Dr. Ovidiu COJOCARU

The development of new materials for short-wavelength infrared (SWIR) optical sensors is of high importance for the fast development of different applications, as, for example, Internet of Things, road safety, and pollution monitoring. Group IV SiGe provides more sustainable As-, Cd-, and Pb-free nanomaterials that are cheaper and ecologic and offer easy integration with CMOS technology. This Review is on Ge and SiGe quantum dots/nanocrystals (QDs/NCs) embedded in dielectrics for VIS-SWIR photodetection, in which we highlight and discuss photocurrent mechanisms, correlation of photodetection parameters and characteristics with crystalline structure, morphology and energy bandgap, and applications as photodetectors, optical sensors, phototransistors, and solar cells. The embedding matrix induces NC surface passivation, stress field, and nanocrystallization effects and brings specific advantages depending on the matrix material. SiGe NCs in oxides for VIS-SWIR sensing represents a niche domain, showing high photosensitivity (photocurrent) in SWIR up to 1.8 mu m at room temperature and 2 mu m at 100 K, deeper in SWIR than Ge. By alloying Ge with a small content of Si, NC thermal stability is much improved as the detrimental Ge fast diffusion in oxides is hindered and SWIR photosensing is enhanced due to light absorption in Ge-rich SiGe NCs.

SiGeSn nanocrystals (NCs) in oxides are of considerable interest for photo-effect applications due to the fine-tuning of the optical bandgap by quantum confinement in NCs. We present a detailed study regarding the silicon germanium tin (SiGeSn) NCs embedded in a nanocrystalline hafnium oxide (HfO2) matrix fabricated by using magnetron co-sputtering deposition at room temperature and rapid thermal annealing (RTA). The NCs were formed at temperatures in the range of 500-800 degrees C. RTA was performed to obtain SiGeSn NCs with surfaces passivated by the embedding HfO2 matrix. The formation of NCs and beta-Sn segregation were discussed in relation to the deposition and processing conditions by employing HRTEM, XRD and Raman spectroscopy studies. The spectral photosensitivity exhibited up to 2000 nm in short-wavelength infrared (SWIR) depending on the Sn composition was obtained. Comparing to similar results on GeSn NCs in SiO2 matrix, the addition of Si offers a better thermal stability of SiGeSn NCs, while the use of HfO2 matrix results in better passivation of NCs increasing the SWIR photosensitivity at room temperature. These results suggest that SiGeSn NCs embedded in an HfO2 matrix are a promising material for SWIR optoelectronic devices.

In this paper, short-wave infrared (SWIR) photosensing of GeSn-HfO2 films with small Si amount is studied in correlation with structure and composition of films. SiGeSnHfO2 films are deposited by magnetron sputtering and nanostructured by subsequent rapid thermal annealing. XRD and Raman spectroscopy investigations are carried out revealing the SiGeSn nanocrystallization in annealed films. Spectral responsivity shows enhanced sensitivity up to 2 mu m due to SiGeSn nanocrystals (NCs) and clusters with contribution from disorder.

This study examines the opto-electric characteristics of Ge:SiO2 composite films produced via magnetron sputtering at substrate temperatures of 300 degrees C, 400 degrees C, and 500 degrees C, with varying Ge concentrations. We employed x-ray diffraction, current-voltage measurements, and spectral photocurrent analysis to investigate the films structural, optical, and opto-electrical properties. Illumination of the samples resulted in a marked increase in current compared to dark conditions. Spectral photocurrent measurements revealed cutoff wavelengths of 1300 nm for films with 25:75 vol% Ge:SiO2 ratio, extending to 1320 nm for compositions with higher Ge content (60:40 vol%). These findings align with observations from I-V curve analyses. Our research highlights the potential of Ge:SiO2 composites for enhancing optoelectronic device performance. The results underscore the importance of continued investigation and innovative applications in this field to drive technological advancements.

Group IV quantum dots (QDs) in HfO2 are attractive for non-volatile memories (NVMs) due to complementary metal-oxide semiconductor (CMOS) compatibility. Besides the role of charge storage centers, SiGeSn QDs have the advantage of a low thermal budget for formation, because Sn presence decreases crystallization temperature, while Si ensures higher thermal stability. In this paper, we prepare MOS capacitors based on 3-layer stacks of gate HfO2/floating gate of SiGeSn QDs in HfO2/tunnel HfO2/p-Si obtained by magnetron sputtering deposition followed by rapid thermal annealing (RTA) for nanocrystallization. Crystalline structure, morphology, and composition studies by cross-section transmission electron microscopy and X-ray diffraction correlated with Raman spectroscopy and C-V measurements are carried out for understanding RTA temperature effects on charge storage behavior. 3-layer morphology and Sn content trends with RTA temperature are explained by the strongly temperature-dependent Sn segregation and diffusion processes. We show that the memory properties measured on Al/3-layer stack/p-Si/Al capacitors are controlled by SiGeSn-related trapping states (deep electronic levels) and low-ordering clusters for RTA at 325-450 degrees C, and by crystalline SiGeSn QDs for 520 and 530 degrees C RTA. Specific to the structures annealed at 520 and 530 degrees C is the formation of two kinds of crystalline SiGeSn QDs, i.e., QDs with low Sn content (2 at.%) that are positioned inside the floating gate, and QDs with high Sn content (up to 12.5 at.%) located at the interface of floating gate with adjacent HfO2 layers. The presence of Sn in the SiGe intermediate layer decreases the SiGe crystallization temperature and induces the easier crystallization of the diamond structure in comparison with 3-layer stacks with Ge-HfO2 intermediate layer. High frequency-independent memory windows of 3-4 V and stored electron densities of 1-2 x 10(13) electrons/cm(2) are achieved.

Orthorhombic HfO2 exhibits nanoscale ferroelectricity that opens the perspective of ultra-scalable CMOS integration of ferroelectric memories. However, many aspects of the metastable orthorhombic crystallization mechanisms still need to be elucidated and new fabrication methods are of high interest. In this paper, the atomically resolved crystal structure of HfO2 is a 3-layer structure with a Ge-rich HfO2 intermediate layer capped by a top (cap) HfO2 layer and cladded by a bottom HfO2 layer. There is a continuity of crystal growth from the top and bottom HfO2 layers into the intermediate layer. A spatial transition from a monoclinic phase to an orthorhombic phase was revealed within a region of a few atomic layers at the interface between capped and intermediate HfO2 layers. This result suggests the mechanism of orthorhombic and monoclinic phase formation by a martensitic-like transformation of the initially grown tetragonal phase. The sample fabrication method we used involved magnetron sputtering deposition of the 3-layer structures, i.e. a stack of top HfO2/Ge-rich HfO2 intermediate/bottom HfO2 layers, followed by rapid thermal annealing. It results in self-optimized orthorhombic crystallization of HfO2 by Ge nanoparticle segregation in the intermediate layer. The ferroelectric effects are revealed by polarization-voltage hysteresis loops and piezoresponse force microscopy measurements. The atomistic computations performed by using the density functional theory support the experimental results by showing that the Ge doping of HfO2 leads to orthorhombic phase stabilization and increased Berry phase polarization.

In this paper, we report studies on Al2O3/Ge/Al2O3 trilayer memory structures deposited by magnetron sputtering at room temperature on p-Si substrates coated with 3 nm SiO2. The changes of the structure, morphology and memory properties induced by rapid thermal annealing (RTA) in a broad temperature range 550-900 degrees C have been carefully investigated. High resolution transmission electron microscopy (HRTEM) revealed the existence of distinct RTA effects for different temperature ranges, in correlation with memory properties measured on Al/Al2O3/Ge/Al2O3/SiO2/p-Si/Al devices. Thus, at temperatures smaller than 650 degrees C, Ge diffuses into adjacent Al2O3, the layers remaining amorphous. The memory window increases from as-deposited samples to those annealed at 600 degrees C reaching the maximum of 5.4 V. After RTA at 700 degrees C, Ge nanocrystals (NCs) in intermediate Ge layer and Ge-rich amorphous nanoparticles in Al2O3 tunnel oxide are formed. Increasing RTA temperature to 800 and 900 degrees C, Ge NCs are no longer formed due to Ge strong diffusion. Instead, Ge-rich mixed GeAl oxide NCs of unknown crystalline structure are evidenced by HRTEM. The memory window continuously decreases with annealing temperature in the range 650-900 degrees C. The ON (OFF) charge loss of only 11% (9.8%) was found by extrapolation to 10 years.

We present a detailed study regarding the bandgap dependence on diameter and composition of spherical Ge-rich GexSi1-x nanocrystals (NCs). For this, we conducted a series of atomistic density functional theory (DFT) calculations on H-passivated NCs of Ge-rich GeSi random alloys, with Ge atomic concentration varied from 50 to 100% and diameters ranging from 1 to 4 nm. As a result of the dominant confinement effect in the DFT computations, a composition invariance of the line shape of the bandgap diameter dependence was found for the entire computation range, the curves being shifted for different Ge concentrations by Delta E(eV)=0.651(1-x). The shape of the dependence of NCs bandgap on the diameter is well described by a power function 4.58/d(1.25) for 2-4 nm diameter range, while for smaller diameters, there is a tendency to limit the bandgap to a finite value. By H-passivation of the NC surface, the effect of surface states near the band edges is excluded aiming to accurately determine the NC bandgap. The number of H atoms necessary to fully passivate the spherical GexSi1-x NC surface reaches the total number atoms of the Ge+Si core for smallest NCs and still remains about 25% from total number of atoms for bigger NC diameters of 4 nm. The findings are in line with existing theoretical and experimental published data on pure Ge NCs and allow the evaluation of the GeSi NCs behavior required by desired optical sensor applications for which there is a lack of DFT simulation data in literature.

The 1600 nm-extended SWIR photoresponse of SiGe/TiO2 multilayers with Ge-rich SiGe nanocrystals (NCs) is demonstrated. The SiGe NCs based multilayers are obtained by magnetron sputtering deposition of TiO2/ 6x(Ge/SiGe/Ge/TiO2) layers on heated p-Si substrate followed by rapid thermal annealing (RTA). Grazing incidence X-ray diffraction and Raman spectroscopy evidence the formation of cubic Ge-rich SiGe NCs and anatase TiO2. ITO/Ge-rich SiGe NCs based multilayer /p-Si heterostructure diodes, fabricated by depositing top ITO and bottom Al contacts, show n-p behavior. Photocurrent-voltage characteristics measured at 100 K under integral light illumination of reverse biased diode present a photocurrent higher with up to 2 orders of magnitude than the dark current. Spectral photocurrent increases with bias voltage increase and presents a bandgap-related cutoff wavelength of similar to 1600 nm due to the high Ge content of SiGe NCs.

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.

Films of amorphous Ge nanoparticles in Si3N4 on heated Si and quartz substrates at 300 degrees C were obtained by co-sputtering Ge, and Si3N4. The films structure and photo-electrical behaviour were studied through transmission electron microscopy and, current voltage and spectral photo-current investigations, respectively. The spectral photo-current were correlated with results obtained from transmission electron microscopy. Under illumination the current present a high increase with about one order of magnitude compared with the dark one. The photo-current spectra show a widening in near infrared to 0.97eV. Internal quantum efficiency values for -1V and 0V were determined.

The VIS-SWIR photosensing properties of Ge and GeSi NCs embedded in TiO2 films are investigated. For this, we deposit GeTiO2 and GeSiTiO2 films, respectively by magnetron sputtering and then we perform rapid thermal annealing (RTA) for Ge NCs and GeSi NCs formation, respectively. Raman studies and spectral photocurrent measurements were carried out. Ge NCs formation is evidenced in the Raman spectrum of GeTiO2 film annealed at 550 degrees C. The photocurrent spectra measured on the Ge NCs-TiO2 film present four peaks separated by deconvolution. The broad peaks at similar to 700, 890, 1010 nm are due to photo-effects in the Ge NCs-TiO2 film. More than that, the photocurrent increases exponentially with the increase of bias voltage. The cut-off wavelength is similar to 1240 nm. We achieve the extension of the photosensitivity limit to similar to 1310 nm in GeSi NCs-TiO2 films (800 degrees C RTA).

GeSi NCs / TiO2 multilayers with enhanced photocurrent properties were prepared and studied. Multilayers of TiO2 /(GeSi/TiO2)x2 /Si-p were deposited by magnetron sputtering and annealed by RTA at 700 degrees C for GeSi NCs formation. A post-annealing hydrogenation in plasma was performed on multilayers for healing of defects acting as traps and/or recombination centers and consequently producing the photocurrent enhancement. We studied the electrical and photoconductive properties of multilayers annealed by RTA and post-annealing hydrogenated. The current - temperature dependence reveals the conduction mechanisms in GeSi NCs / TiO2 multilayers RTA annealed, i.e. thermal activation of carriers to extended states (0.31 eV activation energy), the electron tunneling mechanism to nearest neighbors (T-1/2 behavior) and Mott variable range hopping (T-1/4 dependence). The photocurrent spectra made on multilayers structures hydrogenated for 10, 20 and 30 min evidence the photocurrent increasing up to 50%, showing that the hydrogenation is a suitable treatment for enhancing photocurrent. All photocurrent spectra present a dominant maximum (920 nm) and two shoulders (similar to 770 and similar to 1060 nm).

GeSi NCs / TiO2 multilayers with enhanced photocurrent properties were prepared and studied. Multilayers of TiO2 /(GeSi/TiO2)x2 /Si-p were deposited by magnetron sputtering and annealed by RTA at 700 degrees C for GeSi NCs formation. A post-annealing hydrogenation in plasma was performed on multilayers for healing of defects acting as traps and/or recombination centers and consequently producing the photocurrent enhancement. We studied the electrical and photoconductive properties of multilayers annealed by RTA and post-annealing hydrogenated. The current - temperature dependence reveals the conduction mechanisms in GeSi NCs / TiO2 multilayers RTA annealed, i.e. thermal activation of carriers to extended states (0.31 eV activation energy), the electron tunneling mechanism to nearest neighbors (T-1/2 behavior) and Mott variable range hopping (T-1/4 dependence). The photocurrent spectra made on multilayers structures hydrogenated for 10, 20 and 30 min evidence the photocurrent increasing up to 50%, showing that the hydrogenation is a suitable treatment for enhancing photocurrent. All photocurrent spectra present a dominant maximum (920 nm) and two shoulders (similar to 770 and similar to 1060 nm).

Trilayer MOS capacitors gate HfO2 / floating gate of Ge nanocrystals in HfO2 / tunnel HfO2 / Si substrate were prepared in the aim to be used for the detection of ionizing radiation. Magnetron sputtering and rapid thermal annealing were used for their fabrication. Capacitance-voltage measurements showed that Ge nanocrystals are the most important charge storage centres in our structure. The possibility to use these trilayer MOS capacitors as dosimeters was investigated, and the sensitivity to alpha particle irradiation was extracted.