth of perovskite nanocrystals throughout the entire thickness of the nanoporous films. Low-voltage electroluminescent diodes with narrow, blue-shifted emission fabricated from nanocrystalline perovskites grown in embedded nanoporous alumina thin films substantiate our general concept for next-generation photonic devices.

Alternately deposited heterostructures of α-sexithiophene–para-hexaphenyl on muscovite mica(001) surfaces: crystallographic structure and morphology

Multi-component systems of para-hexaphenyl (p-6P) and α-sexithiophene (α-6T) molecules show great promise for tuning the fluorescence colour of optically active films. As the opto-electronic properties of rod-like molecules in thin films strongly rely on their anisotropic orientation, a technique for preparation of well-defined, anisotropic multicomponent systems is required. We demonstrate that a p-6P film of less than two nanometer thickness grown on muscovite mica(001) substrates acts as an efficient alignment layer for epitaxial growth of α-6T crystallites. On top of such a p-6P alignment layer, multilayer heterostructures of alternately deposited p-6P and α-6T molecules were grown. Combined X-ray diffraction and transmission electron microscopy studies show that molecules forming α-6T crystallites align parallel to those in the p-6P crystallites leading to the perfect adoption of their herring-bone structures. This alignment is desirable for optical applications and we show that it is preserved for heterostructures composed of up to 120 alternately deposited p-6P (0.8 nm) and α-6T (3.4 nm) nominal layers (120 cycles). Although for co-evaporated α-6T–p-6P molecules formation of a mixed crystal polymorph is reported, we show that in periodically deposited α-6T–p-6P heterostructures phase separation occurs and both molecules crystallize in their well-known equilibrium structures.