Dr. Adrian SLAV

The gas sensitivity of field-effect structures with 2D-MoS2 channels selectively grown between Mo electrodes using the Mo-CVD method was investigated by measuring the effect of molecular adsorption from air on the device source-drain current (Isd). The channels were composed of interconnected atomically thin MoS2 grains, with their density and average thickness varied by choosing two different distances (15 and 20 mu m) between the Mo contacts. A high response to the tested stimuli, including molecule adsorption, illumination and gate voltage changes, was observed. A significant, persistent photoconduction was induced by positive charge accumulation on traps, most likely at grain boundaries and associated defects. Isd increased under high vacuum, both in the dark and under illumination. The relative dark current response to the transition from air to high vacuum reached up to 1000% at the turn-on voltage. When monitored during the gradual change in air pressure, Isd exhibited a non-monotonic function, sharply peaking at about 10-2 mbar, suggesting molecular adsorption on different defect sites and orientations of adsorbed H2O molecules, which were capable of inducing electron accumulation or depletion. Despite the screening of disorder by extra electrons, the #20 mu m sample remained more sensitive to air molecules on its surface. The high vacuum state was also investigated by annealing devices at temperatures up to 340 K in high vacuum, followed by measurements down to 100 K. This revealed thermally stimulated currents and activation energies of trapping electronic states assigned to sulfur vacancies (230 meV) and other shallow levels (85-120 meV), possibly due to natural impurities, grain boundaries or disorder defects. The results demonstrate the high sensitivity of these devices to molecular adsorption, making the technology promising for the easy fabrication of chemical sensors.

This study investigates the fabrication of short-wavelength infrared (SWIR) photosensitive amorphous and nanocrystalline Ge1-xSnx:H thin films by magnetron sputtering from separate Ge and Sn targets using different Ar: H mixing ratios as working gas. Amorphous Ge1-xSnx:H films have been obtained on both c-Si and fused quartz substrates at ambient temperature, while dynamic nanocrystallization occurs in-situ when the substrate temperature during deposition is raised to 200 degrees C. Fourier-transform infrared spectroscopy has shown the hydrogen incorporation by detecting an absorption line at 1873 cm(-1), close to the value corresponding to Ge-H bonding, only in the room temperature amorphous films. Based on that, we infer that the hydrogen concentration is very low in the films deposited at high temperature. The higher concentration of hydrogen in the amorphous samples is associated with an increase of the absorption gap to 0.5 eV compared to 0.3 eV in the 200 degrees C samples. In-situ (during deposition) and ex-situ (by subsequent rapid thermal annealing) nanocrystallization have been analyzed by high-resolution transmission electron microscopy, X-ray diffraction and micro-Raman spectroscopy. SWIR spectral photosensitivity up to 2.4 mu m was found to be more than two orders of magnitude improved in hydrogenated amorphous films with high hydrogen content, compared to the nanocrystalline ones that are weakly hydrogenated. These findings demonstrate the potential of hydrogenation to enhance the photoelectric properties of GeSn sputtering films for optoelectronic SWIR infrared applications.

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.

Selective growth of 2D MoS2 layers on patterned substrates is highly desired for easy fabrication of devices. Selectively grown 2D MoS2 on Mo patterned substrates for the formation of intimate metallic contact was obtained by a Mo-CVD method in which MoO2 from an oxidized Mo pattern and S powder are the growth precursors. Mo films were deposited by magnetron sputtering on SiO2(300 nm)/c-Si substrates and patterned by photolithography techniques for obtaining Mo strips and finger contact structures, with the gap between the strips and finger varied from 5 to 20 mu m. The filling of the gap by selectively grown atomically thin MoS2 plates of 1-2 monolayers (MLs) was demonstrated by scanning electron microscopy and atomic force microscopy imaging. Field effect devices for the characterization of the photosensitivity of selectively grown MoS2 have been fabricated from finger contact structures. The dark current is drastically reduced from 10(-9) to 10(-13)-10(-14) A by varying the gate voltage from +7 to -7 V, showing the n-type semiconductor behavior of the selectively grown 2D MoS2. High photosensitivity of 10(5) (%) was obtained for 4.5 x 10(-4) mW/cm(2) at 650 nm wavelength illumination. The spectral responsivity reaches values of 15-25 A/W at 600 nm wavelength and shows an energy onset of 1.72-1.77 eV corresponding to about 2 ML MoS2. The carrier-trapping effect responsible for the slow part of the device response can be caused by structural defects and also by adsorbed molecules like in gas sensors.

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.

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.

The high-k-based MOS-like capacitors are a promising approach for the domain of non-volatile memory devices, which currently is limited by SiO2 technology and cannot face the rapid downsizing of the electronic device trend. In this paper, we prepare MOS-like trilayer memory structures based on high-k ZrO2 by magnetron sputtering, with a 5% and a 10% concentrations of Zr in the Zr-ZrO2 floating gate layer. For crystallization of the memory structure, rapid thermal annealing at different temperatures between 500 degrees C and 700 degrees C was performed. Additionally, Al electrodes were deposited in a top-down configuration. High-resolution transmission electron microscopy reveals that ZrO2 has a polycrystalline-columnar crystallization and a tetragonal crystalline structure, which was confirmed by X-ray diffraction measurements. It is shown that the tetragonal phase is stabilized during the crystallization by the fast diffusion of oxygen atoms. The capacitance-voltage characteristics show that the widest memory window (Delta V = 2.23 V) was obtained for samples with 10% Zr annealed at 700 degrees C for 4 min. The charge retention characteristics show a capacitance decrease of 36% after 10 years.

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.

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 & DEG;C for nanostructuring. The complex characterization of morphology and crystalline structure by X-ray diffraction, mu-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.

The memory properties of a trilayer structure of ZrO2/Ge-ZrO2/ZrO2/Si-p were investigated. The trilayer was prepared by magnetron sputtering deposition followed by a rapid thermal annealing process for obtaining Ge nanocrystals embedded in ZrO2 matrix. The X-ray diffraction patterns obtained on annealed structures show that both trilayer structures are cristallized, with narrow diffraction peaks. Ge as a separated phase is not evidenced in the diffractograms, instead is possible that Ge atoms enters in ZrO2 lattice structure and form a compound of ZrO3GeO8 crystallized in the tetragonal phase. In the case of ZrO2 control structure, the diffractograms show that the ZrO2 layer is crystallized in tetragonal phase. The memory properties are evidenced by C-V characteristics with counterclockwise hysteresis loop and a memory window of Delta V=1.1V for the structure annealed at 570 degrees C and Delta V=0.8 V for the structure annealed at 650 degrees C. The influence of the interface SiO2 layer on the frequency dependence of capacitance was evidenced by C-f characteristics.

The development of short-wave infrared (SWIR) photonics based on GeSn alloys is of high technological interest for many application fields, such as the Internet of things or pollution monitoring. The manufacture of crystalline GeSn is a major challenge, mainly because of the low miscibility of Ge and Sn. The use of embedded GeSn nanocrystals (NCs) by magnetron sputtering is a cost-effective and efficient method to relax the growth conditions. We report on the use of GeSn/SiO2 multilayer deposition as a way to control the NC size and their insulation. The in situ prenucleation of NCs during deposition was followed by ex situ rapid thermal annealing. The nanocrystallization of 20X(11nm_Ge0.865S0.135/1.5nm_SiO2) multilayers leads to formation of GeSn NCs with similar to 16% Sn concentration and similar to 9 nm size. Formation of GeSn domes that are vertically correlated contributes to the nanocrystallization process. The absorption limit of similar to 0.4 eV in SWIR found by ellipsometry is in agreement with the spectral photosensitivity. The ITO/20x(GeSn NC/SiO2)/p-Si/Al diodes show a maximum value of the SWIR photosensitivity at a reverse voltage of 0.5 V, with extended sensitivity to wavelengths longer than 2200 nm. The multilayer diodes have higher photocurrent efficiency compared to diodes based on a thick monolayer of GeSn NCs.

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.

GeSn alloys have the potential of extending the Si photonics functionality in shortwave infrared (SWIR) light emission and detection. Epitaxial GeSn layers were deposited on a relaxed Ge buffer on Si(100) wafer by using high power impulse magnetron sputtering (HiPI-MS). Detailed X-ray reciprocal space mapping and HRTEM investigations indicate higher crystalline quality of GeSn epitaxial layers deposited by Ge HiPI-MS compared to commonly used radio frequency magnetron sputtering (RF-MS). To obtain a rectifying heterostructure for SWIR light detection, a layer of GeSn nanocrystals (NCs) embedded in oxide was deposited on the epitaxial GeSn one. Embedded GeSn NCs are obtained by cosputtering deposition of (Ge1-xSnx)(1-y)(SiO2)(y) layers and subsequent rapid thermal annealing at a low temperature of 400 degrees C. Intrinsic GeSn structural defects give p-type behavior, while the presence of oxygen leads to the n-character of the embedded GeSn NCs. Such an embedded NCs/epitaxial GeSn p-n heterostructure shows superior photoelectrical response up to 3 orders of magnitude increase in the 1.2-2.5 mu m range, as compared to performances of diode based only on embedded NCs.

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-xSnx)(y)(SiO2)(1-y) layers deposited by magnetron sputtering. The nanocrystallization for Ge1-xSnx 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 degrees 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 H-2 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 beta-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 mu m 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.

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).

Trilayer memory capacitors of control HfO2/floating gate of Ge nanoparticles in HfO2/tunnel HfO2/Si substrate deposited by magnetron sputtering and subsequently annealed are investigated for the first time for applications in radiation dosimetry. In the floating gate (FG), amorphous Ge nanoparticles (NPs) are arranged in two rows inside the HfO2 matrix. The HfO2 matrix is formed of orthorhombic/tetragonal nanocrystals (NCs). The adjacent thin films to the FG are also formed of orthorhombic/tetragonal HfO2 NCs. This phase is formed during annealing, in samples with thick control HfO2, in the presence of Ge, being induced by the stress. In the rest of the control oxide, HfO2 NCs are monoclinic. Orthorhombic HfO2 has ferroelectric properties and therefore enhances the memory window produced by charge storage in Ge NPs to above 6 V. The high sensitivity of 0.8 mV Gy(-1) to a particle irradiation from a Am-241 source was measured by monitoring the flatband potential during radiation exposure after electrical writing of the memory.

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).

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 degrees 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.

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 memory capacitors with Ge nanocrystals (NCs) floating gate in HfO2 were obtained by magnetron sputtering deposition on p-type Si substrate followed by rapid thermal annealing at relatively low temperature of 600 degrees C. The frequency dispersion of capacitance and resistance was measured in accumulation regime of Al/HfO2 gate oxide/Ge NCs in HfO2 floating gate/HfO2 tunnel oxide/SiOx/p-Si/Al memory capacitors. For simulation of the frequency dispersion a complex circuit model was used considering an equivalent parallel RC circuit for each layer of the trilayer structure. A series resistance due to metallic contacts and Si substrate was necessary to be included in the model. A very good fit to the experimental data was obtained and the parameters of each layer in the memory capacitor, i.e. capacitances and resistances were determined and in turn the intrinsic material parameters, i.e. dielectric constants and resistivities of layers were evaluated. The results are very important for the study and optimization of the hysteresis behaviour of floating gate memories based on NCs embedded in oxide. (C) 2017 Published by Elsevier B.V.

Photo-induced effects on charging and discharging of nanocrystals (NCs) in capacitor memories with Ge NCs in an HfO2 matrix as a floating gate layer are studied. The sequence of layers HfO2/Ge-HfO2/ HfO2 was deposited on a p-Si substrate using magnetron sputtering. Well separated Ge NCs are obtained after rapid thermal annealing at 600 degrees C. The optoelectric capacitor memories were fabricated with a semi-transparent electrode on top of the structure and an Al electrode on the back side of the Si substrate. Light illumination effects on hysteresis curves were investigated using different operation modes. The hysteresis window increases by increasing the light exposure time. The spectral dependence of the hysteresis window shows the maximum contribution of the light in the wavelength range of 950-1000 nm, corresponding to both contributions from the Si substrate and from Ge NCs. The stored information about the electrical and optical pulses is also investigated in the regime of the flat band potential measurements (retention measurements). It is shown that in our memory structure, the photo-effect on the memory retention corresponds to a tunnelling transfer of negative charges from the Si substrate to Ge NCs, up to a mean value of 1.6 electrons per NC. Published by AIP Publishing.

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.

The photosensing properties related to the structure of GeSi/TiO2 multilayers prepared under different conditions are studied. TiO2 cap/(GeSi/TiO2)(2) multilayers (ML) were deposited by magnetron sputtering (MS) and annealed by rapid thermal annealing. Trilayers of TiO2 cap/GeSi/TiO2 (TL) were also deposited using reactive high power impulse MS (HiPIMS) for TiO2 layers and dc MS for the GeSi layer. For TL samples a two-step annealing was employed, one before and the second after depositing TiO2 cap. Structure and morphology characterization (X-ray diffraction, scanning and transmission electron microscopy) was carried out and photocurrent measurements (voltage dependences, spectral curves) were performed. The annealed ML samples are formed of GeSi NCs with 5 - 10 nm sizes, while in the annealed TL samples, the GeSi NCs are larger (20 - 30 nm). These morphologies determine the multilayers photosensing properties in VIS-NIR of ML structures and in UV in TL ones, respectively.

High performance trilayer memory capacitors with a floating gate of a single layer of Ge quantum dots (QDs) in HfO2 were fabricated using magnetron sputtering followed by rapid thermal annealing (RTA). The layer sequence of the capacitors is gate HfO2/floating gate of single layer of Ge QDs in HfO2/tunnel HfO2/p-Si wafers. Both Ge and HfO2 are nanostructured by RTA at moderate temperatures of 600-700 degrees C. By nanostructuring at 600 degrees C, the formation of a single layer of well separated Ge QDs with diameters of 2-3 nm at a density of 4-5 x 1015 m(-2) 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 HfO2 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 HfO2 NCs boundaries. In the intermediate layer, besides Ge QDs, a part of the Ge atoms is segregated by RTA at the HfO2 NCs boundaries, while another part of the Ge atoms is present inside the HfO2 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 HfO2, distanced from the Si substrate by the tunnel oxide layer with a precise thickness.

The influence of light illumination on the programming of a capacitor floating gate memory based on Ge nanocrystals in HfO2 was studied. The capacitor was fabricated on a c-Si substrate by magnetron sputtering deposition of a layer sequence of HfO2/Ge-HfO2/HfO2 and post-growth rapid thermal annealing for nanocrystals formation at 600 degrees C. The illumination of the structure was performed through a semi-transparent Au contact (20% transparency). A maximum value of the light- induced change of 90% in C-V curve was obtained for 5 mW/cm(2) illumination during +5 V writing programming. The effect of the light exposure on the relative change of the C-V curve can be increased by reducing the writing time at 1 min.

The electrical and photosensing properties correlated with structure and morphology of TiO2/(GeSi/TiO2)(2) multilayers are investigated. The multilayers are prepared by magnetron sputtering followed by rapid thermal annealing. Studies of Raman spectroscopy, transmission electron microscopy and X-ray diffraction are carried out. Measurements of dark current versus voltage and temperature are done. The photosensing properties are studied by measuring photocurrent spectra at different temperatures. We obtain multilayers with 10 - 15 nm Ge0.6Si0.4 nanocrystals (NCs) by annealing at 800 degrees C. We evidence the tunneling mechanism between neighbor NCs (T-1/2 law) in the dark current-temperature dependence. The photocurrent spectrum has a maximum with position shifting from 940 to 980 nm when the measurement temperature increases from 150 to 300 K, being due to the GeSi NCs.

The strain in Si containing group-V impurities is a topical subject of study due to its potential applications in quantum computing. In this paper we study Bi-209 implanted Si concerning the correlation between the strain produced by stopped Bi ions and trapping characteristics of the defects resulted from implantation. The depths distributions of stopped ions and primary defects are simulated and the distributions of permanent defects are modelled for Si implanted with low fluence Bi-209 ions of 28 MeV kinetic energy. For comparison, these depths distributions were similarly calculated for I-127 ions with the same fluence and energy, implanted in Si. The results are compared with each other and correlated with the characteristics of traps in these systems, previously obtained. We demonstrate that the intensity of the strain field is the most important factor in changing of trap parameters, while the superposition between the region with strain and the region where defects are located is a second order effect. (C) 2016 Elsevier Ltd. All rights reserved.

The strong correlation between morphology and charge storage properties of HfO2/Ge/HfO2/Si trilayer structures was evidenced. The morphology of structures deposited by magnetron sputtering and electron beam evaporation was tailored by rapid thermal annealing and investigated by transmission electron microscopy, Raman and X-ray photoelectron spectroscopies. The best hysteresis loops (capacitance-voltage characteristics) were obtained for trilayers with high density Ge nanocrystals located in the position of as-deposited Ge layer. The decrease of Ge nanocrystals density narrows the memory window, by spreading Ge atoms into HfO2 matrix (sputtered trilayers), or by Ge atoms expulsion toward HfO2 nanocrystals surface (evaporated trilayers). (C) 2015 Elsevier Ltd. All rights reserved.

The structure and charge storage properties of a trilayer structure with Ge nanocrystals embedded in HfO2 oxide were studied. The trilayer structure HfO2/Ge-HfO2/HfO2/p-Si was prepared by magnetron sputtering and subsequent rapid thermal annealing at 600 degrees C. The TEM investigations reveal the formation of Ge NCs embedded in crystalline HfO2 at the position of the Ge-HfO2 layer. The capacitors were made by Al evaporation on both front and backside of the trilayer structure. The C-V characteristics show a counterclockwise hysteresis with large memory window of 0.85 V which is given only by the contribution of the Ge NCs embedded in HfO2. The I-V characteristics show an asymmetric behavior, the currents are three times higher for the negative voltage than the positive one.

The charge storage properties of Ge nanocrystals-based MOS-like capacitors with tunnel and gate HfO2 are studied. HfO2/Ge/HfO2/Si trilayer structures were prepared by magnetron sputtering (in Ar) and subsequent rapid thermal annealing (650 degrees C). HfO2/Si structures were also prepared, some under similar conditions, while others were deposited in Ar:O-2. TEM investigations and C-V measurements were performed. TEM on annealed trilayers evidences the formation of ordered and precisely positioned array of Ge nanocrystals embedded in crystalline HfO2. The annealed Al/HfO2/Ge/HfO2/p-Si/Al capacitors present counterclockwise C-V hysteresis (0.8 V memory window) mainly given by Ge nanocrystals, with negligible contribution from crystallized-HfO2 traps.

In this paper, we apply results of analysis of the Raman spectrum from an amorphous carbon film modified with iron (a - C : Fe) which leads to construction of clusters containing fragments of graphene and a layer of iron atoms. Such clusters may be candidates for the role of microwave radiation absorbers. For the Raman experiments we performed deposition of a thin film of a -C : Fe. Details of the film deposition process, together with the corresponding Raman experiments are presented in this paper. Comparison with a literature model was performed for the intensity ratio of the maxima for specific Raman bands, using the letter D to represent " disorder" and the letter G to represent "graphite". Comparison gives evidence for the existence of nanosize fragments of graphene embedded in an amorphous matrix of the a - C : Fe film. The diameter of the fragments is predicted to attain a value of about 1.2 nm. Moreover, in a comparison with experimental data for defective graphite, the position of the maximum of the D band for a- C : Fe appeared to be red shifted. This could support the proposition that damping of Raman-active oscillations occurs by an electron gas in fragments of graphene after introduction of iron, e. g. after intercalation. On the basis of these estimates, we modeled a symmetrical polycyclic aromatic hydrocarbon having a similar size and converted it into fragment of a graphene plane by removal of hydrogen atoms occupying the edge states. To preserve symmetry, we placed atoms of iron on top of the fragment, situating them exactly above the centers of hexagons at a certain distance and placed another fragment of graphene on the top of the iron atoms, symmetrically. For a distance of 2.52 angstrom between the centers of the hexagon and the iron atom, distortions of carbon-carbon valence bonds and angles were found to be minimal, as shown through optimization of the system's geometry using the Avogadro molecular editor. This result supports an hypothesis of graphene fragments during the growth of an amorphous carbon film modified by simultaneous addition of a dopant metal such as iron. This example may illustrate the stability of a two-dimensional electron gas confined between the fragments.

We analyse the influence of the strain field on the parameters of trapping centres. The system under study is high resistivity Si implanted with Bi6+ and I6+ ions respectively, of 28 MeV kinetic energy, 3(O) off axis orientation and 5x10(11) ions/cm(2) fluence. The strain field is the consequence of size and mass difference of the irradiation ions in respect to the atoms of the lattice, and the defects are produced during the slowing-down of ions, as a result of the energy transfer from the ion to Si atoms. These results are of interest for the design and manufacturing of microelectronic devices incorporating strain, particularly for quantum computers with qubits based on the interaction of electronic and nuclear spins of group-V donors in Si.

The effects of strain field are studied in Si wafers implanted with heavy iodine and bismuth ions and in multi-quantum well structures. The experimental method of thermally stimulated currents without applied bias is used, and the trapping centres parameters are determined by modelling the discharge curves. In both cases, the strain field produces temperature-dependent parameters of trapping levels. So, due to the high strain field in the neighbourhood of implanted ions, energy levels broaden and cross sections become temperature dependent. In multilayer structures, for the trapping centres corresponding to strain-induced defects both concentrations and capture cross sections are temperature dependent.

We report on the charge storage properties of trilayer structures consisting in sputtered gate HfO2/co-sputtered Ge-HfO2 layer/rapid thermal tunneling SiO2 oxide. Investigations of transmission electron microscopy and X-ray diffraction evidence the formation of HfO2 with mixed structure of monoclinic and tetragonal in the annealed structures. Capacitance-voltage (C-V) characteristics were measured on Al/HfO2/Ge-HfO2/SiO2/Si/Al metal-oxide-semiconductor capacitors based on as-deposited and annealed structures. Large C-V hysteresis is observed for the as-deposited structures and is controlled by traps present in oxide and interface. The annealing yields a C-V hysteresis with smaller memory window being due to injected charges in Ge nanocrystals.

By implanting Bi in Si, a strong strain field due to the bigger atomic mass and size of stopped Bi ions than Si lattice ones is produced, together with irradiation defects. The controlled doping of Si with Bi leads to modern applications such as quantum information processing. Here we show that the parameters of trapping centres are modified under the strain field. In the literature there are no reports on this subject. We irradiated Si wafers with Bi6+ ions of 28MeV kinetic energy, 3 degrees off [100] axis orientation. The depth distributions of stopped ions and of primary defects were simulated. The traps produced by irradiation were investigated using the thermally stimulated currents method without bias. We recorded and modelled the discharge current curves. The strain field was modelled as a permanent and temperature-independent electric field. The traps of V-2, VO/CiCs, and CiOi and other two not assigned were evidenced. We have found that all trapping levels are broadened, and all capture cross-sections are temperature dependent which we attribute to the strong strain field produced by Bi. These results are important and must be taken into account in designing and manufacturing microelectronic devices incorporating strain, including the topical spin qubit ones. Copyright (C) EPLA, 2014

N-type silicon single crystals with resistivity higher than 8000 Omega cm were irradiated with ions of Bi6+, of 28 MeV kinetic energy. At this energy, the ions are stopped into the wafer. Being much heavier and bigger than the host atoms, they produce major disturbances into the lattice. On the other hand, the produced collision cascade is the source of lattice defects which act as traps. We investigated them using the method of thermally stimulated currents without applied bias. The results are compared with those obtained from the analysis of silicon irradiated with I6+ ions.

N-type P-doped silicon single crystals with resistivity higher than 8000 Omega cm were irradiated with I-127(6+) ions of 28 MeV kinetic energy. The penetration of the ions through the target and the processes of energy loss were simulated using the CTRIM Monte Carlo code, and point defect production was calculated in the frame of our diffusion-reaction model. Trapping phenomena were investigated using the method of thermally stimulated currents without applied bias. The modeling of the current-temperature curves takes into consideration both point defects and stress-type trapping centers, produced by the ions stopped into the crystal.

The effects of 5 x 10(11) cm(-2 6+)I(127) ions of 28 MeV kinetic energy on high resistivity (100) Si were studied. The profile of primary defects was simulated. The defects produced by irradiation which act as traps were investigated. Thermally stimulated current measurements without externally applied bias were used, and for this the traps were charged by illuminating samples with 1000, 800, and 400 nm wavelengths. The discharge currents were recorded and modeled, and therefore the parameters of the traps were determined. The presence of I ions, heavier than Si, stopped into the target was modeled as a temperature independent electric field. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4772015]

Transmission electron microscopy and X-ray photoelectron spectroscopy analyses are performed to investigate Ge nanoparticles embedded in an amorphous SiO2 matrix. GeSiO thin films are prepared by two methods, sol-gel and radio frequency magnetron sputtering. After the deposition, the sol-gel films are annealed in either N-2 (at 1 atm and 800 A degrees C) or H-2 (at 2 atm and 500 A degrees C), and the sputtered films in H-2 (at 2 atm and 500 A degrees C), to allow Ge segregation. Amorphous Ge-rich nanoparticles (3-7 nm size) are observed in sol-gel films. Crystalline Ge nanoparticles in the high pressure tetragonal phase (10-50 nm size) are identified in the sputtered films. The size of the nanoparticles increases with Ge concentration in the volume of the film. At the film surface, the Ge concentration is much larger that in the volume for both sol-gel and sputtered films. At the same time, at the film surface, only oxidized Ge is observed.

The optical band gaps of the nanocomposite TiO2-Ge thin films deposited by reactive co-sputtering method onto quartz and silicon substrates at different oxygen partial pressures have been investigated by the optical characterization method. Using 2%, 4% and 6% oxygen dilution in argon, an atomic content of 3%, 22% and 35% germanium in the TiO2 oxide matrix was obtained. Structural characterization of layers was performed by X-ray diffraction and the result revealed that no crystallization phenomena have occurred after the annealing at 700 degrees C. When increasing the annealing temperature, at 750 degrees C the TiO2 anatase phase crystallizes and subsequently it partially convert to the rutile polymorph (at 800 degrees C). The optical band gaps were analyzed using Tauc plot formula for direct and indirect transitions gap. Intermediate energy levels appear in the TiO2 energy gap and a slight increasing of the indirect transitions gap with germanium content was noticed.

The long time degradation produced by particles and ions in crystalline materials used for devices to work in space, or for detectors in HEP and astroparticles, is characterised by the non-ionising energy loss, which is calculated in the frame of an analytical model. The transient phenomena as short time degradation are characterised by the time and space dependencies of the lattice and electron temperatures near the projectile trajectory. These processes are considered in the frame of a thermal spike model, which takes into account both ionization and nuclear energy loss processes.

The thermal spike model which takes into account both ionization and nuclear energy loss processes of the projectile as distinct electronic and atomic heat sources is used to describe transient processes induced by ions in silicon. The time and space dependencies of the lattice and electron temperatures near the projectile trajectory are calculated. The contribution of the rise in temperature on defect formation and annealing is considered.

A growing need for eco-friendly energy sources have led recently to a frantic search of new compositional systems for photovoltaic applications. The nanocomposite titania-germanium (TiO2-Ge) systems represent a new viable family of optoelectronic materials. Their structural, optical and electronic properties can be easily tailored by customizing the density and size of Ge dots in the TiO2 matrix. Early studies on TiO2-Ge nanocomposites have shown promises for their use as an alternative in photovoltaic applications. In this study we report the TiO2-Ge films synthesis by reactive magnetron co-sputtering. Their properties were evaluated by compositional (EDS), structural (XRD, FTIR) and optical (UV-Vis) characterizations.

Hydroxyapatite (HAp) films, widely used as a biocompatible material for hard tissues repairing. are studied in this paper for a better control and understanding of the crystallization and densification of sol-gel deposited layers. Calcium nitrate and triethyl phosphite diluted in alcohols were used as calcium and phosphorus precursors. HAp coatings were obtained by spinning method, followed by drying and annealing in the range 130-750 degrees C. Specific temperatures of the chemical reactions of HAp formation have been revealed by thermogravimetric analysis (TG-DTA). Structural. chemical and optical characterizations of the films were performed by Scanning Electron Microscopy (SEM) with Energy Dispersive X-ray Analysis (EDX) facilities, X-ray diffraction (XRD). Fourier Transform Infrared Spectroscopy (FTIR) and Spectral Ellipsometry (SE). The film crystallinity increases with file annealing temperature above 550 degrees C. XRD lines of HAp crystallographic planes become narrow at 750 degrees. and correspond to a single crystallographic phase. The Film morphology depends not only on annealing history but also on the synthesis parameters. Thus. layers with large grains of well sinterized HAp nano-crystals can be obtained. Using EDX measurements, the Ca/P ratio was found close to the stoichiometric value in the well sinterized HAp grain regions and slightly increased 1.82 for boundary regions between grains. The density of pores usually observed in sol-gel derived films was estimated for different samples using modeling of SE data.

Bioglass films were prepared by reactive magnetron sputtering from a 45S5 target and than annealed in air tip to 550 T in order to relax the mechanical stresses. The mixtures (0, 7 and 15%) of oxygen and argon were used in order to modify the films stoichiometry. Morphological and compositional studies were performed by SEM coupled with an EDAX system. FTIR and micro Raman measurements were performed in order to investigate the molecular vibrations of the BG structure. A modified composition respect to the target one Was found for all the films, with lower silicon dioxide concentrations. The films displayed rough surfaces with spherical particles of 10-20 mu m diameter embedded in the surfaces. The Raman results evidenced important carbonate lines besides the silica-phosphate bands.

Hydroxyapatite (HA) biocoatings were obtained using two different deposition methods: sol-gel and sputtering. A direct comparison of films obtained using different techniques is necessary because of possible formation of multi-phases and components in HA films. HA films were investigated using spectroscopic ellipsometry (SE) as a powerful method to evaluate composition and structural properties of the films. For both types of films, sputtering and sol-gel, a weak dispersion of the refractive index within the wavelength range 0.4-0.7 pm was found. This corresponds to a high energy bandgap and a high optical transparency in the UV-VIS range. The internal porosity varying in a wide range in the sol-gel films was evaluated using a modeling of SE data. Additionally to SE Studies, structural, chemical and optical characterizations of the Films were performed using Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). Two absorption bands observed in the wavelength ranges 550-600 cm(-1) and 1000-1200 cm(-1) can be attributed to the major absorption modes associated with HA in agreement with published data. Prom XPS analysis, the atom ratio Ca/P was found for sol-gel films close to the stoichiometric value 1.67. For sputtering films, a higher Ca/P ratio of about 2.1 was estimated. However, similar FTIR spectra have been recorded for both sputtering and sol-gel films. XRD Studies show also similar crystallization conditions by annealing at temperatures higher than 500 degrees C. (C) 2008 Elsevier B.V. All rights reserved.

Hydroxyapatite (HAP) thin films (0.2 pm, 0.3 pm and 1.2 mu m thickness) were grown by RF magnetron sputtering in argon atmosphere onto silicon substrates at high deposition rates (0.6 mu m/h). Crystalline HAP films were obtained using a low temperature (100 degrees C) followed by post-deposition annealing at 300 degrees C, 450 degrees C, 500 degrees C and 550 degrees C in environmental air for 1 hour. An important influence of the films thickness upon the crystallization degree was noticed at intermediate annealing temperatures, as obtained from XRD measurements. For low and high temperatures similar values were obtained with a better crystallization degree for the thinner films. FTIR absorption led to the same conclusion considering the shape of stretching and bending PO4 lines. This suggests that the crystallization process has a diffusion component besides usual thermal activation process.

The structure and magnetic properties of films of iron-modified amorphous carbon (a-C:Fe) prepared by magnetron cosputtering of iron and graphite targets are studied. X-ray diffraction measurements show that iron enters the samples in the form of Fe nanocrystals that are typically about 20 nm in size and also forms nanocrystals of hexagonal iron carbide. The temperature dependences of the magnetization, measured under cooling in zero and nonzero magnetic fields, are studied. At temperatures T less than or similar to 8 K, a magnetic transition, which provides evidence for the onset of magnetic ordering in the material, is observed to occur. The magnetization isotherms obtained in the 8- to 20-K temperature range are in agreement with this observation. It is shown that a modified version of Langevin's formalism adequately describes the observed features of a-C:Fe film magnetization. (c) 2005 Pleiades Publishing, Inc.