Substitutional synthesis of sub-nanometer InGaN/GaN quantum wells with high indium content.

InGaN/GaN quantum wells (QWs) with sub-nanometer thickness can be employed in short-period superlattices for bandgap engineering of efficient optoelectronic devices, as well as for exploiting topological insulator behavior in III-nitride semiconductors. However, it had been argued that the highest indium content in such ultra-thin QWs is kinetically limited to a maximum of 33%, narrowing down the potential range of applications. Here, it is demonstrated that quasi two-dimensional (quasi-2D) QWs with thickness of one atomic monolayer can be deposited with indium contents far exceeding this limit, under certain growth conditions. Multi-QW heterostructures were grown by plasma-assisted molecular beam epitaxy, and their composition and strain were determined with monolayer-scale spatial resolution using quantitative scanning transmission electron microscopy in combination with atomistic calculations. Key findings such as the self-limited QW thickness and the non-monotonic dependence of the QW composition on the growth temperature under metal-rich growth conditions suggest the existence of a substitutional synthesis mechanism, involving the exchange between indium and gallium atoms at surface sites. The highest indium content in this work approached 50%, in agreement with photoluminescence measurements, surpassing by far the previously regarded compositional limit. The proposed synthesis mechanism can guide growth efforts towards binary InN/GaN quasi-2D QWs.

The heterogeneous nucleation of threading dislocations on partial dislocations in III-nitride epilayers.

III-nitride compound semiconductors are breakthrough materials regarding device applications. However, their heterostructures suffer from very high threading dislocation (TD) densities that impair several aspects of their performance. The physical mechanisms leading to TD nucleation in these materials are still not fully elucidated. An overlooked but apparently important mechanism is their heterogeneous nucleation on domains of basal stacking faults (BSFs). Based on experimental observations by transmission electron microscopy, we present a concise model of this phenomenon occurring in III-nitride alloy heterostructures. Such domains comprise overlapping intrinsic I1 BSFs with parallel translation vectors. Overlapping of two BSFs annihilates most of the local elastic strain of their delimiting partial dislocations. What remains combines to yield partial dislocations that are always of screw character. As a result, TD nucleation becomes geometrically necessary, as well as energetically favorable, due to the coexistence of crystallographically equivalent prismatic facets surrounding the BSF domain. The presented model explains all observed BSF domain morphologies, and constitutes a physical mechanism that provides insight regarding dislocation nucleation in wurtzite-structured alloy epilayers.

High-quality, large-area MoSe2 and MoSe2/Bi2Se3 heterostructures on AlN(0001)/Si(111) substrates by molecular beam epitaxy.

Atomically-thin, inherently 2D semiconductors offer thickness scaling of nanoelectronic devices and excellent response to light for low-power versatile applications. Using small exfoliated flakes, advanced devices and integrated circuits have already been realized, showing great potential to impact nanoelectronics. Here, high-quality single-crystal MoSe2 is grown by molecular beam epitaxy on AlN(0001)/Si(111), showing the potential for scaling up growth to low-cost, large-area substrates for mass production. The MoSe2 layers are epitaxially aligned with the aluminum nitride (AlN) lattice, showing a uniform, smooth surface and interfaces with no reaction or intermixing, and with sufficiently high band offsets. High-quality single-layer MoSe2 is obtained, with a direct gap evidenced by angle-resolved photoemission spectroscopy and further confirmed by Raman and intense room temperature photoluminescence. The successful growth of high-quality MoSe2/Bi2Se3 multilayers on AlN shows promise for novel devices exploiting the non-trivial topological properties of Bi2Se3.

Sub-surface laser nanostructuring in stratified metal/dielectric media: a versatile platform towards flexible, durable and large-scale plasmonic writing.

Laser nanostructuring of pure ultrathin metal layers or ceramic/metal composite thin films has emerged as a promising route for the fabrication of plasmonic patterns with applications in information storage, cryptography, and security tagging. However, the environmental sensitivity of pure Ag layers and the complexity of ceramic/metal composite film growth hinder the implementation of this technology to large-scale production, as well as its combination with flexible substrates. In the present work we investigate an alternative pathway, namely, starting from non-plasmonic multilayer metal/dielectric layers, whose growth is compatible with large scale production such as in-line sputtering and roll-to-roll deposition, which are then transformed into plasmonic templates by single-shot UV-laser annealing (LA). This entirely cold, large-scale process leads to a subsurface nanoconstruction involving plasmonic Ag nanoparticles (NPs) embedded in a hard and inert dielectric matrix on top of both rigid and flexible substrates. The subsurface encapsulation of Ag NPs provides durability and long-term stability, while the cold character of LA suits the use of sensitive flexible substrates. The morphology of the final composite film depends primarily on the nanocrystalline character of the dielectric host and its thermal conductivity. We demonstrate the emergence of a localized surface plasmon resonance, and its tunability depending on the applied fluence and environmental pressure. The results are well explained by theoretical photothermal modeling. Overall, our findings qualify the proposed process as an excellent candidate for versatile, large-scale optical encoding applications.

Incineration of tannery sludge under oxic and anoxic conditions: study of chromium speciation.

A tannery sludge, produced from physico-chemical treatment of tannery wastewaters, was incinerated without any pre-treatment process under oxic and anoxic conditions, by controlling the abundance of oxygen. Incineration in oxic conditions was performed at the temperature range from 300°C to 1200°C for duration of 2h, while in anoxic conditions at the temperature range from 400°C to 600°C and varying durations. Incineration under oxic conditions at 500°C resulted in almost total oxidation of Cr(III) to Cr(VI), with CaCrO4 to be the crystalline phase containing Cr(VI). At higher temperatures a part of Cr(VI) was reduced, mainly due to the formation of MgCr2O4. At 1200°C approximately 30% of Cr(VI) was reduced to Cr(III). Incineration under anoxic conditions substantially reduced the extent of oxidation of Cr(III) to Cr(VI). Increase of temperature and duration of incineration lead to increase of Cr(VI) content, while no chromium containing crystalline phase was detected.

Nanostructure and strain in InGaN/GaN superlattices grown in GaN nanowires.

The structural properties and the strain state of InGaN/GaN superlattices embedded in GaN nanowires were analyzed as a function of superlattice growth temperature, using complementary transmission electron microscopy techniques supplemented by optical analysis using photoluminescence and spatially resolved microphotoluminescence spectroscopy. A truncated pyramidal shape was observed for the 4 nm thick InGaN inclusions, where their (0001¯) central facet was delimited by six-fold {101¯l} facets towards the m-plane sidewalls of the nanowires. The defect content of the nanowires comprised multiple basal stacking faults localized at the GaN base/superlattice interface, causing the formation of zinc-blende cubic regions, and often single stacking faults at the GaN/InGaN bilayer interfaces. No misfit dislocations or cracks were detected in the heterostructure, implying a fully strained configuration. Geometrical phase analysis showed a rather uniform radial distribution of elastic strain in the (0001¯) facet of the InGaN inclusions. Depending on the superlattice growth temperature, the elastic strain energy is partitioned among the successive InGaN/GaN layers in the case of low-temperature growth, while at higher superlattice growth temperature the in-plane tensile misfit strain of the GaN barriers is accommodated through restrained diffusion of indium from the preceding InGaN layers. The corresponding In contents of the central facet were estimated at 0.42 and 0.25, respectively. However, in the latter case, successful reproduction of the experimental electron microscopy images by image simulations was only feasible, allowing for a much higher occupancy of indium adatoms at lattice sites of the semipolar facets, compared to the invariable 25% assigned to the polar facet. Thus, a high complexity in indium incorporation and strain allocation between the different crystallographic facets of the InGaN inclusions is anticipated and supported by the results of photoluminescence and spatially resolved microphotoluminescence spectroscopy.

Optical encoding by plasmon-based patterning: hard and inorganic materials become photosensitive.

The photosensitivity of nanocomposite AlN films with embedded silver nanospheres is reported. It stems from localized surface plasmon resonances (LSPR) whose modulation is photoinduced by laser annealing that induces a combined effect of metallic nanoparticle enlargement and dielectric matrix recrystallization; the photoindunced changes of the refractive index of the matrix result in strong spectral shift of LSPR. We demonstrate the utilization of this process for spectrally selective optical encoding into hard, durable, and chemically inert films.