J. P. Leitão

Influence of the layer thickness in plasmonic gold nanoparticles produced by thermal evaporation

Metallic nanoparticles (NPs) have received recently considerable interest of photonic and photovoltaic communities. In this work, we report the optoelectronic properties of gold NPs (Au-NPs) obtained by depositing very thin gold layers on glass substrates through thermal evaporation electron-beam assisted process. The effect of mass thickness of the layer was evaluated. The polycrystalline Au-NPs, with grain sizes of 14 and 19 nm tend to be elongated in one direction as the mass thickness increase. A 2 nm layer deposited at 250°C led to the formation of Au-NPs with 10-20 nm average size, obtained by SEM images, while for a 5 nm layer the wide size elongates from 25 to 150 nm with a mean at 75 nm. In the near infrared region was observed an absorption enhancement of amorphous silicon films deposited onto the Au-NPs layers with a corresponding increase in the PL peak for the same wavelength region.

Hopping conduction and persistent photoconductivity in Cu2ZnSnS4 thin films

The temperature dependence of electrical conductivity and the photoconductivity of polycrystalline Cu2ZnSnS4 were investigated. It was found that at high temperatures the electrical conductivity was dominated by band conduction and nearest-neighbour hopping. However, at lower temperatures, both Mott variable-range hopping (VRH) and Efros?Shklovskii VRH were observed. The analysis of electrical transport showed high doping levels and a large compensation ratio, demonstrating large degree of disorder in Cu2ZnSnS4. Photoconductivity studies showed the presence of a persistent photoconductivity effect with decay time increasing with temperature, due to the presence of random local potential fluctuations in the Cu2ZnSnS4 thin film. These random local potential fluctuations cannot be attributed to grain boundaries but to the large disorder in Cu2ZnSnS4.

Thermodynamic pathway for the formation of SnSe and SnSe2 polycrystalline thin films by selenization of metal precursors

In this work, tin selenide thin films (SnSex) were grown on soda lime glass substrates by selenization of dc magnetron sputtered Sn metallic precursors. Selenization was performed at maximum temperatures in the range 300 °C to 570 °C. The thickness and the composition of the films were analysed using step profilometry and energy dispersive spectroscopy, respectively. The films were structurally and optically investigated by X-ray diffraction, Raman spectroscopy and optical transmittance and reflectance measurements. X-Ray diffraction patterns suggest that for temperatures between 300 °C and 470 °C, the films are composed of the hexagonal-SnSe2 phase. By increasing the temperature, the films selenized at maximum temperatures of 530 °C and 570 °C show orthorhombic-SnSe as the dominant phase with a preferential crystal orientation along the (400) crystallographic plane. Raman scattering analysis allowed the assignment of peaks at 119 cm−1 and 185 cm−1 to the hexagonal-SnSe2 phase and those at 108 cm−1, 130 cm−1 and 150 cm−1 to the orthorhombic-SnSe phase. All samples presented traces of condensed amorphous Se with a characteristic Raman peak located at 255 cm−1. From optical measurements, the estimated band gap energies for hexagonal-SnSe2 were close to 0.9 eV and 1.7 eV for indirect forbidden and direct transitions, respectively. The samples with the dominant orthorhombic-SnSe phase presented estimated band gap energies of 0.95 eV and 1.15 eV for indirect allowed and direct allowed transitions, respectively.

Comparison of fluctuating potentials and donor-acceptor pair transitions in a Cu-poor Cu2ZnSnS4 based solar cell

The structure of the electronic energy levels of a single phase Cu2ZnSnS4 film, as confirmed by Raman Scattering and x-ray diffraction, is investigated through a dependence on the excitation power of the photoluminescence (PL). The behavior of the observed asymmetric band, with a peak energy at ∼1.22 eV, is compared with two theoretical models: (i) fluctuating potentials and (ii) donor-acceptor pair transitions. It is shown that the radiative recombination channels in the Cu-poor film are strongly influenced by tail states in the bandgap as a consequence of a heavy doping and compensation levels. The contribution of the PL for the evaluation of secondary phases is also highlighted.

Structural and optical characterization of Mg-doped GaAs nanowires grown on GaAs and Si substrates

We report an investigation on the morphological, structural, and optical properties of large size wurtzite GaAs nanowires, low doped with Mg, grown on GaAs(111)B and Si(111) substrates. A higher density of vertical nanowires was observed when grown upon GaAs(111)B. Very thin zinc-blende segments are observed along the axis of the nanowires with a slightly higher linear density being found on the nanowires grown on Si(111). Low temperature cathodoluminescence and photoluminescence measurements reveal an emission in the range 1.40–1.52 eV related with the spatial localization of the charge carriers at the interfaces of the two crystalline phases. Mg related emission is evidenced by cathodoluminescence performed on the GaAs epilayer. However, no direct evidence for a Mg related emission is found for the nanowires. The excitation power dependency on both peak energy and intensity of the photoluminescence gives a clear evidence for the type II nature of the radiative transitions. From the temperature dependence on the photoluminescence intensity, non-radiative de-excitation channels with different activation energies were found. The fact that the estimated energies for the escape of the electron are higher in the nanowires grown on Si(111) suggests the presence of wider zinc-blende segments.

Hydrogen plasma treatment of very thin p-type nanocrystalline Si films grown by RF-PECVD in the presence of B(CH3)3

Abstract We have characterized the structure and electrical properties of p-type nanocrystalline silicon films prepared by radio-frequency plasma-enhanced chemical vapor deposition and explored optimization methods of such layers for potential applications in thin-film solar cells. Particular attention was paid to the characterization of very thin (∼20 nm) films. The cross-sectional morphology of the layers was studied by fitting the ellipsometry spectra using a multilayer model. The results suggest that the crystallization process in a high-pressure growth regime is mostly realized through a subsurface mechanism in the absence of the incubation layer at the substrate-film interface. Hydrogen plasma treatment of a 22-nm-thick film improved its electrical properties (conductivity increased more than ten times) owing to hydrogen insertion and Si structure rearrangements throughout the entire thickness of the film.

New insights into the temperature-dependent photoluminescence of Mg-doped GaAs nanowires and epilayers

The intentional introduction of impurities in semiconductor nanowires is very important in view of device applications. Doping affects the electronic energy level structure which in the case of III–V nanowires can also be strongly influenced by the simultaneous occurrence of two polytypes, zinc-blende (ZB) and wurtzite (WZ). In this work, we report a study on GaAs nanowires with different Mg-acceptor doping levels through temperature dependent photoluminescence. A comparable investigation is presented for Mg-doped GaAs epilayers. For the later, only a band is observed which is ascribed to the involvement of the Mg acceptor due to the observed bandgap energy narrowing effect with increasing the doping level, and the temperature dependent behaviour. A different behaviour is reported for nanowires: several radiative transitions are observed whose temperature dependence follows that of bulk GaAs, in accordance with spatially indirect recombination. Although the polytypic regions mask the role of doping in nanowires it favours the charge separation required for photovoltaic applications.

Photoconduction in tunnel-coupled Ge/Si quantum dot arrays

The photoconduction in a tunnel-coupled Ge/Si quantum dot (QD) array has been studied. The photoconductance (PC) sign can be either positive or negative, depending on the initial filling of QDs with holes. The PC kinetics has a long-term character (102−104 s at T = 4.2 K) and is accompanied by persistent photoconduction (PPC), whereby the PC value is not restored on the initial level even after relaxation for several hours. These phenomena are observed upon illumination by light with photon energies both greater and smaller than the silicon bandgap. A threshold light wavelength corresponding to a long-term PC kinetics depends on the QD filling with holes. A model describing the observed PC kinetics is proposed, according to which the main contribution to the PC is related to the degree of QD filling with holes. By applying the proposed model to the analysis of PC kinetics at various excitation levels, it is possible to determine the dependence of the hopping conductance on the number of holes per QD. The rate of the charge carrier density relaxation exponentially depends on the carrier density.

Ag and Sn Nanoparticles to Enhance the Near-Infrared Absorbance of a-Si:H Thin Films

Silver (Ag) and tin (Sn) nanoparticles (NPs) were deposited by thermal evaporation onto heated glass substrates with a good control of size, shape and surface coverage. This process has the advantage of allowing the fabrication of thin-film solar cells with incorporated NPs without vacuum break, since it does not require chemical processes or post-deposition annealing. The X-ray diffraction, TEM and SEM properties are correlated with optical measurements and amorphous silicon hydrogenated (a-Si:H) films deposited on top of both types of NPs show enhanced absorbance in the near-infrared. The results are interpreted with electromagnetic modelling performed with Mie theory. A broad emission in the near-infrared region is considerably increased after covering the Ag nanoparticles with an a-Si:H layer. Such effect may be of interest for possible down-conversion mechanisms in novel photovoltaic devices.

Cd and Cu Interdiffusion in Cu(In, Ga)Se 2 /CdS Hetero-Interfaces

We report a detailed characterization of an industry-like prepared Cu(In, Ga)Se2 (CIGS)/CdS heterojunction by scanning transmission electron microscopy and photoluminescence (PL). Energy dispersive X-ray spectroscopy shows the presence of several regions in the CIGS layer that are Cu deprived and Cd enriched, suggesting the segregation of Cd–Se. Concurrently, the CdS layer shows Cd-deprived regions with the presence of Cu, suggesting a segregation of Cu–S. The two types of segregations are always found together, which, to the best of our knowledge, is observed for the first time. The results indicate that there is a diffusion process that replaces Cu with Cd in the CIGS layer and Cd with Cu in the CdS layer. Using a combinatorial approach, we identified that this effect is independent of focused-ion beam sample preparation and of the transmission electron microscopy grid. Furthermore, PL measurements before and after an HCl etch indicate a lower degree of defects in the postetch sample, compatible with the segregates removal. We hypothesize that Cu