Enhancing SiGeSn nanocrystals SWIR photosensing by high passivation in nanocrystalline HfO2 matrix.

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 °C. RTA was performed to obtain SiGeSn NCs with surfaces passivated by the embedding HfO2 matrix. The formation of NCs and ß-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.

A Two-Step Magnetron Sputtering Approach for the Synthesis of Cu2ZnSnS4 Films from Cu2SnS3\ZnS Stacks.

Cu2ZnSnS4 (CZTS) is regarded as one of the emerging materials for next-generation thin film solar cells. However, its synthesis is complex, and obtaining a single-phase CZTS thin film is difficult. This work reports the elaboration of Cu2ZnSnS4 thin films by a sequential magnetron sputtering deposition of Cu2SnS3 (CTS) and ZnS as stacked films. Initially, the CTS films were prepared on a soda lime glass substrate by annealing Cu and SnS2 stacked layers. Second, ZnS was deposited by magnetron sputtering on the CTS films. The CTS\ZnS stacks were then annealed in Sn + S or S atmospheres. The tetragonal CZTS structure was obtained and confirmed by grazing incidence X-ray diffraction and Raman spectroscopy. The morphological and compositional characteristics, measured by scanning electron microscopy and energy-dispersive spectroscopy, revealed large grains and dense surfaces with the elemental composition close to the intended stoichiometry. Additional X-ray photoemission spectroscopy measurements were performed to determine the surface chemistry and particularities of the obtained films. The optical properties, determined using conventional spectroscopy, showed optimal absorber layer band gap values ranging between 1.38 and 1.50 eV. The electrical measurements showed that all the films are p-type with high carrier concentrations in the range of 1015 to 1020 cm-3. This new synthesis route for CZTS opens the way to obtain high-quality films by an industry-compatible method.

Effects of Solvent Additive and Micro-Patterned Substrate on the Properties of Thin Films Based on P3HT:PC70BM Blends Deposited by MAPLE.

Lately, there is a growing interest in organic photovoltaic (OPV) cells due to the organic materials' properties and compatibility with various types of substrates. However, their efficiencies are low relative to the silicon ones; therefore, other ways (i.e., electrode micron/nanostructuring, synthesis of new organic materials, use of additives) to improve their performances are still being sought. In this context, we studied the behavior of the common organic bulk heterojunction (P3HT:PC70BM) deposited by matrix-assisted pulsed laser evaporation (MAPLE) with/without 0.3% of 1,8-diiodooctane (DIO) additive on flat and micro-patterned ITO substrates. The obtained results showed that in the MAPLE process, a small quantity of additive can modify the morphology of the organic films and decrease their roughness. Besides the use of the additive, the micro-patterning of the electrode leads to a greater increase in the absorption of the studied photovoltaic structures. The inferred values of the filling factors for the measured cells in ambient conditions range from 19% for the photovoltaic structures with no additive and without substrate patterning to 27% for the counterpart structures with patterning and a small quantity of additive.

GeSi Nanocrystals Photo-Sensors for Optical Detection of Slippery Road Conditions Combining Two Classification Algorithms.

One of the key elements in assessing traffic safety on the roads is the detection of asphalt conditions. In this paper, we propose an optical sensor based on GeSi nanocrystals embedded in SiO2 matrix that discriminates between different slippery road conditions (wet and icy asphalt and asphalt covered with dirty ice) in respect to dry asphalt. The sensor is fabricated by magnetron sputtering deposition followed by rapid thermal annealing. The photodetector has spectral sensitivity in the 360-1350 nm range and the signal-noise ratio is 102-103. The working principle of sensor setup for detection of road conditions is based on the photoresponse (photocurrent) of the sensor under illumination with the light reflected from the asphalt having different reflection coefficients for dry, wet, icy and dirty ice coatings. For this, the asphalt is illuminated sequentially with 980 and 1064 nm laser diodes. A database of these photocurrents is obtained for the different road conditions. We show that the use of both k-nearest neighbor and artificial neural networks classification algorithms enables a more accurate recognition of the class corresponding to a specific road state than in the case of using only one algorithm. This is achieved by comparing the new output sensor data with previously classified data for each algorithm and then by performing an intersection of the algorithms' results.

SiGe nanocrystals in SiO2 with high photosensitivity from visible to short-wave infrared.

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.

Fabrication and characterization of Si1- x Ge x nanocrystals in as-grown and annealed structures: a comparative study.

Multilayer structures comprising of SiO2/SiGe/SiO2 and containing SiGe nanoparticles were obtained by depositing SiO2 layers using reactive direct current magnetron sputtering (dcMS), whereas, Si and Ge were co-sputtered using dcMS and high-power impulse magnetron sputtering (HiPIMS). The as-grown structures subsequently underwent rapid thermal annealing (550-900 °C for 1 min) in N2 ambient atmosphere. The structures were investigated using X-ray diffraction, high-resolution transmission electron microscopy together with spectral photocurrent measurements, to explore structural changes and corresponding properties. It is observed that the employment of HiPIMS facilitates the formation of SiGe nanoparticles (2.1 ± 0.8 nm) in the as-grown structure, and that presence of such nanoparticles acts as a seed for heterogeneous nucleation, which upon annealing results in the periodically arranged columnar self-assembly of SiGe core-shell nanocrystals. An increase in photocurrent intensity by more than an order of magnitude was achieved by annealing. Furthermore, a detailed discussion is provided on strain development within the structures, the consequential interface characteristics and its effect on the photocurrent spectra.

Rapid thermal annealing for high-quality ITO thin films deposited by radio-frequency magnetron sputtering.

In this work, rapid thermal annealing (RTA) was applied to indium tin oxide (ITO) films in ambient atmosphere, resulting in significant improvements of the quality of the ITO films that are commonly used as conductive transparent electrodes for photovoltaic structures. Starting from a single sintered target (purity 99.95%), ITO thin films of predefined thickness (230 nm, 300 nm and 370 nm) were deposited at room temperature by radio-frequency magnetron sputtering (rfMS). After deposition, the films were subjected to a RTA process at 575 °C (heating rate 20 °C/s), maintained at this temperature for 10 minutes, then cooled down to room temperature at a rate of 20 °C/s. The film structure was modified by changing the deposition thickness or the RTA process. X-ray diffraction investigations revealed a cubic nanocrystalline structure for the as-deposited ITO films. After RTA, polycrystalline compounds with a textured (222) plane were observed. X-ray photon spectroscopy was used to confirm the beneficial effect of the RTA treatment on the ITO chemical composition. Using a Tauc plot, values of the optical band gap ranging from 3.17 to 3.67 eV were estimated. These values depend on the heat treatment and the thickness of the sample. Highly conductive indium tin oxide thin films (ρ = 7.4 × 10-5 Ω cm) were obtained after RTA treatment in an open atmosphere. Such films could be used to manufacture transparent contact electrodes for solar cells.

Ge nanoparticles in SiO2 for near infrared photodetectors with high performance.

In this work we prepared films of amorphous germanium nanoparticles embedded in SiO2 deposited by magnetron sputtering on Si and quartz heated substrates at 300, 400 and 500 °C. Structure, morphology, optical, electrical and photoconduction properties of all films were investigated. The Ge concentration in the depth of the films is strongly dependent on the deposition temperature. In the films deposited at 300 °C, the Ge content is constant in the depth, while films deposited at 500 °C show a significant decrease of Ge content from interface of the film with substrate towards the film free surface. From the absorption curves we obtained the Ge band gap of 1.39 eV for 300 °C deposited films and 1.44 eV for the films deposited at 500 °C. The photocurrents are higher with more than one order of magnitude than the dark ones. The photocurrent spectra present different cutoff wavelengths depending on the deposition temperature, i.e. 1325 nm for 300 °C and 1267 nm for 500 °C. These films present good responsivities of 2.42 AW-1 (52 µW incident power) at 300 °C and 0.69 AW-1 (57 mW) at 500 °C and high internal quantum efficiency of ∼445% for 300 °C and ∼118% for 500 °C.

Magnetism and magnetoresistance of single Ni-Cu alloy nanowires.

Arrays of magnetic Ni-Cu alloy nanowires with different compositions were prepared by a template-replication technique using electrochemical deposition into polycarbonate nanoporous membranes. Photolithography was employed for obtaining interdigitated metallic electrode systems of Ti/Au onto SiO2/Si substrates and subsequent electron beam lithography was used for contacting single nanowires in order to investigate their galvano-magnetic properties. The results of the magnetoresistance measurements made on single Ni-Cu alloy nanowires of different compositions have been reported and discussed in detail. A direct methodology for transforming the magnetoresistance data into the corresponding magnetic hysteresis loops was proposed, opening new possibilities for an easy magnetic investigation of single magnetic nanowires in the peculiar cases of Stoner-Wohlfarth-like magnetization reversal mechanisms. The magnetic parameters of single Ni-Cu nanowires of different Ni content have been estimated and discussed by the interpretation of the as derived magnetic hysteresis loops via micromagnetic modeling. It has been theoretically proven that the proposed methodology can be applied over a large range of nanowire diameters if the measurement geometry is suitably chosen.

Nanostructured germanium deposited on heated substrates with enhanced photoelectric properties.

Obtaining high-quality materials, based on nanocrystals, at low temperatures is one of the current challenges for opening new paths in improving and developing functional devices in nanoscale electronics and optoelectronics. Here we report a detailed investigation of the optimization of parameters for the in situ synthesis of thin films with high Ge content (50 %) into SiO2. Crystalline Ge nanoparticles were directly formed during co-deposition of SiO2 and Ge on substrates at 300, 400 and 500 °C. Using this approach, effects related to Ge-Ge spacing are emphasized through a significant improvement of the spatial distribution of the Ge nanoparticles and by avoiding multi-step fabrication processes or Ge loss. The influence of the preparation conditions on structural, electrical and optical properties of the fabricated nanostructures was studied by X-ray diffraction, transmission electron microscopy, electrical measurements in dark or under illumination and response time investigations. Finally, we demonstrate the feasibility of the procedure by the means of an Al/n-Si/Ge:SiO2/ITO photodetector test structure. The structures, investigated at room temperature, show superior performance, high photoresponse gain, high responsivity (about 7 AW-1), fast response time (0.5 µs at 4 kHz) and great optoelectronic conversion efficiency of 900% in a wide operation bandwidth, from 450 to 1300 nm. The obtained photoresponse gain and the spectral width are attributed mainly to the high Ge content packed into a SiO2 matrix showing the direct connection between synthesis and optical properties of the tested nanostructures. Our deposition approach put in evidence the great potential of Ge nanoparticles embedded in a SiO2 matrix for hybrid integration, as they may be employed in structures and devices individually or with other materials, hence the possibility of fabricating various heterojunctions on Si, glass or flexible substrates for future development of Si-based integrated optoelectronics.

Nanostructuring of GeTiO amorphous films by pulsed laser irradiation.

Laser pulse processing of surfaces and thin films is a useful tool for amorphous thin films crystallization, surface nanostructuring, phase transformation and modification of physical properties of thin films. Here we show the effects of nanostructuring produced at the surface and under the surface of amorphous GeTiO films through laser pulses using fluences of 10-30 mJ/cm(2). The GeTiO films were obtained by RF magnetron sputtering with 50:50 initial atomic ratio of Ge:TiO2. Laser irradiation was performed by using the fourth harmonic (266 nm) of a Nd:YAG laser. The laser-induced nanostructuring results in two effects, the first one is the appearance of a wave-like topography at the film surface, with a periodicity of 200 nm and the second one is the structure modification of a layer under the film surface, at a depth that is related to the absorption length of the laser radiation. The periodicity of the wave-like relief is smaller than the laser wavelength. In the modified layer, the Ge atoms are segregated in spherical amorphous nanoparticles as a result of the fast diffusion of Ge atoms in the amorphous GeTiO matrix. The temperature estimation of the film surface during the laser pulses shows a maximum of about 500 °C, which is much lower than the melting temperature of the GeTiO matrix. GeO gas is formed at laser fluences higher than 20 mJ/cm(2) and produces nanovoids in the laser-modified layer at the film surface. A glass transition at low temperatures could happen in the amorphous GeTiO film, which explains the formation of the wave-like topography. The very high Ge diffusivity during the laser pulse action, which is characteristic for liquids, cannot be reached in a viscous matrix. Our experiments show that the diffusivity of atomic and molecular species such as Ge and GeO is very much enhanced in the presence of the laser pulse field. Consequently, the fast diffusion drives the formation of amorphous Ge nanoparticles through the segregation of Ge atoms in the GeTiO matrix. The nanostructuring effects induced by the laser irradiation can be used in functionalizing the surface of the films.

Electrical behavior of multi-walled carbon nanotube network embedded in amorphous silicon nitride.

The electrical behavior of multi-walled carbon nanotube network embedded in amorphous silicon nitride is studied by measuring the voltage and temperature dependences of the current. The microstructure of the network is investigated by cross-sectional transmission electron microscopy. The multi-walled carbon nanotube network has an uniform spatial extension in the silicon nitride matrix. The current-voltage and resistance-temperature characteristics are both linear, proving the metallic behavior of the network. The I-V curves present oscillations that are further analyzed by computing the conductance-voltage characteristics. The conductance presents minima and maxima that appear at the same voltage for both bias polarities, at both 20 and 298 K, and that are not periodic. These oscillations are interpreted as due to percolation processes. The voltage percolation thresholds are identified with the conductance minima.