Widely applicable nonaqueous solution routes have been employed for the syntheses of crystalline nanostructured tungsten oxide particles from a tungsten hexachloride precursor. Here, a systematic study on the crystallization and assembly behavior of tungsten oxide products made by using the bioligand deferoxamine mesylate (DFOM) (product I), the two chelating ligands hexadecyltrimethylammoniumbromide (CTAB) (II) and poly(alkylene oxide) block copolymer (Pluronic P123) (III) is presented. The mechanistic pathways for the material synthesis are also discussed in detail. The tungsten oxide nanomaterials and reaction solutions are characterized by Fourier transform IR, 1H, and 13C NMR spectroscopies, powder X‐ray diffraction, scanning electron microscopy, transmission electron microscopy (TEM), high‐resolution TEM, and selected‐area electron diffraction. The indexing of the line pattern suggests WO3 is in its monoclinic structure with a = 0.7297 nm, b = 0.7539 nm, c = 0.7688 nm, and β‐i; = 90.91 °. The nanoparticles formed have various architectures, such as chromosomal shapes (product I) and slates (II), which are quite different from the mesoporous one (III) that has internal pores or mesopores ranging from 5 to 15 nm. The nanoparticles obtained from all the synthetic procedures are in the range of 40–60 nm. The investigation of the gas‐sensing properties of these materials indicate that all the sensors have good baseline stability and the sensors fabricated from material III present very different response kinetics and different CO detection properties. The possibility of adjusting the morphology and by that tuning the gas‐sensing properties makes the preparation strategies used interesting candidates for fabricating gas‐sensing materials.

Continuous development of Si photonics requires ecological and cost-effective materials. In this work, SiGe nanocrystals (NCs) embedded in TiO2 are investigated as a photosensitive material for visible (VIS) to short-wave infrared (SWIR) broad-range detection. The TiO2 matrix has the advantage of a lower band gap than SiO2, facilitating transport of photogenerated carriers in NCs. The advantage of SiGe NCs over Ge NCs is emphasized by elucidating the mechanisms involved in rapid thermal annealing (RTA)-induced nanocrystallization. An efficiently increased NC stabilization is achieved by avoiding the detrimental fast Ge diffusion. For this, the structure, morphology, and composition were carefully characterized by high-resolution transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, and Raman spectroscopy. Two types of structures were investigated, a film of SiGe–TiO2 alloy and a multilayer of a stack of six SiGe/TiO2 pairs. The layers have been deposited on Si wafers using magnetron sputtering of Si, Ge, and TiO2 followed by RTA in an inert atmosphere. The stabilization of SiGe NCs is achieved by the formation during RTA of protective SiO2 thin layers through Si oxidation at the SiGe NC surface, acting as a barrier for Ge diffusion. Thus, embedded Ge-rich SiGe NCs are obtained, resulting in the SWIR extension of the spectral photocurrent up to 1700 nm for films and 1600 nm for multilayers. This study has shown that in multilayers, the local anisotropy of crystallization is compensated by the stress field developed in the SiGe lattice, highly visible in the bottom part. Also, SiGe crystallizes faster than TiO2 in the rutile phase, and therefore, TiO2 remains mainly amorphous.

Detection in short-wave infrared (SWIR) has become a very stringent technology requirement for developing fields like hyperspectral imaging or climate changes. In a market dominated by III–V materials, GeSn, a Si compatible semiconductor, has the advantage of cost efficiency and inerrability by using the mature Si technology. Despite the recent progress in material growth, the easy fabrication of crystalline GeSn still remains a major challenge, and different methods are under investigation. We present the formation of GeSn nanocrystals (NCs) embedded in oxide matrix and their SWIR characterization. The simple and cost-effective fabrication method is based on thermal treatment of amorphous (Ge1–x Sn x ) y (SiO2)1–y layers deposited by magnetron sputtering. The nanocrystallization for Ge1–x Sn x with 9–22 at. % Sn composition in SiO2 matrix with 9% to 15% mole percent was studied under low thermal budget annealing in the 350–450 °C temperature range. While the Sn at.% content is the main parameter influencing the band-structure of the NCs, the SWIR sensitivity can be optimized by SiO2 content and H2 gas component in the deposition atmosphere. Their role is not only changing the crystallization parameters but also to reduce the carrier recombination by passivation of NCs defects. The experiments indicate a limited composition dependent temperature range for GeSn NCs formation before β-Sn phase segregation occurs. NCs with an average size of 6 nm are uniformly distributed in the film, except the surface region where larger GeSn NCs are formed. Spectral photovoltaic current measured on SiO2 embedded GeSn NCs deposited on p-Si substrate shows extended SWIR sensitivity up to 2.4 μm for 15 at. % Sn in GeSn NCs. The large extension of the SWIR detection is a result of many factors related to the growth parameters and also to the in situ or ex situ annealing procedures that influence the uniformity and size distribution of NCs.

Films of SiGe nanocrystals (NCs) in oxide have the advantage of tuning the energy band gap by adjusting SiGe NCs composition and size. In this study, SiGe-SiO2 amorphous films were deposited by magnetron sputtering on Si substrate followed by rapid thermal annealing at 700, 800 and 1000 °C. We investigated films with Si:Ge:SiO2 compositions of 25:25:50 vol.% and 5:45:50 vol.%. TEM investigations reveal the major changes in films morphology (SiGe NCs with different sizes and densities) produced by Si:Ge ratio and annealing temperature. XPS also show that the film depth profile of SiGe content is dependent on the annealing temperature. These changes strongly influence electrical and photoconduction properties. Depending on annealing temperature and Si:Ge ratio, photocurrents can be 103 times higher than dark currents. The photocurrent cutoff wavelength obtained on samples with 25:25 vol% SiGe ratio decreases with annealing temperature increase from 1260 nm in SWIR for 700 °C annealed films to 1210 nm for those at 1000 °C. By increasing Ge content in SiGe (5:45 vol%) the cutoff wavelength significantly shifts to 1345 nm (800 °C annealing). By performing measurements at 100 K, the cutoff wavelength extends in SWIR to 1630 nm having high photoresponsivity of 9.35 AW−1.

Various mesoporous silica supported Pd materials were prepared by different methodologies in order to control and optimize the metal nanoparticle sizes for catalytic applications. The catalytic activities (conversion, mol% and selectivity to methyl-cinnamate) of the supported palladium catalysts were investigated in the Heck reaction under microwave irradiation using various haloarenes. Pd materials prepared by co-precipitation exhibited a very poor activity in the Heck reaction compared to that of Pd impregnated samples. Impregnated materials prepared without the use of a specific reducing agent had comparable activities to those of APTS-NaBH 4 reduced Pd materials, validating the simplicity of the methodology. High selectivities to methylcinnamate were obtained for all materials.

The formation of Ni silicides is studied by transmission electron microscopy during in situ heating experiments of 12 nm Ni layers on blanket silicon, or in patterned structures covered with a thin chemical oxide. It is shown that the first phase formed is the NiSi 2 which grows epitaxially in pyramidal crystals. The formation of NiSi occurs quite abruptly around 400°C when a monosilicide layer covers the disilicide grains and the silicon in between. The NiSi phase remains stable up to 800°C, at which temperature the layer finally fully transforms to NiSi 2. The monosilicide grains show different epitaxial relationships with the Si substrate. Ni 2 Si is never observed.

High performance trilayer memory capacitors with a floating gate of a single layer of Ge quantum dots (QDs) in HfO were fabricated using magnetron sputtering followed by rapid thermal annealing (RTA). The layer sequence of the capacitors is gate HfO /floating gate of single layer of Ge QDs in HfO/tunnel HfO /p-Si wafers. Both Ge and HfO are nanostructured by RTA at moderate temperatures of 600-700 °C. By nanostructuring at 600 °C, the formation of a single layer of well separated Ge QDs with diameters of 2-3 nm at a density of 4-5 × 10 m is achieved in the floating gate (intermediate layer). The Ge QDs inside the intermediate layer are arranged in a single layer and are separated from each other by HfO nanocrystals (NCs) about 8 nm in diameter with a tetragonal/orthorhombic structure. The Ge QDs in the single layer are located at the crossing of the HfO NCs boundaries. In the intermediate layer, besides Ge QDs, a part of the Ge atoms is segregated by RTA at the HfO NCs boundaries, while another part of the Ge atoms is present inside the HfO lattice stabilizing the tetragonal/orthorhombic structure. The fabricated capacitors show a memory window of 3.8 ± 0.5 V and a capacitance-time characteristic with 14% capacitance decay in the first 3000-4000 s followed by a very slow capacitance decrease extrapolated to 50% after 10 years. This high performance is mainly due to the floating gate of a single layer of well separated Ge QDs in HfO, distanced from the Si substrate by the tunnel oxide layer with a precise thickness.

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