Rodrigo Martins

The charge transfer dynamics at interfaces are fundamental to know the mechanism of photovoltaic processes. The internal potential in solar cell devices depends on the basic processes of photovoltaic effect such as charge carrier generation, separation, transport, recombination, etc. Here we report the direct observation of the surface potential depth profile over the cross-section of the ZnO nanorods/Cu2O based solar cell for two different layer thicknesses at different wavelengths of light using Kelvin probe force microscopy. The topography and phase images across the cross-section of the solar cell are also observed, where the interfaces are well-defined on the nanoscale. The potential profiling results demonstrate that under white light illumination, the photoinduced electrons in Cu2O inject into ZnO due to the interfacial electric field, which results in the large difference in surface potential between two active layers. However, under a single wavelength illumination, the charge carrier generation, separation, and transport processes between two active layers are limited, which affect the surface potential images and corresponding potential depth profile. Because of changes in the active layer thicknesses, small variations have been observed in the charge carrier transport mechanism inside the device. These results provide the clear idea about the charge carrier distribution inside the solar cell in different conditions and show the perfect illumination condition for large carrier transport in a high performance solar cell. © 2016 American Chemical Society.

High visible to near infrared (NIR) transparent Mo (0-1 at%) doped In2O3 (IMO) thin films with high carrier mobility were deposited on Corning-1737 glass substrates at 400 °C by spray pyrolysis experimental technique. The films were annealed in vacuum (∼1×10-4 mbar) at 550 °C for 45 min. XRD analysis confirmed that indium oxide belongs to cubic bixbyite structure. The preferred growth orientation along (2 2 2) plane for low Mo doping level shifts to (4 0 0) for higher Mo doping levels. Crystallite sizes extracted from the XRD data corroborate the changes in full-width at half-maximum due to the variation in Mo doping. Scanning electron microscopy study illustrates the evolution in surface microstructures as a function of Mo doping. The negative sign of Hall coefficient confirmed n-type conductivity. Films with high mobility of ∼149 cm2/(V s), carrier concentration of ∼1.0×1020 cm-3, resistivity of ∼4.0×10-4 Ω cm and high figure of merit of ∼1.02×10-2 Ω-1 were observed for post-annealed films (0.5 at% Mo). The obtained high average transparency of ∼83% in the wavelength range 400-2500 nm confirms that transmittance is well extended into the NIR region. © 2009 Elsevier B.V. All rights reserved.

The high visible-near infrared transparent and high carrier mobility (μ) Mo doped (0.5 at%) indium oxide (IMO) films were deposited by the spray pyrolysis technique. The deposited films were irradiated by 50MeV Li 3+ ions with different fluences of 1×1011, 1×1012 and 1×1013 ions cm-2. X-ray diffraction analysis confirmed the cubic bixbyite structure of indium oxide. A fascinating feature is that the ion irradiation process has introduced a fraction of the molybdenum oxide phase. The μ of as-deposited IMO films is decreased from ̃122.4 to 93.3 cm2 V-1 s-1, following the ion irradiation. The theoretically calculated μ and carrier density values were correlated with those measured experimentally. The transport mechanism has been analysed based on the ionized and neutral impurity scattering centres. The average transmittance (400-2500 nm) of the as-deposited IMO films is decreased from 83% to 60% following irradiation. © 2011 IOP Publishing Ltd.

Molybdenum doped indium oxide (IMO) thin films were deposited on the glass substrates preheated to 450 °C by spray pyrolysis technique. The Mo doping was varied between 0 and 2.0 at.%. The films were characterized by their structural, electrical and optical properties. The films are confirmed to be cubic bixbyite In2O3 with a strongest orientation along (222) plane, which is shifted to (400) plane for the increase in Mo doping to 1.25 and 2 at.%. The film deposited with 0.5 at.% Mo doping shows high mobility of 76.9 cm2V- 1s- 1 , resistivity of 1.8 × 10- 3 Ω-cm and high carrier concentration of 4.6 × 1019 cm- 3 with 81.3% transmittance in the visible range between 500 and 800 nm. Further, the transparency extents well into the near-IR range. © 2008 Elsevier B.V. All rights reserved.

Molybdenum doped (0-1 at. %) indium oxide thin films with high near infrared (NIR) transparency and carrier mobility were deposited on Corning-1737 glass substrates at 400 °C by spray pyrolysis experimental technique. Films with mobility as high as ∼149 cm2 /V s were obtained when annealed in vacuum at 550 °C, which also possess carrier concentration of ∼1× 1020 cm-3 and resistivity as low as ∼4.0× 10-4 cm. Further, both the average visible transmittance (500-800 nm) and the average NIR transmittance are >83%. This clearly shows that the transmittance is extended well into the NIR region. © 2009 American Institute of Physics.

Molybdenum (0-1 at. %) doped indium oxide thin films with high near-infrared (NIR) transparency and high carrier mobility were deposited on Corning-1737 glass substrates at 400 °C by a spray pyrolysis experimental technique. X-ray diffraction (XRD) analysis confirmed the cubic bixbyite structure of indium oxide. The preferred growth orientation along the (222) plane for the low Mo doping level (0.5 at. %) shifts to (400) for higher Mo doping levels (<0.6 at. %). The crystallite size extracted from the XRD data corroborates the changes in full width at half maximum due to the variation in Mo doping. A scanning electron microscopy study illustrated the evolution in the surface microstructure as a function of Mo doping. The negative sign of the Hall coefficient confirmed the n -type conductivity. A high carrier mobility of ∼122.4 cm2 /V s, a carrier concentration of ∼9.5× 1019 cm-3, a resistivity of ∼5.3× 10-4cm, and a high figure of merit of ∼4.2× 10-2 -1 are observed for the films deposited with 0.5 at. % Mo. The obtained high average transparency of ∼83% in the wavelengths ranging from 400 to 2500 nm confirmed the extension of transmittance well into the NIR region. © 2009 American Institute of Physics.

Molybdenum doped indium oxide (IO) thin films were deposited on the Coring F1737 glass substrates at 400 °C by spray pyrolysis technique. TheModoping was varied between 0 and 4 at.%. The films were characterized by their structural, electrical and optical properties. The films are confirmed to be cubic bixbyite In 2O 3 with a strongest orientation along (222) for 0.5 at.% Mo, which is shifted to (400) plane when the Mo doping is increased to ≥1.2 at.%. The films deposited with 0.5 at.% Mo showed high mobility of ̃90 cm 2/Vs, resistivity of ̃6.8×10 -4ωcm and carrier concentration of ̃1.01× 1020 cm -3 with >̃73% transmittance in the visible range between 500 and 800 nm. The transmittance is well extended into near infrared region.

This paper deals with high transparent and high conductive oxides based on polycrystalline titanium (Ti) doped (0.5-3 at.%) indium oxide (IO) thin films produced on glass substrates at 400 °C by spray pyrolysis technique. X-ray diffraction analysis confirmed the cubic bixbyite structure of indium oxide. A high mobility of ∼ 97 cm2 V- 1 s- 1, a carrier concentration of ∼ 1.55 × 1020 cm- 3 and a resistivity of ∼ 4.11 × 10- 4 Ω-cm with ∼ 83% of transmittance in the wavelength ranging between 400 and 2500 nm were obtained for 2 at.% Ti doping films, rivalling so to the best known transparent conducting oxide based on indium tin oxide. Moreover, the transmittance in the broad wavelength ranging between 400 and 2500 nm is over 83%, leading so to an increasing carrier generation towards the near infrared region of the spectrum, as required for applications such as solar cells. We also notice that increasing the doping concentration widened the optical band gap and caused a small Burstein-Moss shift, due to mobility decrease, as expected. © 2012 Published by Elsevier B.V.

Molybdenum-doped indium oxide (IMO) thin films were deposited at 450 °C for varying molybdenum concentrations in the range of 0.5-2 at% by the spray pyrolysis technique. These films confirmed the cubic bixbyite structure of polycrystalline In2O3. The preferred growth orientation along the (2 2 2) plane shifts to (4 0 0) on higher Mo doping levels. The films doped with 0.5 at% Mo showed high mobility of 76.9 cm2/(V s). The high visible transmittance extends well into the near-infrared region. A possibility of using the produced IMO films in nanocrystalline (nc) silicon solar cell applications is discussed in this article. The morphological studies showed a change in the microstructure, which is consistent with the change in crystallographic orientation. © 2008 Elsevier B.V. All rights reserved.

In this work, we report results concerning the performances of thin-film transistors (TFTs) where the channel layer is based on microcrystalline zinc tin oxide (ZTO) processed by spray pyrolysis technique. TFTs made with 30 nm thick ZTO channel layer deposited at a substrate temperature of 400 C and 300 Cexhibited, respectively, a saturation mobility of 2.9 cm V s and 1.45 cm V s ; voltage of 0.15 V, and 0.2 V; a sub-threshold swing of 400 mV/dec and 500 mV/dec; ON/OFF ratio at the onset of hard saturation current of 3.5 10 and 6 10 , for a drain to source voltage of 10 V (close to or below the gate to source voltage). This indicates that the substrate temperature is relevant in determining the devices' electronic performances. © 2013 IEEE.

Shape memory alloys (SMA) represents a class of metallic materials that has the capability of recovering a previously defined initial shape when subject to an adequate thermomechanical treatment. The present work aims to study the influence of thermal cycles on the transition temperatures of a Ni-Ti alloy. In this system, small variations around the equiatomic composition give rise to significant transformation temperature variations ranging from 173 to 373 K. SMA usually presents the shape memory effect after an annealing treatment at ca. 973 K. The optimisation of the thermomechanical treatment will allow to "tune" the material to different transformation temperature ranges from the same starting material, just by changing the processing conditions. Differential scanning calorimeter (DSC) and in situ high-temperature X-ray diffraction (XRD) have been used to identify the transformation temperatures and the phases that are present after different thermal cycles. The results concerning a series of thermal cycles with different heating and cooling rates (from 1.67×10-2 to 1.25×10-1 K/s) and different holding temperatures (from 473 to 1033 K) are presented. © 2004 Elsevier B.V. All rights reserved.

Here we present for the first time a TiO2/Cu2O all-oxide heterojunction solar cell entirely produced by spray pyrolysis onto fluorine doped tin oxide (FTO) covered glass substrates, using silver as a back contact. A combinatorial approach was chosen to investigate the impact of the TiO2 window layer and the Cu2O light absorber thicknesses. We observe an open circuit voltage up to 350 mV and a short circuit current density which is strongly dependent of the Cu2O thickness, reaching a maximum of  0.4 mA/cm2. Optical investigation reveals that a thickness of 300 nm spray pyrolysis deposited Cu2O is sufficient to absorb most photons with an energy above the symmetry allowed optical transition of 2.5 eV, indicating that the low current densities are caused by strong recombination in the absorber that consists of small Cu2O grains. © 2014 Elsevier Ltd. All rights reserved.

Hafnium oxide-aluminum oxide (HfAlO) dielectric films were cosputtered using HfO2 and Al2 O3 targets, and their properties are studied in comparison with pure HfO2 films. The X-ray diffraction studies confirmed that the HfO2 films are nanocrystalline with a monoclinic phase. The as-deposited HfAlO films with a chemical composition of (HfO2) 0.86 (Al2 O3) 0.14 are amorphous even after annealing at 500°C. Further, the cosputtered films show a slight reduction in leakage current. The leakage current density may be significantly reduced below 3× 10-10 A cm-2 at an electric field of 0.25 MV/cm when applying the proper radio-frequency bias to the substrate. © 2009 The Electrochemical Society.

In this paper we present results concerning the optimisation of the electronic and mechanical properties presented by amorphous silicon (a-Si:H) thin films produced on polyimide (Kapton® VN) substrates with different thicknesses (25, 50 and 75 μm) by the plasma enhanced chemical vapour deposition (PECVD) technique. The purpose of this study is to obtain a low defect density as well as low residual stresses (specially at the interface) in order to provide good performances for large area (10 mm wide by 80 mm long) flexible position sensitive detectors. The electrical and optical properties presented by the films will be correlated to the sensor characteristics. The properties of samples have been measured by dark/photoconductivity, constant photocurrent measurements (CPM) and the results have been compared with films deposited on Corning 7059 glass substrates during the same run deposition. The residual stresses were measured using an active optical triangulation and angle resolved scattering. The preliminary results indicate that the thinner polymeric substrate with 25 μm presents the highest density of states, which is associated to the residual stresses and strains associated within the film. © 2002 Elsevier Science B.V. All rights reserved.

In this work metal induced crystallization (MIC) using nickel (Ni) was employed to obtain poly-Si by crystallization of amorphous films for application as active layer in TFTs. Ni layers with thicknesses of 0.5 nm, 1 nm and 2 nm were used to crystallize the silicon. The TFTs were produced with a bottom gate configuration using a multi-layer Al2O3/TiO2 insulator produced by atomic layer deposition (ALD) as gate dielectric. The best performances of the TFT produced were obtained when using very thin Ni layers for the crystallization. This is attributed to a lower metal contamination and to the enhancement of grain size, as a result of the lower nucleation density achieved, when using the thinnest Ni layer. Devices that exhibit effective mobility of 45.5 cm2V-1s-1 and an on/off ratio of 5.55×104 were produced using a 0.5 nm Ni layer to crystallize the active channel area.

The aim of this paper is to study the role of gold (Au) induced crystallization on amorphous silicon (a-Si) films produced by low pressure chemical vapor deposition (LPCVD) at low process temperatures (550 °C) to allow the use of glass substrates. Concerning the crystallization process Au was deposited by e-beam thermal evaporation over the silicon (Si), using different metal thickness, from 5 to 100 Å. The samples were then annealed at 450, 500 and 550 °C and the crystallization time was changed from 5 up to 30 h. The structure of the films was analyzed by X-ray diffraction (XRD) and spectroscopic ellipsometry (SE) while electrical conductivity measurements were performed to obtain the electrical properties of the films produced, namely the activation energy (EA) and how it changes with the Au thickness used. The data achieved show that the increase of the metal layer thickness decreases the time needed to get full crystallization. However this leads to lower conduction activation energy (EA) meaning that there is also an increase of Au incorporation that leads to the production of doped films. © 2004 Elsevier B.V. All rights reserved.

This paper deals with the role the substrate on the structure of undoped and n-doped polycrystalline silicon (poly-Si) films produced by Low Pressure Chemical Vapour Deposition (LPCVD). The structural and electrical properties of the films deposited on glass, glass covered with molybdenum (Mo), oxidised crystalline silicon and oxidised crystalline silicon covered with Mo were analysed using X-ray diffraction and Spectroscopic Ellipsometry, dark conductivity and Hall effect measurements. Undoped poly-Si films deposited over Mo present modifications in the crystalline structure relatively to those deposited on the other substrates. The presence of Mo changes the preferential growth orientation, enhancing the Si {111} grains orientation, leading to more compact films. The electrical measurements also confirm that the films grown on Mo substrates present better characteristics. Some differences are also observed during the initial growth stages when using glass or oxidised silicon. Very thin n-doped films present a less effective doping effect when deposited on oxidised silicon than the ones deposited on glass substrates.

In this paper a new approach is presented for the simulation of spectroscopic ellipsometry (SE) data to estimate the level of nickel (Ni) contamination in silicon crystallized by metal induced crystallization (MIC). The method employs the addition of Ni as reference for a Bruggemann effective medium approximation (BEMA) to simulate the optical response of the crystallized silicon. This new approach is sensitive to changes in the initial average metal thickness used on the crystallization process to thickness values as low as 0.05 nm. This corresponds to a volume fraction of 0.24%, confirmed by Rutherford backscattering spectrometry (RBS) where it was observed that the Ni volume fraction detected by SE varies linearly with the metal amount inside the crystallized films determined by RBS. © 2008.

The aim of this work is to present a spectroscopic ellipsometry study focused on the annealing time effect on nickel metal induced crystallization of amorphous silicon thin films. For this purpose silicon layers with 80 and 125 nm were used on the top of which a 0.5 nm Ni thick layer was deposited. The ellipsometry simulation using a Bruggemann Effective Medium Approximation shows that films with 80 nm reach a crystalline fraction of 72% after 1 h annealing, appearing to be full crystallized after 2 h. No significant structural improvement is detected for longer annealing times. On the 125 nm samples the crystalline volume fraction after 1 h is only around 7%, requiring 5 h to get a similar crystalline fraction than the one achieved with the thinner film. This means that the time required for full crystallization will be strongly determined by the Si layer thickness. Using a new fitting approach the Ni content within the films was also determined by SE and related to the silicon film thickness. © 2006 Elsevier B.V. All rights reserved.

This work focuses on the role of the native oxide layer (SiO2) on the nickel (Ni)-assisted crystallization of amorphous silicon (a-Si). In some samples, the native oxide was removed using a HF-diluted solution before Ni layers with 0.5 nm be deposited on a-Si. The results show that the presence of a thin SiO2 layer of about 3 nm between the a-Si and the Ni delays the crystallization process. Ellipsometry data show that, after annealing for 5 h at 500 °C, the HF-cleaned sample presents a crystalline fraction of 88%, while the one with the native oxide has only 35%. This difference disappears after 20 h where both samples present similar crystalline fraction. These facts are also reflected on the film's electrical properties, where the activation energy for samples annealed for 5 h rises from 0.42 eV to 0.55 eV, when the oxide layer is removed. After 20 h and 30 h, the activation energy is around 0.55 eV for both kinds of samples, meaning that films with similar electrical properties are now obtained. However, the XRD data suggest the presence of some structural differences attributed to slight differences on the crystallization process. © 2005 Elsevier B.V. All rights reserved.

In this work hafnium oxide (HfO2) was deposited by r.f. magnetron sputtering at room temperature and then annealed at 200 °C in forming gas (N2+H2) and oxygen atmospheres, respectively for 2, 5 and 10 h. After 2 h annealing in forming gas an improvement in the interface properties occurs with the associated flat band voltage changing from -2.23 to -1.28 V. This means a reduction in the oxide charge density from 1.33×1012 to 7.62×1011 cm-2. After 5 h annealing only the dielectric constant improves due to densification of the film. Finally, after 10 h annealing we notice a degradation of the electrical film's properties, with the flat band voltage and fixed charge density being -2.96 V and 1.64×1012 cm-2, respectively. Besides that, the leakage current also increases due to crystallization. On the other hand, by depositing the films at 200 °C or annealing it in an oxidizing atmosphere no improvements are observed when comparing these data to the ones obtained by annealing the films in forming gas. Here the flat band voltage is more negative and the hysteresis on the C-V plot is larger than the one recorded on films annealed in forming gas, meaning a degradation of the interfacial properties. © 2006 Elsevier Ltd. All rights reserved.

The search for new dielectric materials to be used in metal-insulator- semiconductor (MIS) structures to replace the silicon oxide (SiO2) has been growing up. The aim is to have materials with high dielectric constants that could allow the use of thicker films and so, to reduce the role of leakage currents that happens in devices using very thin SiO2 layers or to allow the MIS devices to support high currents, besides having a retain memory effect. In this work, we present data concerning the production of hafnium oxide (HfO2) thin films by radio frequency (rf) sputtering that present suitable characteristics to be used as a gate dielectric, taking advantage of its high dielectric constant and stoichiometry reached under certain deposition conditions. Data concerning the role of the deposition parameters in the films structure and in the electrical properties of the films produced using capacitance-voltage (C-V) and current-voltage (I-V) measurements will be shown, together with data concerning the degree of films' compactness measured by spectroscopic ellipsometry (SE). © 2003 Elsevier B.V. All rights reserved.

This paper describes the development of a novel microfluidic platform for multifactorial analysis integrating four label-free detection methods: electrical impedance, refractometry, optical absorption and fluorescence. We present the rationale for the design and the details of the microfabrication of this multifactorial hybrid microfluidic chip. The structure of the platform consists of a three-dimensionally patterned polydimethylsiloxane top part attached to a bottom SU-8 epoxy-based negative photoresist part, where microelectrodes and optical fibers are incorporated to enable impedance and optical analysis. As a proof of concept, the chip functions have been tested and explored, enabling a diversity of applications: (i) impedance-based identification of the size of micro beads, as well as counting and distinguishing of erythrocytes by their volume or membrane properties; (ii) simultaneous determination of the refractive index and optical absorption properties of solutions; and (iii) fluorescence-based bead counting. © 2016 by the authors.

In this work Spectroscopic Ellipsometry (SE) was used to study metal induced crystallization (MIC) on amorphous silicon films in order to analyze the influence of different annealing conditions on their structural properties. The variation of the metal thickness has shown to be determinant on the time needed to full crystallize silicon films. Films of 100 nm thickness crystallize after 2h at 500°C using 1 nm of Ni deposited on it. When reducing the average metal thickness down to 0.05 nm the same silicon film will need almost 10 hours to be totally crystallized. Using a new approach on the modelling procedure of the SE data we show to be possible to determine the Ni remaining inside the crystallized films. The method consists in using Ni as reference on the Bruggeman Effective Medium Approximation (BEMA) layer that will simulated the optical response of the crystallized silicon. Silicon samples and metal layers with different thicknesses were analyzed and this new method has shown to be sensible to changes on the initial metal/silicon ratio. The nickel distribution inside the silicon layers was independently measured by Rutherford Backscattering Spectroscopy (RBS) to check the data obtained from the proposed approach. © 2006 Materials Research Society.

Silicon nitride films were produced on glass and crystalline silicon substrates using r.f. magnetron sputtering to select the best process conditions (substrate temperature, gas pressure and r.f. power) to grow dielectrics for device applications such as low temperature thin film transistors, where special care has to be taken concerning the film's compactness and bulk defects. The films produced were analysed by different techniques such as ultra violet - visible - near infrared spectroscopy Fourier transformed infrared spectroscopy and capacitance measurements, aiming to correlate the films properties with its composition and degree of compactness. The role of the deposition pressure is notorious since films deposited at high pressures are more compact, presenting low oxygen incorporation after deposition. The increase of the substrate temperature up to 373 °K has the same effect, not changing the film's amorphous structure. These data will be discussed aiming to produce films with the required compactness and stoichiometry to grow very thin insulating layers (<10 nm) to be used in MIS structures or devices like thin film transistors.