Rodrigo Martins

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.

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.

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.

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 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.

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 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.

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 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 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 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.

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.

The linearity and sensitivity of linear Position Sensitive Detectors (PSD) are the two principal characteristics of sensors to be optimised in sensor fabrication. This work presents several efforts made to understand the internal and external parameters that influence the linearity and sensitivity of Metal Insulator Semiconductor (MIS) linear PSD with an active length of 6 cm. The use of long sensitive areas allows the PSD to achieve greater resolution without the need of a highly accurate light spot integration mechanism. The PSD is built in a multi-layered 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 Modified Triode Plasma Enhanced Chemical Vapour Deposition (MTPECVD), which allows the deposition of good electronic grade material with a low (≈ 1 × 1015 cm-3) defect density inferred by CPM. The sensor linearity and sensitivity shows dependence on the sensor width to length ratio, SiOx layer and on the value of the 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 in the near-UV region and has its maximum response at 540 nm. © 2005 Springer Science + Business Media, Inc.

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.

This work presents a study performed on the deposition of pm-Si:H by plasma enhanced chemical vapor deposition using excitation frequencies of 13.56 and 27.12 MHz, where the interest of increasing the excitation frequency relies on higher plasma dissociation and reduced energy of ion bombardment, thus allowing the deposition of superior grade material at higher growth rates. The plasma impedance, which allows the monitoring of particle formation in the plasma, was correlated to the film properties, characterized by spectroscopic ellipsometry and hydrogen exodiffusion experiments. The set of data obtained show that by using the 27.12-MHz excitation frequency the hydrogen dilution and the r.f. power density needed to produce pm-Si:H can be reduced. Growth rates above 3.1 Å/s were obtained, the films being more dense and chemically more stable than those obtained with the standard 13.56 MHz. © 2003 Elsevier 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.

This work presents a study performed on several Au contacts deposited by evaporation on oxide free and oxidised (5-20Å of oxide) a-Si:H surfaces. The characterisation of the films was performed on as deposited, aged and annealed at 150°C structures. SIMS and RBS measurements show that the Au diffuses very easily on oxide free a-Si:H surfaces, even at room temperature, resulting in the formation of an oxide at the device surface that acquires a blue colour instead of the gold colour of the contacts. This was also visible in the SEM pictures of the cross section of the structures produced and on the changes of the surface morphology observed by AFM measurements. On the other hand, when the Au is deposited on oxidised a-Si:H surfaces, the results show that the oxide prevents the Au from diffusing and the nature of the contact is preserved. That is, better rectifying and stability performances are obtained in MIS like structures than in Schottky 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.

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.

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 presents a study on the effect of an interfacial silicon oxide layer placed between Au and a-Si:H MIS (metal-insulator-semiconductor) photodiodes in their performances, by stopping the Au diffusion towards the a-Si:H. The results show that the Au diffuses very easily to the oxide free a-Si:H surface, even at room temperature, degrading the photodiode performance. On the other hand, the MIS photodiodes with the interfacial oxide show an improvement of their characteristics after annealing, function of its thickness, and degree of film's compactness. This effect is associated with the presence of oxide of thicknesses ≥5 Å at the Au/a-Si:H interface that prevents the Au diffusion and improves the photodiode characteristics, which does not happen when the interfacial oxide is absent. © 2004 Elsevier B.V. All rights reserved.

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.

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 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 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.