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Applied Surface Science 190 (2002) 390394

Fabrication of high quality siliconpolyaniline heterojunctions

Jane M.G. Laranjeiraa, Helen J. Khourya, Walter M. de Azevedob, Eronides F. da Silva Jr.c,*, Elder A. de Vasconcelosc

ria, 50740-540 Recife, Pernambuco, Brazil Departamento de Energia Nuclear, Universidade Federal de Pernambuco, Cidade Universita b mica Fundamental, Universidade Federal de Pernambuco, Cidade Universita ria, Departamento de Qu 50670-901 Recife, Pernambuco, Brazil c sica, Universidade Federal de Pernambuco, Cidade Universita ria, 50670-901 Recife, Pernambuco, Brazil Departamento de F

Abstract A high quality siliconpolyaniline heterojunction is produced by spin-coating of soluble polyaniline on silicon substrates. The devices have excellent reproducibility of their electrical characteristics and high rectication ratio. The rectication ratio is 60,000 at 1.0 V at room temperature, and typical reverse current at 1.0 V is 3 nA. A G=I G plot is used to analyze the currentvoltage characteristics, yielding typical series resistance of 4 kO and ideality factor in a range from 1.0 to 2.0. The devices present great potential for use as radiation and/or gas sensors. # 2002 Elsevier Science B.V. All rights reserved. PACS: 71.20.Rv; 72.80.Le; 73.40.Lq; 85.30.Kk
Keywords: Heterojunction; Silicon; Polyaniline; Sensor; Electrical properties

1. Introduction Conjugated polymers are a new class of material of great potential for fabrication of solid state devices. The electrical conductivity of these polymers can be changed from insulating to metallic by chemical or electrochemical doping and they can be used to produce electronic devices such as Schottky diodes, eld effect transistors, light-emitting diodes, and photodetectors, among others [16]. The polymers used on these reports are promising for applications in the medical and environmental elds due to their conductivity sensitivity to specic photon energies or chemical species [6]. Recent studies [7] have shown that conducting polymers are sensitive to radiation, and also sensitive to a
Corresponding author. Tel.: 55-81-3271-8450; fax: 55-81-3271-0359. E-mail address: (E.F. da Silva Jr.).

wide range of gases and vapor. Among several polymers studied, polyaniline presents advantages for application in electronic devices since its electrical properties can be changed by oxidation or protonation of imine nitrogen backbone, and additionally it presents thermal and environmental stability. However, despite their potential, polymeric devices still need much improvement in their electrical and interfacial characteristics. The devices often present poor reproducibility of electrical characteristics [8]. Early reports on electrochemically deposited polyaniline/silicon heterojunction [9,10] describe devices with very low rectication ratio (approximately 50 at biases of 5 V) and using relatively thick lms. In this work, we describe a technique to form high quality siliconpolyaniline heterojunctions with excellent reproducibility of electrical characteristics and high rectication ratio. These characteristics, in part, are a requirement for further use of the devices in a variety of sensor applications.

0169-4332/02/$ see front matter # 2002 Elsevier Science B.V. All rights reserved. PII: S 0 1 6 9 - 4 3 3 2 ( 0 1 ) 0 0 9 0 1 - 1

J.M.G. Laranjeira et al. / Applied Surface Science 190 (2002) 390394


2. Experimental details Rectifying heterojunctions were formed by using the spin-coating technique, where a highly uniform lm of polyaniline of 40 nm was deposited onto a silicon substrate (n-type, (1 0 0), 1 O cm). All procedures were done in a clean room (class 1000). Electronic grade chemicals were used in a modied RCA cleaning of silicon wafers [11] and for the polymer synthesis, analytical grade chemicals. Aniline was three times distillated at atmospheric pressure and stored in dark at low temperature. The devices were stored in vacuum before electrical characterization. The polyaniline synthesis was made following the procedure of MacDiarmid et al. [12]. The polyemeraldine salt obtained was treated with 0.1 M NH4OH to form polyemeraldine base soluble in organic solvents. The solution obtained was used to form the polyaniline thin lm over silicon substrate by spin-coating. This lm was treated with 1 M H2SO4 solution to form the polyemeraldine salt. The thickness of polyaniline lm was measured by ellipsometry (Rudolf Research Auto-EL IV Ellipsometer). Electrical contacts were deposited by vacuum evaporation at a pressure below 106 Torr. A circular gate contact area 0:0036 cm2 450 nm thick was obtained by gold evaporation on polyaniline lm and a large area backside contact (50 nm thick) was obtained by aluminum evaporation. The backside contact was not optimized to be perfectly ohmic and it has a low barrier height, which results in increased series resistance. However, experience showed that this increased series resistance was acceptable at this stage of device development. Power loss during device operation is not necessarily a concern, since these devices are intended to be used as radiation detectors or gas detectors and this kind of devices are usually polarized at reverse bias or can be polarized at low forward bias, so that the effect of an increased series resistance is not so important. The currentvoltage characteristics were measured with a Hewlett Packard HP 4155A Semiconductor Parameter Analyzer.

Fig. 1. Currentvoltage characteristics of 20 different heterojunction diodes. The device structure is depicted in the inset.

3. Results and discussion Fig. 1 shows the forward and reverse current voltage I V characteristics of 20 polyaniline

silicon heterojunction diodes. The reproducibility of characteristics is apparent. Measurements of the main heterojunction properties indicate high uniformity of electrical characteristics with a variation in the parameters of less than 5%. Average reverse current at 1.0 V is 3 nA and the rectication ratio is typically 60,000 at 1.0 V. The achievement of such values on polymer-based heterojunction strongly indicate the high quality of the polymer lm as well as the excellent characteristics of the gold/polyaniline and polyaniline/silicon interfaces. Preliminary results obtained by atomic force microscopy and Auger spectroscopy (not shown) points to a surface roughness on the top of the polymer lm of less than 4 nm and an abrupt polyanilineSi interface formation, although with some minor degree of gold and silicon inter-diffusion into the polymer lm. Certainly, the care taken during the silicon substrate preparation and spin-coating has contributed for the substantial improvements of the junction electrical properties. Fig. 2 shows in more detail the forward characteristic of one of the devices illustrated in Fig. 1. At low forward voltages, the current follows an exponential dependence with ideality factor equal to 1.05. At higher voltages, the current follows an exponential dependence with an ideality factor equal to 1.90. In a


J.M.G. Laranjeira et al. / Applied Surface Science 190 (2002) 390394

Fig. 2. Forward I V characteristic of a typical diode. Ideal curves calculated with n 1 and n 2 are also shown for comparison. The inset shows the G=I G plot (Werners plot A [14]) and calculated device parameters.

rst analysis approach, one can consider these exponential currentvoltage characteristics to be due to similar mechanisms as in a standard pn homojunction [13]. It is known that the forward I V characteristics of standard pn junctions can have four distinct regimes: (1) the current can be dominated by generationrecombination mechanisms within the depletion region (giving n 2); (2) the current can be dominated by diffusion and generationrecombination outside the spacecharge region (giving n 1); (3) the so-called high-injection regime, where the injected minority-carrier density is comparable with the majority concentration (giving n 2); (4) the regime where the resistivity in the quasi-neutral regions of the junctions and contact resistances absorb an appreciable amount of the voltage drop between the diode terminals, so that I V characteristics deviate from an exponential behavior and become linear. In Fig. 2, we observe a transition from n 1 at low forward voltages to n 2 at higher forward voltages and, for even higher voltages (above 0.6 V), the series resistance begins to dominate the characteristics. If our structure were a standard pn homojunction, in the

light of the discussion above, this would correspond to a transition from regime (2) to regime (3). A transition from region (2) to (1) is not possible because the generationrecombination current within the spacecharge region ( exp(qV/2kT)) and the diffusion current ( exp(qV/kT)) are additive and the ( exp(qV/kT)) term would always dominate at higher voltages. However, in our experiments, we do not have a p/n homojunction and the analysis above, although correct, is not completely applicable. Since our main concern here is to show the quality and reproducibility of the electrical characteristics and potential applications of our devices, we will postpone the detailed discussion to a future paper. In this future paper, we will analyze the device characteristics in the light of an appropriate p/n heterojunction theory, such as that proposed by Chattopadhyay and Haldar [15,16]. A simple method to obtain reliable information from I V curves of Schottky contacts and pn junctions has been proposed by Werner [14]. His method involves the use of the small signal conductance to improve the accuracy of parameter extraction. A conductancecurrent versus conductance plot

J.M.G. Laranjeira et al. / Applied Surface Science 190 (2002) 390394


G=I G can be used to analyze the device characteristics. If the G=I G plot is linear, one is assured that the series resistance (Rs), saturation current (Is) and ideality factor (n) of the device are voltage independent, and therefore usual pn junction theory may be applied to the device. From a linear G=I G plot, it is possible to evaluate accurately important device parameters, such as series resistance and the ideality factor of the junction. We used this method to calculate the series resistance and ideality factor of our devices, as shown in the inset of Fig. 2. In order to obtain the value of series resistance appropriately, the G=I G analysis needs to be done with data points in a voltage range where the effect of series resistance on the current is important. Therefore, we used data points in the voltage range above 0.35 V up to 1.25 V. In this voltage range, the ideality factor is approximately 2. The G=I G is highly linear, indicating that the device is adequately described by a model where Is, Rs and n are not voltage-dependent. This is another indication of high quality of the device and good interfacial properties. Devices with poor interfaces and voltage-dependent parameters do not show such a linearity in the G=I G characteristics. Indeed, Werner [14] has shown some examples of surface damaged (plasma treated Au/Si) diodes, which indicated a strong deviation from a linear G=I G behavior, despite showing apparently good exponential I V characteristics with n 2:20. We stress here that in several reports of polymer-based junction devices the series resistance (Rs), saturation current (Is) and ideality factor (n) have been extracted from I V plots without careful consideration of shunt and series resistance, which distort the linear behavior in the semi-logarithmic I V characteristic. Moreover, ts to exponential I V characteristics with ideality factor above 2 are not uncommon in the literature for polymer-based devices. Such ts should be regarded with caution. From the G=I G plot, the series resistance and ideality factor of our devices were 4 kO 5% and 1:9 0:5%, respectively. We are presently performing experiments to investigate the conduction mechanisms and heterojunction parameters in more detail. Regardless of these details, the results shown here already demonstrate the potential for the fabrication of high quality polyanilinesilicon heterojunctions, which may have important applications as sensors in the medical eld, such as ionizing radiation

Fig. 3. (a) Electrical response of the heterojunction diode to gamma-ray radiation; (b) electrical response of the heterojunction diode to different gases.

detection as well as in the biosensor or environmental eld as gas sensors. Preliminary results indicate that the devices described in this work are very sensitive to gamma-rays and to exposure to several gas moistures. Fig. 3 illustrates the use of the heterojunction as a sensor. In Fig. 3(a) we show the device response to a 11 kGy dose of gamma radiation and in Fig. 3(b) we show devices responses after exposure to trichloroetylene (TCE) for 5 min and to ammonia (NH3) for 1 min. The sensitivity to these agents is evident. These results lead to calibration curves for the devices as a sensors. Further details about the sensor responses described above will be published elsewhere.


J.M.G. Laranjeira et al. / Applied Surface Science 190 (2002) 390394

4. Summary We have succeeded in fabricating high quality polyanilinesilicon heterojunctions. The devices present reproducibility of electrical characteristics, good rectifying behavior, with rectication ratio 60,000 at 1.0 V. At low forward voltages, the currentvoltage characteristic is dominated by the diffusion mechanism, giving an ideality factor close to 1 and at higher forward voltages the ideality factor becomes close to 2. The last being a signature of generationrecombination within the spacecharge region or, more probably, of high-injection condition. At even higher voltages, the series resistance dominates the characteristics. A G=I G plot was used to analyze the currentvoltage characteristics and its linearity indicate that the devices are adequately described by a model where Is, Rs and n are voltage independent. The series resistance is 4 kO 5% and the ideality factors lie in a range from 1.0 to 2.0. Atomic force microscopy and Auger spectroscopy indicate a highly uniform polymer lm making a good and abrupt heterojunction with silicon. The heterojunction is presently been evaluated as a strong candidate for different type of sensor applications.

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Acknowledgements The authors are thankful to the nancial support received during the development of this work from CNPq, PADCT/FINEP under contract No.