Current-voltage characteristics in macroporous silicon/SiOx/SnO2:F heterojunctions
© Garcés et al.; licensee Springer. 2012
Received: 9 May 2012
Accepted: 5 July 2012
Published: 25 July 2012
We study the electrical characteristics of macroporous silicon/transparent conductor oxide junctions obtained by the deposition of fluorine doped-SnO2 onto macroporous silicon thin films using the spray pyrolysis technique. Macroporous silicon was prepared by the electrochemical anodization of a silicon wafer to produce pore sizes ranging between 0.9 to 1.2 μ m in diameter. Scanning electronic microscopy was performed to confirm the pore filling and surface coverage. The transport of charge carriers through the interface was studied by measuring the current-voltage curves in the dark and under illumination. In the best configuration, we obtain a modest open-circuit voltage of about 70 mV and a short-circuit current of 3.5 mA/cm2 at an illumination of 110 mW/cm2. In order to analyze the effects of the illumination on the electrical properties of the junction, we proposed a model of two opposing diodes, each one associated with an independent current source. We obtain a good accordance between the experimental data and the model. The current-voltage curves in illuminated conditions are well fitted with the same parameters obtained in the dark where only the photocurrent intensities in the diodes are free parameters.
Fluorine-doped tin oxide SnO2:F(FTO) and porous silicon (PS) are two types of materials that have been extensively investigated for sensor applications [1, 2]. Tin oxide is a transparent conductive oxide with electrical transport properties extremely sensitive to the environment [3–6]. Porous silicon is a material that can exhibit efficient visible photoluminescence [7, 8], and several sensing applications using PS layers have been reported in, for example, humidity sensors , gas sensors [10–13], and biological sensors . Since both materials, PS and FTO, exhibit an elevated specific surface, they are potentially attractive for these types of applications. It is expected that combining both materials in a single device will lead to an enhancement of their sensing properties. In this way, the current-voltage or capacitance-voltage characteristics in such materials are modified when these devices are subjected to altered environments [15–17]. In this work, we study the properties of the junctions made by FTO deposited on macroporous silicon. The development of this work should help in understanding the response of these heterojunctions to gaseous analytes. The progress in PS optoelectronics depends on the understanding of the operating principles of PS devices. However, little work has been done on the electrical transport of macro-PS device structures in comparison to the research done on the optical and electrical properties of nano-PS and meso-PS [13, 18, 19]. Up to now, several models have been proposed for the transport of carriers in PS-based metal/PS/c-Si device structures [20–23]. These reports explain the behavior assuming that reverse current is determined by the surface mechanism associated with hopping  or with carrier generation from the surface states on the boundary between PS and the c-Si substate . The transport properties of oxidized (metal/PS/p-Si) structures have been hardly investigated, although relatively effective and stable electroluminescent device and photodetector structures based on oxidized PS were fabricated . Typically, the PS layer is sandwiched between the c-Si substrate and a metallic contact. This contact is usually gold or aluminium. Not much is known about the interfaces since band alignment depends on PS electronic properties. Nevertheless, in most literatures, the PS layer was considered to behave like a wide band gap semiconductor and assumed a Schottky barrier formed between the metal and the PS. In some cases, these metal contacts are replaced by transparent conductive oxide (TCO), such as tin oxide  or zinc oxide , modified with dopants such as fluoride or aluminium, respectively. In these cases, knowledge about the contact properties is very scarce. In this work, we present the results obtained for metal/c-Si/PS/FTO and metal/c-Si/PS/SiOx/FTO heterojunctions. We measured the J-V characteristic in the dark and under illumination for the prepared junctions. The transport parameters were obtained by fitting the characteristic J-V curves. The effect of illumination on the heterojunctions and transport properties is discussed as well. Morphology characterization was completed with scanning electron microscopy (SEM).
Porous silicon layers were obtained by electrochemical anodization of p-type boron-doped crystalline silicon wafers, with an orientation of (100) and resistivity of 10 to 20 Ω cm, in a hydrofluoric acid 50% and N,N dimethylformamide electrolyte solution in proportions of 1:9 in volume. The galvanostatic process was carried out for 1,800 s using a 10-mA/cm2 current density in darkness. A Teflon®anodization cell with platinum contact as the cathode and the silicon wafer as the anode was used. Aluminium 99.99% was evaporated as a backside contact of the Si wafer to improve the distribution of the current density in the anodization stage and to achieve an ohmic contact on the backside of the silicon substrate. Prior to the FTO deposition, some samples were oxidized in a rapid thermal annealing furnace. This oxidation was carried out at atmospheric pressure using a two-step process: (1) 450°C for 10 min followed by (2) 550°C for 30 min. The FTO, the n-type region in our devices, was fabricated starting from a synthesized precursor in order to get tin oxide by the sol-gel method . Subsequently, with this precursor, we proceeded with the deposition of a layer of SnO2:F using a spray pyrolysis method . The deposition temperature was set at 380°C, and it was controlled within ±2°C. The deposited thickness was about 900 nm with 20 min deposition. In this way, two types of heterojunctions were fabricated: Al/c-Si/PS/SnO2:F (abbreviated in the following as PS/FTO) and Al/c-Si/PS/SiOx/SnO2:F (abbreviated as PS/Ox/FTO). The J-V measurements were performed in a sandwich configuration using a Keithley 6487 digital picoammeter/voltage source (Keithley Instruments, Inc., Cleveland, OH, USA). The voltage was applied between the top FTO contact and the ohmic back contact. For forward bias, the ohmic back contact was grounded, and the FTO contact was biased negatively. The photoresponse of the device was measured by illuminating the sample with a halogen MR16 lamp with a light intensity of 110 mW/cm2. A set of optical density (OD) filters was used to obtain different illumination intensities from 110 mW/cm2 (OD = 0) to 1.10 × 10−1mW/cm2 (OD = 3). These measurements were made at 300 K. All layers were characterized by SEM in a JEOL J5M-35C microscope (JEOL Ltd., Akishima, Tokyo, Japan).
Results and discussion
It is possible to observe in the reverse bias region an increase in the photogenerated current when the light intensity is augmented. The current is significantly modified by the illumination only for reverse bias. The inset in Figure 3a shows a detail of the current behavior under illumination for the range between −2 and 0 V.
The current increases more than two orders of magnitude with respect to the current in dark condition. The junction has, in this case, an open-circuit voltage of 50 mV, similar to that shown in Figure 2, but the short-circuit current is 85 μ A/cm2 (almost two orders of magnitude lower than that in Figure 2) at illumination of 110 mW/cm2.
In the combination of back-to-back diodes, the current is limited for both polarities of the device. In this configuration, D1is associated to the junction PS/SiOx/FTO on the top of the pore, in which the presence of silicon oxide at the interface allows the formation of a MIS-type diode, and the second diode D2corresponds to the interface of crystalline silicon with porous silicon (c-Si/PS).
From the fit, the ideality factor we obtain for diodes D1and D2 is n=1. 6 and n3=3 for D3; the saturation currents are I01=5. 3×10−2mA/cm2, I02=6×10−5 mA/cm2 and I03=1. 25×10−4 mA/cm2; the serial resistance is Rs=43 Ω and parallel resistance is Rp=4. 6×105Ω. In this case, the values of I0for all the diodes are lower than obtained in the single diode of the PS/FTO heterojunction. In particular, the value of I02 is negligibly small, which prevents the current flow in forward bias on the two diode components of the circuit accordingly with the reduced photoelectric effect in the PS/Ox/FTO heterojunction. The ideality factors of diodes D1 and D2are similar to that obtained in the PS/FTO heterojunction in dark conditions, while the n3value is more similar to that obtained in the PS/FTO heterojunction in light conditions. The values of Rs and Rp are similar to the PS/FTO heterojunction.
We prepared two types of heteroestructures, Al/c-Si/PS/SnO2:F and Al/c-Si/PS/SiOx/SnO2:F, on macroporous silicon substrates with high coverage of the pore walls using the spray pyrolysis technique. The J-V characteristics were measured in the dark and under illumination. We found that the characteristics of PS/FTO devices are well fitted using a simple diode model in both cases. Nevertheless, the fitting parameters (saturation current and ideality factor) that produce a good accordance with the experimental data are not the same in dark and illuminated conditions. This fact is an indication that this heterojunction is actually more complex than a single diode. The J-V characteristics of the PS/Ox/FTO heterojunction are in accordance to a more complex equivalent circuit where a second component of two back-to-back diodes is connected in parallel. Although this model incorporates three more free parameters in dark conditions, all the illumination conditions are well fitted with the same parameters obtained in the dark, where only the photocurrent intensities in the diodes are free parameters.
This work was partially supported with grants ANPCyT project PICT 32515, the Universidad Nacional del Litoral project CAID 2009 Nro 68-343. We acknowledge the technical support from Ramon Saavedra.
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