Renewable Energy 20 (2000) 155165 www.elsevier.

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Study of the electrical and junction properties of ITO thin lms deposited on CdTe and InP substrates
H. Yakubu a, c,*, P. Thilakan b, c
a Physics Department, University of Cape Coast, Cape Coast, Ghana Crystal Growth Center, Anna University, Chennai, Tamil-Nadu, India c ENEA-Centro Ricerche, Localita Granatello, 80055, Portici (NA), Italy b

Received 13 June 1999; accepted 27 June 1999

Abstract Thin lms of indium tin oxide (ITO) have been deposited on fused quartz substrates by the spray deposition and rf-magnetron sputtering methods and their optical and electrical properties investigated. The junction properties of fabricated ITO/pCdTe and ITO/pInP structures have also been studied and their electrical properties presented. It is established that the deposited ITO lms have a lattice constant of 10.14 A and grow in cubic modications along the (400) direction. Their transmittance value rises up to between 85% and 90% and extends well beyond the visible range of the spectrum. In the forward direction of the ITO/pCdTe structure, it is suggested that tunnelling dominated processes determine the current ow mechanism. Recombination currents at the interface region and thermionic-emission currents, however, dominate in the ITO/pInP structure at low bias and high bias respectively. The two structures can best be described as heterojunctions. # 1999 Elsevier Science Ltd. All rights reserved.
Keywords: Heterojunction; Indium tin oxide; Indium phosphide; Cadmium telluride

* Corresponding author. Tel.: +233-42-33942; fax: +1-233-42-32446. E-mail address: csucc@ghana.com (H. Yakubu). 0960-1481/00/$ - see front matter # 1999 Elsevier Science Ltd. All rights reserved. PII: S 0 9 6 0 - 1 4 8 1 ( 9 9 ) 0 0 0 9 7 - X

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1. Introduction The numerous uses of ITO has of recent times made it one of the most popular semiconductor oxides. It has attracted lots of attention because of its applications in the optoelectronic and photovoltaic industries, in heat reecting mirrors and in some biological systems [1]. It can be deposited by a variety of methods including evaporation, reactive electron beam evaporation, reactive thermal deposition, spray deposition and rf-magnetron sputtering [1,2]. Particularly attractive among these methods are the spray deposition and rf-magnetron sputtering methods because they are relatively simple. The spray deposition method is also vacuumless and relatively fast, whereas the rf-magnetron sputtering method has been identied as a controlled method for quality lms irrespective of the conductivity of the target [3]. ITO is a particularly suitable front layer material because of its favourable wide bandgap and low resistivity. ITO/pInP junctions have attracted a lot of interest owing to their uncomplicated fabrication process and high eciencies. Notwithstanding this relative success, there is still a lot to be understood about their operating mechanisms [4]. ITO/CdTe on the other hand, has been widely studied, but not much attention has been paid to the transport properties, particularly for ITO/ pCdTe where ohmic contact formation is relatively complicated [5,6]. The purpose of this paper is to report on studies on ITO deposited on fuzed quartz substrates by the spray deposition and rf-magnetron sputtering methods. The result of studies on ITO/pInP and ITO/pCdTe junctions has also been presented. This paper attempts to further the understanding of the junction properties of these two structures, particularly, their current ow mechanisms.

Fig. 1. Transmittance and sheet resistance of spray deposited ITO vs deposition time.

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2. Experimental procedure 2.1. Deposition of indium tin oxide Thin lms of ITO were deposited by spray deposition and rf-magnetron sputtering methods for comprehensive study. Using a method described elsewhere [7,8], ITO was deposited by spraying an alcohol solution of indium chloride (InCl3) and tin chloride (SnCl4) mixed in dierent proportions and which, upon deposition on an appropriate substrate, formed ITO. ITO is formed by virtue of an endothermic reaction which occurs on the substrates, in the presence of oxygen, converting the chlorides into oxides. The proportion of indium oxide (In2O3) and tin oxide (SnO2) in the lms necessary for attaining maximum transmission and low sheet resistance was determined by depositing lms from solutions of (In2O3)1x (SnO2)x with varying X. The solution was sprayed onto heated fused quartz substrates at a rate of 1000 A/min for 45 s (see Fig. 1). Argon served as the main transport agent and the deposition temperature, measured by means of an alumel-chromel thermocouple, was between 723 K and 773 K. Transmittance and sheet resistance measurements as a function of the deposition time, as shown in Fig. 1, were used to establish the optimum conditions for ITO deposition. The Van der Pauw method was used to measure the properties of the deposited lms. They were found to be in good agreement with values obtained elsewhere [1,9,10]. The properties of the ITO lms were found to depend on the concentration of InCl3 and SnCl4 in the solution used for deposition, the substrate temperature, spraying time and deposition rate. The composition of the lms with the best parameters was also found to be (In2O3)0.93 (SnO2)0.07. The rf-magnetron sputtering method has been identied as one of the controlled deposition methods for high quality ITO lms irrespective of the target conductivity [3]. A Leybold Z-400 rf-magnetron sputtering system was used for deposition. By this method, ITO was deposited on fused quartz substrates. Hot pressed ITO target of In2O3:SnO2 (90:10 wt%) was used and the deposition rate of the lms monitored with a calibrated quartz crystal oscillator. The system chamber was evacuated to a vacuum of 1 105 Torr and an argon gas of 99.99% purity then admitted into the chamber. During the sputtering process, a
Table 1 The properties of deposited ITO lms Parameters Conductivity, s (ohm1 cm1) Concentration, N (cm3) Mobility, m (cm2V1s1) Transmittance, T (%) Orientation Spray-deposited ITO 82 102 19.0 1020 27 89 (400) Rf-magnetron sputtered ITO 42 102 14.2 1020 21 85 (400)

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substrate holder temperature of 298 K and argon partial pressure of 2 102 Torr was maintained. Deposition rates of 90 A/min and 160 A/min were used for deposition on the quartz substrates at power levels of 160 W/cm2 and 260 W/cm2 with rf-frequency of 13.56 MHz. The thickness of the lms was controlled at 2000 A. The parameters of the deposited ITO lms obtained by the two deposition methods are presented in Table 1. 2.2. Device fabrication For junction formation and study, substrates of p-CdTe and p-InP were prepared. The CdTe monocrystals were grown by the zone sublimation method and sliced along the (110) plane into 2.5 cm diameter substrates. It had conductivity of 0.16 ohm1 cm1, carrier concentration of 2.7 1016 cm3 and mobility of 42.5 cm2 V1 s1. The InP substrates were 5 cm in diameter, liquidencapsulated Czockralski (LEC) grown, semi-insulating h111i oriented monocrystals with a carrier concentration of 3 1017 cm3. The parameters of the monocrystals were conrmed by Hall measurements. Using standard proceedure, the substrates were prepared by mechanically polishing with alumina powder of grain size 1 micron, followed by cleaning in organic solvents. The CdTe was chemically etched in a dichromate solution as suggested in [11,12] for 50 s to obtain substrates of 0.5 mm thick and a nal etching step was done to obtain a residue free surface. On the other hand, the InP wafers were polished using a bromine methanol solution to obtain mirror polished wafers. The mirror polished wafers were further cleaned in acetone to obtain residue free surfaces. In both cases, care was taken to remove the damage created by the slicing or grinding processes. The CdTe samples were mounted and thin lms of ITO deposited on them by spray deposition forming an ITO/CdTe junction. The solution with the optimum parameters for spray deposited ITO lms (In2O3)0.93 (SnO2)0.07, was used in the deposition process. The InP samples were mounted in the deposition chamber of the rf-magnetron sputtering system and ITO deposited on them obtaining an ITO/ InP junction. Deposition was facilitated according to the methods described in Section 2.1. To conrm the quality of the deposited ITO lms, during deposition on the CdTe and InP samples, ITO was also deposition on clean fused quartz substrates. Ohmic contacts to pCdTe was formed by vacuum deposition of gold after polishing the surface in a chemical etchant. The etchant was chosen to etch away the Cd component of the CdTe, thereby, exposing a rich Te surface to enhance contact formation [11,12]. A Ag:Zn/Ag structure of deposited Ag:Zn (86:16 wt%) alloy, followed by vacuum deposition of Ag was used as ohmic contacts to the pInP [13]. The fabricated contacts were annealed for 23 min. Repeated measurements were made on the contacts and they showed no signs of instability or degradation.

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3. Results and discussion 3.1. Characteristics of deposited ITO lms Figs. 2 and 3 represent the x-ray diraction tracing of the ITO lms. Upon analyses, the deposited lms were found to grow in cubic modications with a lattice constant of 10.14 A in the direction of the (400) plane which is in good agreement with the American Society for Testing and Materials (ASTM) value. ITO deposited on InP was however, annealed for improved crystallisation. Its lattice constant decreased from 10.245 A to 10.135 A upon annealing. This could be attributed to the removal of some structural defects and the re-arrangement of Sn atoms in the In2O3 lattice structure. Figs. 4 and 5 show the optical transmittance of the deposited ITO lms. It seems from the plots that the lms have transmittance values that rise to a maximum at between 85% to 90% after which it attains a plateau. This extends well over the visible range of the spectrum and signies that, the lms could be successfully used as window material in heterojunction structures. From optical measurements, the bandgap of the lms was found to be 3.45 eV and 3.75 eV for the spray and rf-magnetron sputtered lms respectively.

Fig. 2. X-ray diraction tracing of ITO by the spray deposition method.

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Fig. 3. X-ray diraction tracing of ITO by the rf-magnetron sputtering method.

3.2. Junction characteristics Figs. 6 and 7 are typical representations of the dark forward current-voltage characteristics of the ITO/pCdTe and ITO/pInP junctons plotted in the semilogarithmic scale respectively. In Fig. 6, the curves are almost parallel straight lines at low voltages up to 0.3 V (diusion potential) and high temperatures T > 270 K. The nature of the curves in this structure indicates a tunnelling process as the main current ow mechanism and conforms to the Riben and Feucht tunnelling model [14]. Since the doping level in the CdTe is quite low for direct tunnelling through the potential barrier, electrons tunnel from the conduction band of the ITO to traps in the interface region and subsequently recombine with holes from the valence band of the CdTe. According to this model [14], the forward current can be expressed as J Jt expAV expBT 1

with Jt proportional to the density of traps and A and B constants independent of temperature and voltage respectively. The value of A is expressed as

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Fig. 4. Optical transmittance of the spray-deposited ITO lms.

Fig. 5. Optical transmittance of the rf-magnetron sputtered ITO lms

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Fig. 6. Current-voltage characteristics of the ITO/pCdTe structure.

dln J 8 me, h Es s dV 3h Na, d

!1a2

where me,h is the eective mass of electron or hole, Es is the permittivity of the semiconductor, Na,d is the concentration of acceptors or donors and s is the fractional change in the carrier energy for each step in the tunnelling process. The number of steps in the tunnelling process is consequently expressed as 1/s. The ln J vs T plot is represented in Fig. 8. From the ln J vs V and ln J vs T plots, A was

Fig. 7. Current-voltage characteristics of the ITO/pInP structure.

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found to be 27.0 V and B to be 0.037 K1 respectively. This agrees with the typical values of A which are between 24 and 30 V while J varies between 104 106 A/cm2 [15]. Subsequently, the number of steps in the tunnelling process was found to be 249. A similar proceedure was used to explain the behaviour of the dark forward current mechanism in spray deposited ITO/Si junctions [7]. From the capacitance-voltage measurements obtained by computer software, the diusion potential was found to be 0.31 V and the concentration of charge carriers 2.65 1016 cm3. These results conrmed the values earlier obtained from the current-voltage studies and Hall measurements. Fig. 7 shows the dark forward current-voltage characteristics of ITO/InP. The curve display two distinct regions from 0 to 0.6 V and above 0.6 V. This behaviour has been commonly observed for ITO/pInP junctions [4,16] and the current-voltage characteristics represented by   qV 3 J Jo exp AKT where Jo is the saturation current obtained by extrapolating the current-voltage curve to the zero bias, K is the Boltzmann's constant, T is the absolute

Fig. 8. The ln J vs T plot of the ITO/pCdTe structure.

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temperature and q is the electronic charge. A is the diode ideality factor whose value helps determine the transport mechanism carriers. In the rst region, between 0 and 0.6 V, the diode ideality factor determined from the slope of the curve is 2.03 and the reverse saturation current is 1.8 106 A. This suggests that, the dominant mechanism in the current ow can be due to recombination at the interface region as suggested in [4]. A value of the order of 106108 A/cm2 for Jo and a diode ideality factor A = 2 can be attributed to recombination [15]. This type of recombination current conduction in the low voltage region could be a result of damage induced by processing at the interface region [16]. The second region, shows a characteristic feature similar to that of a schottky diode with an ideality factor A = 1. This indicates the dominance of thermionic emission currents [4]. Current-voltage measurements on junctions annealed at 573 K are shown in Fig. 9. This reveals that the change from recombination conduction to thermionic emission is limited below 0.1 V due to the reduction of the defects at the interface upon annealing. The dark current also reduced from 1.8 106 to 2 108 A/cm2. This observation is in good agreement with reports on similar structures cited in [17].

4. Conclusion The deposited ITO lms were found to grow in cubic modications with a lattice constant of 10.14 A along the (400) direction. Their transmittance values rose up to 90% and extended beyond the visible range of the spectrum signifying that the deposited lms could be used as window materials. The junction studies on ITO/pCdTe and ITO/pInP showed that dierent processes dominate in the current ow. In the ITO/CdTe structure, the tunnelling mechanism

Fig. 9. Current-voltage characteristics of annealed ITO/pInP structure.

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dominates in the forward direction, whereas, recombination currents at the interface region and thermionic-emission currents dominate at the ITO/InP junction. The behaviour of the structures can best be described as that of heterojunctions. Acknowledgements The authors wish to express their sincere gratitude to the TRIL oce of the Abdus Salam International centre for theoretical Physics for their generous funding and support. They also wish to express their gratitude to the Italian national agency for renewable energy and environment, ENEA-Portici (Naples), where some of the measurements were made.

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