Rodrigo Martins

A glass was made using bottom ash produced by a Portuguese municipal solid waste (MSW) incinerator. The bottom ash was the single batch material used in the formation of the glass, which was obtained through a conventional melt-quenching method. The glass was then converted to glass-ceramic for further recycling to construction materials. After submitting the glass samples to several heat treatments, between 820 and 1050°C and during different times, it was verified that the optimum heat treatment schedule for the ceramization of the glass was at 1000°C for 10h, as confirmed by microstructural observation and by X-ray diffraction. The major crystalline phases precipitated in the glass-ceramic were wollastonite (CaSiO3) and diopside (Ca(Mg,Al)(Si,Al)2O6). Microstructural analysis of the glass-ceramic revealed that the crystalline phases were present as dendrites and fiber-like structures that were homogeneously distributed in the material. The glassceramic showed good mechanical properties with a hardness of 5.6 MPa and a bending strength of 101 MPa. This material had a density of 2.8 gcm-3 and a thermal expansion coefficient of 9.10-6°C-1. The glass and the glass-ceramic showed an excellent chemical stability against leaching in acidic solution and in alkaline solution. In summary, both the glass and the glass-ceramic have good chemical and mechanical properties and can, therefore, be applied as construction materials.

This work presents a comparative study between MIS photodiodes produced using high quality amorphous silicon (a-Si:H), deposited by PECVD at 2Å/s, using 13.56 MHz frequency and polymorphous silicon (pm-Si) deposited at 3Å/s using a 27.12 MHz frequency. The results show that the pm-Si:H outperforms the a-Si:H MIS photodiodes by having a rectification ratio of 107, and photosensitivity at AM1.5 conditions of 107, under 1V reverse bias. Apart from that, the pm-Si:H photodiode presents a higher open circuit voltage and better fill factor than a-Si:H MIS photodiode. These results prove that quality devices can be produced at high growth rates by using pm-Si:H. In this work the photodiode performances were correlated to the films properties, aiming to determine the characteristics responsible for the performances exhibited by the pm-Si:H devices.

Transparent metal oxides thin films are a class of inorganic conductors and semiconductors with significant importance for use in portable electronics, displays, flexible electronics, multi-functional windows and solar cells. Due to the recent development of transparent and flexible electronics, there is a growing interest in depositing metal-oxide thin-film on plastic substrates that can offer flexibility, lighter weight, and potentially lead to cheaper manufacturing by allowing printing and rollto- roll processing. The plastic substrates, however, limit device processing to below 200oC. In this context, the deposition of high-performance semiconductor thin films from dispersions of pre-prepared oxide nanoparticles at temperatures below 200oC represents a potential key route. This paper reports on the preparation of ZnO transparent thin films using solutionprocessed nanoparticles (NPs) precipitated from zinc acetate alcoholic solution with potassium hydroxide. The nanoparticles size distribution, microstructure and crystallinity were measured by dynamic light scattering (DLS), Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). The thin films were deposited by spin-coating onto soda lima glass substrate, using a dispersion of 1wt% ZnO NPs. The morphology of the films annealed at 120 and 180oC, observed by atomic force microscopy and cross-section scanning electron microscopy, shows columnar grains with diameter ranging between 20 and 70 nm, depending on the conditions of depositions. Optical measurements indicated high transparency, between 85 and 94 %, in the visible range, a direct nature of band-to-band transitions and band gap values between 3,22 and 3,32 eV. The refractive index and extinction coefficient have been calculated from optical transmittance and reflectance spectra.

Gallium-doped zinc oxide films were prepared by r.f. magnetron sputtering at room temperature as a function of the substrate-target distance. The best results were obtained for a distance of 10 cm, where a resistivity as low as 2. 7 × 10-4 Ω cm, a Hall mobility of 18 cm2/Vs and a carrier concentration of 1.3 × 1021 cm-3 were achieved. The films are polycrystalline presenting a strong crystallographic c-axis orientation (002) perpendicular to the substrate. The films present an overall transmittance in the visible part of the spectra of approximately 85%, on average. © 2003 Elsevier B.V. All rights reserved.

This work aims to study the role of the r.f. electrode configuration on the plasma characteristics of a PECVD asymmetric reactor. The configurations used are the usual diode configuration, the triode configuration and a new configuration that we named short-circuited grid electrode (SGE). The plasma generated was characterized with the use of a Langmuir probe and an impedance probe. We demonstrate that the plasma parameters are highly dependent on the reactor geometry. The results achieved show that by changing the r.f. electrode configuration the DC self-bias varies from about 100 to close to 0 V. This variation causes changes in the ion bombardment of the reactor surfaces, which can affect the growing of the films deposited. We also demonstrate that for the SGE configuration the area seen by the plasma does not correspond to the exposed physical area of the electrode, and we suggest a model to explain this phenomenon.

Despite of a growing interest in this material, until now the studies on polymorphous silicon (pm-Si:H) have been performed on small laboratory reactors working at 13.56 MHz. Envisaging an industrial application of pm-Si:H, the technology was transferred to a large area plasma enhanced chemical vapour deposition reactor (25 × 40 cm2) working at excitation frequencies of 13.56 and 27.12 MHz. The plasma was characterized by impedance probe measurements and the films were characterized by spectroscopic ellipsometry, infrared spectroscopy and hydrogen evolution experiments, which are techniques that allow a rapid and reliable identification of pm-Si:H structure. Conductivity measurements were also performed to determine their transport properties. The results show that scaling up using the 13.56 MHz was successfully done and pm-Si:H films were deposited at a growth rate of ≈ 12 nm/min. Moreover, by using the 27.12 MHz excitation frequency the growth rate was even further increased to above 18 nm/min, as desired for industrial production. © 2002 Elsevier Science B.V. All rights reserved.

This work refers to a study performed on polymorphous silicon (pm-Si:H) at excitation frequencies of 13.56 and 27.12 MHz in a large area PECVD reactor. The plasma was characterised by impedance probe measurements, aiming to identify the plasma conditions that lead to produce pm-Si:H films. The films produced were characterised by spectroscopic ellipsometry, infrared and Raman spectroscopy and hydrogen exodiffusion experiments, which are techniques that permit the structural characterisation of the pm-Si films and to study the possible differences between the films deposited at 13.56 and 27.12 MHz. Conductivity measurements were also performed to determine the transport properties of the films produced. The set of data obtained show that the 27.12 MHz pm-Si:H can be grown at higher rates with less hydrogen dilution and power density, being the resulting films denser, chemically more stable and with improved performances than the pm-Si:H films grown at 13.56 MHz.

The driving force behind the work herein presented is the importance of budgeting in a competitive market. The problem at hands is the creation of a budgeting methodology for reverse engineering applications, involving laser scanning, that has the ability to generate budgets for different customer accuracy requirements and for parts of different morphologic characteristics, such as: shape, dimension and/or detail complexity. A breakup approach was used to implement the methodology: the reverse engineering process was broken in nine basic identified steps and elementary sources of cost were defined at the different reverse engineering stages as well. Particular budgeting methodologies for each step of the process were created. The obtained results so far point to the possibility of creating a complete budgeting system based on the proposed methodology. © 2008 Taylor & Francis Group.

We report the effect of a disperse carbon interlayer between the n-a-Si:H layer and an aluminium zinc oxide (AZO) back contact on the performance of amorphous silicon solar cells. Carbon was incorporated to the AZO film as revealed by x-ray photoelectron spectroscopy and energy-dispersive x-ray analysis. Solar cells fabricated on glass substrates using AZO in the back contact performed better when a disperse carbon interlayer was present in their structure. They exhibited an initial efficiency of 11%, open-circuit voltage Voc = 1.6 V, short-circuit current JSC = 11 mA cm -2 and a filling factor of 63%, that is, a 10% increase in the J SC and 20% increase in the efficiency compared to a standard solar cell. © 2013 National Institute for Materials Science.

In this work we present a study of influence of ion bombardment on the optical, electrical and compositional properties of the intrinsic amorphous silicon films deposited in a modified triode plasma-enhanced chemical vapour deposition (PECVD) reactor. The application of a DC voltage to a grid placed in front of the r.f. electrode allowed us to control the energy and polarity of the ions striking the substrate during film growth. The results show a variation by two orders of magnitude in the dark conductivity from 10-10 to 6.2 × 10-12 (Ω cm)-1, while the photosensitivity varied from 2 × 105 to 2 × 107. A process plasma that takes place in the γ-type regime was associated with the use of a negative bias, while a process plasma like the one of the α-type regime was associated with the use of a positive bias. The films deposited with a bias ≈ 38 V are highly intrinsic and the abrupt change in the conductivity properties observed at this bias is attributed to a change in the density of the states ascribed to the position of the Fermi level. That is, a precise control of the energy of the ions striking the substrate during the film growth leads to improved film optoelectronic properties, very important for device applications. © 2001 Elsevier Science Ltd. All rights reserved.

In this work, we study the influence of the hydrogenated amorphous silicon (a-Si:H) surface treatment on the J-V characteristics of a-Si:H/Pd Schottky barrier photodiodes. The a-Si:H surface were etched, thermally oxidised and wet oxidised by H2O2. The a-Si:H films were characterised by spectroscopic ellipsometry, were we found that all the oxidation techniques promote an increase of the surface oxide thickness that was confirmed by the increase of the barrier height. The highest barrier was achieved by the H2O2 oxidation where a value of 1.17 eV was found. As a result of the barrier height increase, the dark reverse current density decreases up to 10-10 A/cm2 and the signal to noise ratio increases up to 106. The open circuit voltage under AM1.5 illumination conditions also increases from 0.4 to 0.5 V. These results reveal the importance of the a-Si:H surface preparation prior to metallization to improve the Schottky photodiodes properties. © 2002 Elsevier Science B.V. All rights reserved.

In this work we present the current/voltage characteristics of Si:H/Pd Schottky structures using high quality, low defect density amorphous silicon (a-Si:H) deposited by a non-conventional, modified triode PECVD method. This new configuration allows the deposition of compact and high quality a-Si:H with a photosensitivity of 107, yielding films with low bulk defects. AFM measurements also revealed that these films have a very smooth surface allowing a low defect interface between the metal and the a-Si:H. As a result, we show that by using these a-Si:H films and by proper control of the i-layer thickness the reverse dark current of the diode can be highly reduced achieving signal to noise ratio of 106, surpassing the results usually achieved by p-i-n structures.

In this work we present results of studies performed on Schottky and metal-insulator-semiconductor (MIS) position sensitive detectors (PSD) structures: substrate (glass)/ Cr (300 nm) / a-Si:H [n] (37 nm) / a-Si:H [i] (600 nm) / SiO2 (1.5 nm - for the MIS) / Au (7 nm). The effect of the interfacial oxide layer between Au and a-Si:H, for the MIS structures, was studied and compared with the Schottky, in order to determine how beneficial it could be for device performances and time degradation. For doing so, the Au thickness of 70Å was deposited by thermal evaporation on an oxide free (Schottky) and oxidized (≈20Å) (MIS) a-Si:H surfaces. These structures were characterized by SIMS, RBS, SEM and AFM in order to correlate the obtained diffusion profile of Au at the interface and the topography with the presence of the oxide at the interface. The results show that the Au inter-diffuses very easily in the oxide free a-Si:H surface, even at room temperature, degrading the devices performance. On the other hand, the MIS structures, with their interfacial oxide present no structural changes after annealing and the PSD produced are stable. We believe that this effect is associated with the barrier effect of the interfacial oxide that prevents the Au diffusion. The optimized 1D MIS sensors are stable and exhibit a linearity error as low as 0.8 % and sensitivities of 33 mV/cm for a 5 mW spot beam intensity at a wavelength of 532 nm, while the Schottky sensors showed a time degradation of their characteristics. © 2006 Materials Research Society.

In this work we present results of structural composition and morphological characteristics of polymorphous silicon (pm-Si:H) films deposited by PECVD at 13.56 and 27.12 MHz. In addition, the role of the excitation frequency on the growth rate will be also analyzed. The results show that by using the 27.12 MHz excitation frequency the hydrogen dilution in the plasma needed to produce pm-Si:H can be reduced by more than 50% as well as the rf power density, leading to an increase on the growth rate to values higher than 3 Å/s. Spectroscopic ellipsometry and Raman spectroscopy show that the 27.12 MHz pm-Si:H films are more ordered than the pm-Si:H films produced at 13.56 MHz, while the infrared spectroscopy show that the SiH2 concentration in the films is strongly reduced. AFM measurements reveal that the films produced at 27.12 MHz films are more structured, presenting also higher roughness. © 2004 Elsevier B.V. All rights reserved.

Trimethylboron (TMB) has been receiving attention as a valid alternative to diborane and methane mixtures for the deposition of p-type silicon films for applications in optoelectronic devices such as solar cells. In this paper we report on p-type hydrogenated nanocrystalline silicon carbide (nc-Si:C:H) films produced by standard 13.56 MHz plasma enhanced chemical vapour deposition technique, using TMB as gas source, under high hydrogen dilution (98%) and using high deposition pressures (3 Torr). The films obtained were characterized by spectroscopic ellipsometry (SE), Raman spectroscopy (RS), and electrical measurements to determine their optical, structural and electrical properties. We achieved conductivities as high as 8.3 (Ω cm) -1, one of the highest values of conductivity published to date using TMB with standard rf-PECVD. Spectroscopic ellipsometry modeling revealed that the films growth mechanism proceeds through a sub-surface layer mechanism that leads to the formation of nanocrystalline silicon. Copyright © 2010 American Scientific Publishers All rights reserved.

Nanostructured silicon single junction thin film solar cells were deposited on commercial red clay roof tiles with engobe surfaces and earthenware wall tiles with glazed surfaces, with a test area of 24 mm 2. We studied the influence of the type of substrate tile, back contact, buffer layer and SiO x passivation layer on the optoelectronic performance of the solar cells. Despite the fact that typical micrometre-sized defects on the surfaces of the tiles and the porous nature of the ceramic substrates make deposition of homogeneous thin films on them quite challenging, we have been able to achieve a cell efficiency of 5% and a quantum efficiency of 80% on non-fully optimized cells on commercial tiles. The method is industrially employable utilizing pre-existing plasma-enhanced chemical vapour deposition technologies. The cost-effectiveness and industrial feasibility of the technique are discussed. Our study shows that photovoltaic tiles can combine energy generation with architectural aesthetics leading to significant implications for advancement in building integrated photovoltaics. © 2011 The Royal Society of Chemistry.

In this work, spectroscopic ellipsometry was used to characterise oxide films produced by anodic oxidation of amorphous silicon using an ethylene glycol (0.04 M KNO3) solution. The data obtained show that the growth of the oxide is not only a function of the voltage applied, but also of the current density and of the time process. An empiric model based on a power law is proposed for the growth of the oxide using, as parameters, the voltages and the time process. The oxide produced shows porosity of approximately 12%, which can be reduced down to 6% under well-controlled growth conditions. © 2002 Elsevier Science B.V. All rights reserved.

Co-doped TiO 2 films were characterized by spectroscopic ellipsometry to determine their thickness, deposition rate and optical properties as function of substance temperature and background gas composition. To fit the data we used a combination of a single Tauc-Lorentz oscillator with the Drude free electron model to take in account the free electrons present in the film. The Co doping and addition of H 2 to the gas phase during film growth cause the formation of a titanium oxide which containsfree electrons that absorb the energy of the red part of the spectrum, causing k to increase. The n of the film at 1.5 eV is about 2.3 eV. The fittings also show that the n of films decreases and k increase at the surface. This can be related to a segregation of Co to the surface, which in some cases, of high substrate temperature and high H 2 flow during deposition, can lead to and even higher concentration of free electrons at the surface. © 2008 WILEY-VCH Verlag GmbH & Co. KGaA.

High-quality SrBi2Nb2O9 (SBN) single crystals were grown from a melt using a high-temperature self-flux solution method and Bi2O3 added with B2O3 as a flux. A suitable thermal profile involving slow cooling rates allowed growing large and translucent SBN crystals exhibiting platelet morphology with typical size ∼5 × 5 mm2 and thickness approximately 400 μm. X-ray diffraction revealed a dominant (001)-orientation of the major face of the platelet crystals and edges oriented parallel to the [110] directions. The dielectric properties were evaluated along the ab-plane and in the c-axis direction. The ferro-paraelectric phase transition was observed at TC = 440°C with Curie-Weiss relationship above TC. The anisotropy of dielectric permittivity, i.e., the ratio between permittivity in the ab-plane and along c-axis was about 10 at TC-The obtained results are used to discuss the observed correlations between anisotropy, crystalline orientation, and electrical properties.

Zinc oxide is getting an enormous attention due to its potential applications in a variety of fields such as optoelectronics, spintronics and sensors. The renewed interest in this wide band gap oxide semiconductor relies on its direct high energy gap (Eg ∼ 3.437 eV at low temperatures) and large exciton binding energy. However to reach the stage of device production the difficulty to produce in a reproducible way p-type doping must be overcome. In this study we discuss the structural and optical properties of ZnO films doped with nitrogen, a potential p-type dopant. The films were deposited by magnetron sputtering using different conditions and substrates. The composition and structural properties of the films were studied combining X-ray diffraction (XRD), Rutherford backscattering (RBS), and heavy ion elastic recoil detection analysis (HI-ERDA). The results show an improvement of the quality of the films deposited on sapphire with increasing radio-frequency (RF) power with a preferentially growth along the c-axis. The ERDA analysis reveals the presence of H in the films and a homogeneous composition over the entire thickness. The photoluminescence of annealed samples evidences an improvement on the optical quality as identified by the well structured near band edge recombination. © 2009 Elsevier Ltd. All rights reserved.

In the present work one host natural matrix - agar - has been doped with magnesium triflate (Mg(CF3SO3)2) with the goal of developing electrolytes for the fabrication of solid-state devices. The resulting samples have been represented by the notation Agar nMg(CF3SO3)2, where n represents the percentage of the magnesium triflate salt proportion in the electrolyte samples. The samples investigated, with n between 0.00% and 37.56%, have been obtained as transparent and thin films. The samples have been characterized by conductivity measurements, thermal analysis, cyclic voltammetry, X-ray diffraction (XRD), and scanning electron microscopy (SEM). The agar-based electrolytes were also tested as ionic conductor in an electrochromic device with the following configuration: glass/indium tin oxide (ITO)/WO 3/agar-based electrolyte/CeO2-TiO2/ITO/glass. © 2013 Copyright Taylor and Francis Group, LLC.

To evaluate the evolution of a dark film formation on silver surface objects, several coupons were catalogued and place inside a museum, located in an urban area. The changes on these samples were measured by spectroscopic ellipsometry, in periods of months. This technique allows the reduction of the coupons exposure time, in several months, due to its high sensitivity to surface modifications, with acceptable results for the evaluation of its degradation. The thicknesses of the degradation layers and the optical properties of silver oxide, chloride and sulphide reference samples were determined using a mixture of Tauc-Lorentz and Drude models. The composition of the silver corrosion layer was determined by fitting the layer using a Bruggeman Effective Medium Approximation (BEMA) of the three products plus voids. It was found that the thickness of the layer depends in the placement of the coupons, namely, inside or outside displayers. The average film thickness after 6 months was of 180 Å and 280 Å, inside and outside the displayers, respectively. The main compounds found in the layers were the silver chlorides and sulphides, which composition changed with the thickness of the layer, and the exposition time. © 2008 Wiley-VCH Verlag GmbH & Co. KGaA.

In this work we present a study performed in a plasma-enhanced chemical vapour deposition reactor, where different rf electrode configurations were used with the aim of achieving conditions that lead to growth of highly uniform amorphous silicon films, with the required electronic quality, at high growth rates. This study consists in determining the plasma characteristics under different electrode configurations, in an argon plasma, using as diagnostic tools a Langmuir probe and impedance probe. These results were correlated with the hydrogenated amorphous silicon films produced, thereby allowing us to establish the best electrode configuration to grow electronic-grade-quality amorphous silicon films.

This work reports on the fabrication process and performances presented by metal insulator semiconductor (MIS) linear position sensitive detectors (PSD) with an active length of 6 cm. The use of long sensitive areas allows the PSD to achieve higher resolution without the need of a highly accurate light spot integration mechanism. The PSD is built in a multilayered structure consisting of Cr/a-Si:H (n+ doped)/a-Si:H (intrinsic)/SiOx (passivation layer)/Au, where the active a-Si:H layers were deposited by a modified triode plasma enhanced chemical vapour deposition (MTPECVD), which allows the deposition of highly electronic grade material with a low (≈ × 1015 cm-3) defect density inferred by CPM. The sensor linearity and sensitivity shows dependence on the sensor width to length ratio and on the value of load resistance. Sensitivities of more than 30 mV/cm were achieved with linearity near 99%. Besides that, this type of MIS structure allows an improved spectral response near the UV region and has the maximum response at 540 nm. © 2004 Published by Elsevier B.V.

The present development of non-wafer-based photovoltaics (PV) allows supporting thin film solar cells on a wide variety of low-cost recyclable and flexible substrates such as paper, thereby extending PV to a broad range of consumer-oriented disposable applications where autonomous energy harvesting is a bottleneck issue. However, their fibrous structure makes it challenging to fabricate good-performing inorganic PV devices on such substrates. The advances presented here demonstrate the viability of fabricating thin film silicon PV cells on paper coated with a hydrophilic mesoporous layer. Such layer can not only withstand the cells production temperature (150 C), but also provide adequate paper sealing and surface finishing for the cell's layers deposition. The substances released from the paper substrate are continuously monitored during the cell deposition by mass spectrometry, which allows adapting the procedures to mitigate any contamination from the substrate. In this way, a proof-of-concept solar cell with 3.4% cell efficiency (41% fill factor, 0.82 V open-circuit voltage and 10.2 mA cm-2 short-circuit current density) is attained, opening the door to the use of paper as a reliable substrate to fabricate inorganic PV cells for a plethora of indoor applications with tremendous impact in multi-sectorial fields such as food, pharmacy and security. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.