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.

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.

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.

In this work we investigate the properties of a polymorphous silicon (pm-Si:H) metal-insulator-semiconductor (MIS) structure used in 3D position sensitive detectors (PSD). For the first time a 3D sensor made-up by pm-Si:H/SiO2/Au layers is presented. MIS structures present several advantages over p-i-n structures, such as easier fabrication, fast response time and higher resolution. The 1D MIS PSD that constitute the array were extensively studied aiming its application in 3D pattern recognition. The results obtained show that MIS PSD can achieve non-linearities below 2% and sensitivities of 3.2 μA/cm over 6 mm length sensors. The miniaturization of the sensors length to arrays of 6 and 16 mm, respectively showed average non-linearities of about 1.9% for the 16 mm sensor which proved to be the best solution for this MIS structure. © 2006 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.

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.

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 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.

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.

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 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.

It is experimentally known that the linearity and sensitivity of the position sensitive detectors (PSD) are dependent on the resistance of the collecting layer and of the load resistance, mainly if the detection is based on the measurement of the photo-lateral voltage. To determine the value of the load resistance to be used in metal - insulator - semiconductor (MIS) PSDs structures that lead to the maximum value of sensitivity and linearity, we propose an electrical model through which it is able to simulate the proper sensor response and how the load resistance influence the results obtained. This model is valid for PSDs where the resistance of the collecting resistive layer is quite low (≤ 500 Ω), leading to a low output impedance. Under these conditions we conclude that the value of the load resistance should be of about 1 kΩ in order to achieve a good compromise between the linearity and the sensitivity of the PSD. This result is in agreement with the set of experiments performed. © 2005 Materials Research Society.

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 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 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.

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.

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 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.

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.

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 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 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.

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.