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.

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.

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.

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.

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.

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 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.

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.

In this work the electrical and structural properties of two high k materials as hafnium oxide (HfO2) and tantalum oxide (Ta2O5) produced at room temperature are exploited. Aiming low temperature processing two techniques were employed: r.f. sputtering and electron beam evaporation. The sputtered HfO2 films present a nanocrystalline structure when deposited at room temperature. The same does not happen for the evaporated films, which are essentially amorphous. The density and the electrical performance of both sputtered and evaporated films are improved after annealing them at 200 °C. On the other hand, the Ta2O5 samples deposited at room temperature are always amorphous, independently of the technique used. The density and electrical performance are not so sensitive to the annealing process. The set of data obtained show that these dielectrics processed at temperatures below 200 °C present promising properties aiming to produce devices at low temperature with improved interface properties and reduced leakage currents. © 2007 Elsevier B.V. All rights reserved.

In this work we have focused our attention on the role of the gas mixture (O2/Ar) used during HfO2 thin film processing by r.f. magnetron sputtering, to produce dielectrics with suitable characteristics to be used as gate dielectric. Increasing the O2/Ar ratio from 0 to 0.2, the films properties (optical gap, permittivity, resistivity and compactness) are improved. At these conditions, films with a band gap around 5 eV were produced, indicating a good stoichiometry. Also the flat band voltage has a reduction of almost three times indicating also a reduction of the same order on the fixed charge density at the semiconductor-insulator interface. The dielectric constant is around 16 which is very good, since the surface of the silicon where the HfO2 films were deposited contains a SiO 2 layer of about 3 nm that gives an effective dielectric constant above 20, close to the HfO2 stoichiometric value (∼25). Further increase on the O2/Ar ratio does not produce significant improvements. © 2004 Elsevier B.V. All rights reserved.

The aim of this work is to optimize the metal/silicon ratio on nickel metal induced crystallization of silicon. For this purpose amorphous silicon layers with 80, 125 and 220 nm thick were used on the top of which 0.5 nm of Ni was deposited and annealed during the required time to full crystallize the a-Si. The data show that the 80 nm a-Si layer reaches a crystalline fraction of 95.7% (as detected by spectroscopic ellipsometry) after annealed for only 2 hours. No significant structural improvement is detected by ellipsometry neither by XRD when annealing the films for longer times. However, on 125 nm thick samples, after annealing for 2 hours the crystalline fraction is only 59.7%, reaching a similar value to the one with 80 nm only after 5 hours, with a crystalline fraction of 92.2%. Here again no significant improvements were achieved by using longer annealing times. Finally, the 220 nm thick a-Si sample is completely crystallized only after 10 hours annealing. These data clear suggest that the crystallization of thicker a-Si layers requires thicker Ni films to be effective for short annealing times. A direct dependence of the crystallization time on the metal/silicon ratio was observed and estimated. © 2005 Materials Research Society.

In this work, it is demonstrated the application of a high k dielectric, as hafnium oxide (HfO2), in poly-Si thin film transistors (TFTs) obtained by metal induced lateral crystallization (MILC). The dielectric layer was deposited at room temperature by sputtering, using argon and oxygen as process gases. As produced TFTs exhibit field effect mobility around 45 cm2 V-1 s-1and Ion/Ioff ratio of about 2 × 105. After annealing in a forming gas atmosphere for about 1 h at 200 °C, the threshold voltage and the sub-threshold slope are reduced, respectively from 4.8 to 2 V and from 1.6 to 1.4 V/dec. Nevertheless, by doing so, we notice a reduction on the field effect mobility of about 45% and a decrease of about 2.5 times on the Ion/Ioff ratio. Longer annealing time will not improve the TFT's performance. © 2008 Elsevier B.V. All rights reserved.

In this work, the optical and structural properties of high k materials such as tantalum oxide and titanium oxide were studied by spectroscopic ellipsometry, where a Tauc-Lorentz dispersion model based in one (amorphous films) or two oscillators (microcrystalline films) was used. The samples were deposited at room temperature by radio frequency magnetron sputtering and then annealed at temperatures from 100 to 500 °C. Concerning the tantalum oxide films, the increase of the annealing temperature, up to 500 °C does not change the amorphous nature of the films, increasing, however, their density. The same does not happen with the titanium oxide films that are microcrystalline, even when deposited at room temperature. Data concerning the use of a four-layer model based on one and two Tauc-Lorentz dispersions is also discussed, emphasizing its use for the detection of an amorphous incubation layer, normally present on microcrystalline films grown by sputtering. © 2006 Elsevier B.V. All rights reserved.

The aim of this paper is to study the role of different metals (aluminium, molybdenum, nickel and titanium) in inducing crystallization in films produced by LPCVD at high and low temperature processes and to compare the structural, morphological, optical and electrical properties of the various films produced. This work envisages the use of the most suitable conditions that lead to the production of films for optoelectronic applications such as solar cells. © 2003 Elsevier B.V. All rights reserved.