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.

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.

Si and Ge nanocrystals in oxides are of a large interest for photo-effect applications due to the fine-tuning of the optical bandgap by quantum confinement in nanocrystals. In this work, dense Ge nanocrystals suitable for enhanced photoconduction were fabricated from 60% Ge in TiO2 amorphous layers by low temperature rapid thermal annealing at 550 °C. An exponential increase of the photocurrent with the applied voltage was observed in coplanar structure of Ge nanocrystals composite films deposited on oxidized Si wafers. The behaviour was explained by field effect control of the Fermi level at the Ge nanocrystals-TiO2 layer/substrate interfaces. The blue-shift of the absorption gap from bulk Ge value to 1.14 eV was evidenced in both photocurrent spectra and optical reflection-transmission experiments, in good agreement with quantum confinement induced bandgap broadening in Ge nanocrystal with sizes of about 5 nm as found from HRTEM and XRD investigations. A nonmonotonic spectral dependence of the refractive index is associated to the Ge nanocrystals formation. The nanocrystal morphology is also in good agreement with the Coulomb gap hopping mechanism of T–1/2 -type explaining the temperature dependence of the dark conduction.

Group IV nanocrystals (NCs), in particular from the Si–Ge system, are of high interest for Si photonics applications. Ge-rich SiGe NCs embedded in nanocrystallized HfO2 were obtained by magnetron sputtering deposition followed by rapid thermal annealing at 600 °C for nanostructuring. The complex characterization of morphology and crystalline structure by X-ray diffraction, μ-Raman spectroscopy, and cross-section transmission electron microscopy evidenced the formation of Ge-rich SiGe NCs (3–7 nm diameter) in a matrix of nanocrystallized HfO2. For avoiding the fast diffusion of Ge, the layer containing SiGe NCs was cladded by very thin top and bottom pure HfO2 layers. Nanocrystallized HfO2 with tetragonal/orthorhombic structure was revealed beside the monoclinic phase in both buffer HfO2 and SiGe NCs–HfO2 layers. In the top part, the film is mainly crystallized in the monoclinic phase. High efficiency of the photocurrent was obtained in a broad spectral range of curves of 600–2000 nm at low temperatures. The high-quality SiGe NC/HfO2 matrix interface together with the strain induced in SiGe NCs by nanocrystallization of both HfO2 matrix and SiGe nanoparticles explain the unexpectedly extended photoelectric sensitivity in short-wave infrared up to about 2000 nm that is more than the sensitivity limit for Ge, in spite of the increase of bandgap by well-known quantum confinement effect in SiGe NCs.