Rodrigo Martins

In this work metal-insulator-semiconductor (MIS) photodiodes with a structure: Cr/a-Si:H(n+)/a-Si:H(i)/oxide/Au were studied, where the main objective was to determine the influence of the oxide layer on the performance of the devices. The results achieved show that their performance is a function of both oxide thickness and oxide density. The a-Si:H oxidation method used was the immersion in H2O2 solution. By knowledge of the oxide growth process it was possible to fabricate photodiodes exhibiting an open circuit voltage of 0.65V and short circuit current density under AM1.5 illumination of 11mA/cm2, with a response times less than 1μs for load resistance <400Ω, and a signal to noise ratio of 1×107. © 2003 Elsevier B.V. All rights reserved.

In this work we present results of a study performed on metal-insulator-semiconductor (MIS) diodes with the following structure: substrate (glass)/Cr (2000 Å)/a-Si:H n+(400 Å)/a-Si:H i (5500 Å)/oxide (0-40 Å)/Au (100 Å) to determine the influence of the oxide passivation layer grown by different techniques on the electrical performance of MIS devices. The results achieved show that the diodes with oxides grown using hydrogen peroxide present higher rectification factor (2×106) and signal to noise (S/N) ratio (1×10 7 at -1 V) than the diodes with oxides obtained by the evaporation of SiO2, or by the chemical deposition of SiO2 by plasma of hexamethyldisiloxane. However, in the case of deposited oxides, the breakdown voltage is higher, 30 V instead of 3-10 V for grown oxides. The ideal oxide thickness, determined by spectroscopic ellipsometry, is dependent on the method used to grow the oxide layer and is in the range between 6 and 20 Å. The reason for this variation is related to the degree of compactation of the oxide produced, which is not relevant for applications of the diodes in the range of ±1 V, but is relevant when high breakdown voltages are required. © 2003 Elsevier B.V. All rights reserved.

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.

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.

In this work we present results of a study performed on MIS diodes with the following structure: substrate (glass) / Cr (2000Å) / a-Si:H n + (400Å) / a-Si:H i (5500Å) / oxide (0-40Å) / Au (100Å) to determine the influence of the oxide passivation layer grown by different techniques on the electrical performance of MIS devices. The results achieved show that the diodes with oxides grown using hydrogen peroxide present higher rectification factor (2×106) and signal to noise (S/N) ratio (1×107 at -1V) than the diodes with oxides obtained by the evaporation of SiO2, or by the chemical deposition of SiO 2 by plasma of HMDSO (hexamethyldisiloxane), but in the case of deposited oxides, the breakdown voltage is higher, 30V instead of 3-10 V for grown oxides. The ideal oxide thickness, determined by spectroscopic ellipsometry, is dependent on the method used to grow the oxide layer and is in the range between 6 and 20 Å. The reason for this variation is related to the degree of compactation of the oxide produced, which is not relevant for applications of the diodes in the range of ± 1V, but is relevant when high breakdown voltages are required.

Highly conducting and transparent gallium doped zinc oxide thin films have been deposited at high growth rates by r.f. magnetron sputtering at room temperature on inexpensive soda lime glass substrates. The argon sputtering pressure was varied between 0.15 and 2.1 Pa. The lowest resistivity was 2.6 × 10-4 Ω cm (sheet resistance ≈6 Ω/sq. for a thickness ≈600 nm) and was obtained at an argon sputtering pressure of 0.15 Pa and a r.f. power of 175 W. The films present an overall transmittance in the visible spectra of approximately 90%. The increase on the resistivity for higher sputtering pressures is due to a decrease of both, mobility and carrier concentration, and is associated to a change on the surface morphology. The low resistivity, accomplished with a high growth rate (290 Å/min) and with a room temperature deposition enables these films deposition onto polymeric substrates for flexible optoelectronic devices. © 2002 Elsevier Science B.V. All rights reserved.

This work presents for the first time a study on the deposition of polymorphous silicon at an excitation frequency of 27.12 MHz in a large-area plasma enhanced chemical vapor deposition (PECVD) reactor. Moreover, the films produced at 13.56 MHz were also investigated to compare their performance with that of the films produced at 27.12 MHz. The SiH4/H2 plasma was characterized by impedance probe measurements, aiming to identify the plasma conditions that lead to produce polymorphous films, under quasi-isothermal conditions. The films were characterized by spectroscopic ellipsometry, infrared absorption, Raman spectroscopy, and hydrogen exodiffusion experiments. These techniques enable a detailed structural characterization of the polymorphous films and a study of the differences between the films deposited at 27.12 MHz and 13.56 MHz. Conductivity measurements were also performed to determine the transport properties of the films. The results show that by using a 27.12 MHz frequency, the growth rate increased by 70% and a more stable, relaxed and denser structure was obtained.

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.

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.

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.

In this work, we study the electro-optical behaviour of cellulose/liquid crystal-based composite systems, in particular the influence of the flexible substrates and its conductive layers in the electro-optical behaviour of these kind of cells. Four cells were made using, respectively, two different substrates (a flexible polymer (poly(ethylene terephthalate) (PET)) and a soda lime glass) and two different conductive layers (indium tin oxide (ITO) and aluminium zinc oxide (AZO)). The conductive layer (AZO) was deposited in both, flexible and rigid substrates, for the same conditions, and the same substrates coated with ITO are commercially available. The cells were prepared from solid films of hydroxypropylcellulose (HPC) (30 μm thick) cross linked with 1,4-diisocyanatobutane (BDI) (7% w/w) and the nematic liquid crystal E7 (Merck, UK). The four different substrates were electrically and morphologically characterised. We have analysed all samples by light transmission and determined the maximum transmission, contrast and Von. We show a comparison of the results obtained for both flexible and rigid cells and discuss them in terms of the proposed working mechanism for these systems. © 2002 Elsevier Science B.V. All rights reserved.

This work presents the I-V results of a-Si:H/SiOx/Pd MIS (metal-insulator-semiconductor) structures. The a-Si:H was deposited by non-conventional modified triode PECVD. This new configuration allows the deposition of high quality a-Si:H with a photosensitivity of 106, indicating the presence of low density of defects. Spectroscopic ellipsometry measurements revealed that these films are highly dense and present a very smooth surface so allowing a low defect interface between the Pd and the a-Si:H. As a result, we could make MIS photodiodes with barrier heights of 1.17 eV, which give a high reduction of the reverse dark current, an increase of the signal to noise ratio of 106 and an open circuit voltage VOC = 0.5 V. © 2002 Elsevier Science B.V. All rights reserved.

In this work we show that it is possible to control the plasma regime in the region close to the substrate in r.f. silane discharges. The PECVD reactor works in a modified triode configuration, where the control over the plasma regime is performed by polarising a grid electrode, placed close to the r.f. electrode, with a DC power source. Besides that, the DC grid allows also to control the energy of the ion bombardment, because the plasma potential will be a function of the voltage (Vpol) applied to the DC grid. The silane plasma was characterised with a Langmuir probe and an impedance probe. We were able to identify three plasma regimes in the region close to the substrate: γ′ regime for Vpol<0 V; γ′-α regime for 0 V<Vpol<40 V; and α regime for Vpol40 V. The γ′ regime is associated with a high concentration of dust particles in plasma and high electron energy (≈8eV), while the α regime is associated with a free dust plasma and low electron energy (≈2eV). The intermediate regime, γ′-α, is characterised by the presence of smaller particles (≈2-5nm) that can be beneficial for the film's properties. © 2002 Elsevier Science Ltd. All rights reserved.

In this work we show that it is possible to control the plasma species present near the substrate surface, from what is usually associated with an α regime (a plasma free of particles) to a γ' regime (a plasma where particles are present) and simultaneously control the energy of the ions striking the substrate during a-Si:H deposition from a silane glow discharge in a modified triode (MT) type PECVD reactor, where a DC mesh electrode biased with Vpol is located in front of the r.f electrode. The presence of large particles in the plasma leads to the deposition of the films with the poorest optoelectronic properties. When the particle size in the plasma decrease the film properties improve, but, when particles are no longer present in the plasma region close to the substrate, like in a α like regime, the properties of the films deteriorate again. The results show that the best transport properties are achieved for the films deposited in the α-γ' transition regime corresponding to 0V<Vpol<51V. Under this condition the films present a dark conductivity, σ d ≈ 10-11 (Ωcm)-1, photosensitivity, S ≈ 107, activation energy, ΔE ≈ 0.9 eV, hydrogen content, CH ≈ 10%, factor of microstructure, R ≈ 0.085 and an optical gap, Eop ≈ 1.77 eV.

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 order to correlate the MIS devices performance with different surface oxidation methods, AFM, spectroscopic ellipsometry and infrared spectroscopy measurements were performed in a-Si:H films, before and after surface oxidation, using different oxidation techniques and oxides: thermal dry (in air), wet (in H2O2) and by oxygen plasma, while MIS (metal-insulator-semiconductor) devices were characterized by I-V curves, under dark and AM1.5 illumination conditions. The a-Si:H films were grown by the PECVD technique, in a modified triode configuration reactor to allow a precise control of the ion bombardment during the film deposition. We found that the growth of a thin layer of oxide by chemical processes on the top of the a-Si:H surface can cause changes on the surface morphology that are reflected in the electrical behaviour of the devices. The oxygen plasma treatment, cause the rearrangement of the surface atoms leading to a change of their morphology and to the improvement of the electrical properties of the surface for a MIS applications.

This work presents a fast method to determine qualitatively the uniformity and the thickness of transparent or semitransparent thin films in the visible to near-infrared region. The method proposed is based on the information recorded by a colour scanner in the form of coloured regions, due to the constructive interferences caused by multibeam wavelength light sources as function of the film thickness and refractive index. The method is well applied in transparent films, where the uniformity cannot be seen by visual inspection. This paper shows that the results obtained for ZrO2 films are satisfactory enabling the application of this technique to determine the films uniformity in fast and cheap way.

In this work a new structure is proposed for position sensitive detectors consisting of glass/Cr/aSi:H(n+)/a-Si:H(i)/ZnO, where the ZnO forms an heterojunction with the a-Si:H(i). The results show that this structure works with success in the fabrication of linear position sensitive detectors. The devices present a good nonlinearity of ≈ 2% and a good sensitivity to the light intensity. The main advantages of this structure over the classical p-i-n are an easier to built topology and a higher yield due to a better immunity to the a-Si:H pinholes, since the ZnO does not diffuse so easily into a-Si:H as the metal does, which are the cause of frequent failure in the p-i-n devices due to short-circuits caused by the deposition of the metal over the a-Si:H. In this structure the illumination is made directly on the ZnO, so a transparent substrate is not needed and a larger range of substrates can be used.

{In this work we report how it is possible to control the plasma regime near the substrate surface, from predominantly α to predominantly γ', passing trough and intermediate α-γ' regime, and simultaneously control the energy of the ions striking the substrate during a-Si:H deposition from a silane glow discharge in a modified triode type PECVD reactor. To do so, we apply a DC voltage (Vpol to a set of grids placed in front of the r.f. electrode and by doing this, we control the energy of the ions striking the substrate during the film's growth and the plasma regime near the substrate. Under a plasma of the γ' regime, the surface roughness is high and the films are poorly compact. In the α-γ' regime, the ion bombardment is moderate and the films are highly smooth and compact. In the α regime the ion bombardment is higher and so the films can become more compact but the surface roughness increases and the electrical properties deteriorate. The results achieved show that the best transport properties are achieved for the films deposited in the α-γ' regime corresponding to a Vpol of 38 V. Under this condition the films presented a dark conductivity, σd = 6.2×10-12 (Ωcm)-1, activation energy, ΔE ≈ 0.9 eV, hydrogen content

In order to understand the kinetics of formation of interface/surface states and its correlation on the final device performance, a preliminary study was performed on MIS structures, before and after surface oxidation/passivation, using different oxidation techniques and oxides: thermal (in air), chemical (in H2O2) and oxygen plasma. The devices used in this work are based on a glass/Cr/a-Si:H(n+)/a-Si:H(i)/SiOx/Pd structures, where the amorphous silicon intrinsic layer (i a-Si:H) with a photosensitivity of 107 was deposited by a modified plasma enhanced chemical vapour deposition (PECVD) triode system. The electrical properties of a-Si:H MIS structures were investigated by measuring their diode current-voltage characteristics in the dark and under illumination as well as the spectral response, as a function of the various oxidation techniques. Infrared spectroscopy and spectroscopic ellipsometry were used as a complementary tool to characterise the oxidised surface.

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.

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.