Thin Solid Films 520 (2011) 680683

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Thin Solid Films

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / t s f

A detailed study of the series resistance effect on CdS/CdTe solar cells with Cu/Mo back contact
J.L. Pea a, b,, O. Ars a, V. Rejn a, A. Rios-Flores a, Juan M. Camacho a, N. Romeo b, A. Bosio b
a b

Applied Physics Department, CINVESTAV-IPN Mrida, C.P. 97310 Mrida, Yucatn, Mexico Dipartimento di Fisica, Universit di Parma, Campus Universitario, Parco Area delle Scienza, 43100 Parma, Italy

a r t i c l e

i n f o

a b s t r a c t
CdS/CdTe thin lm solar cells with an area of 1 cm2 were obtained and studied in detail. A ZnO buffer layer was deposited by reactive RF-sputtering on commercial ITO substrates. The CdS layer was grown on ZnO also by using RF-sputtering and CdTe thin lm was deposited by conventional CSS technique. The chlorination of the solar cells is performed into Freon atmosphere at 400 C. The CdTe thin lm surface was chemically etched by using BrMethanol solution. The back contact was deposited using RF-sputtering from a pure Cu and Mo targets. The procedure developed in this work led us to make systematically solar cells with good efciency. However, the series resistance has a high value for an area of 1 cm 2 (22 cm 2). In order to make more detailed study, the solar cell with an area of 1 cm 2 was divided in a 3 3 matrix. A good homogeneity in cell properties is observed and the efciency increases to more than 11%, fundamentally through decreasing series resistance. 2011 Elsevier B.V. All rights reserved.

Available online 4 May 2011 Keywords: Solar cell CdS/CdTe Back contact Series resistance

1. Introduction Series resistance (Rs) is a very important parameter in solar cells, since a high value of it limits the efciency of the cell through the ll factor (FF) [1,2]. In the case of CdTe cells, it is a very important aspect, as the back contact can have a strong contribution at Rs due to the high work function of the CdTe semiconductor [3,4]. Wu [5] has pointed out that the Rs in CdTe cells is closely associated with the quality of the CdS/CdTe junction and its record cell, with efciency of 16.5% has a Rs = 1 cm 2. In this work, we make a detailed study of Rs in CdTe cells contacted with Cu/Mo [6,7]. This contact is poorly studied in the case of cells grown on glass substrate [8] in comparison to others such as Cu/Au [9] and with buffer layers [10]. In the case of cells grown on Mo foils a thin layer of Au is used between Cu and Mo to improve this contact [11]. Back contacts of Cu/Mo have been reported without roll over and metallization with this element, yield long-term stable CdTe solar cells [12]. An ohmic Cu free back contact with MoOx as the contact buffer has been found recently with a minimum Rs of 4.7 cm 2 [13]. 2. Experimental details The CdS/CdTe cell developed in this work is prepared on glass substrate coated with indium tin oxide (ITO) as a transparent conducting oxide (TCO). We used a buffer layer of ZnO (200 nm)
Corresponding author at: Applied Physics Department, CINVESTAV-IPN Mrida, C.P. 97310 Mrida, Yucatn, Mexico. E-mail address: jlpena@mda.cinvestav.mx (J.L. Pea). 0040-6090/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.tsf.2011.04.193

lm deposited by RF magnetron sputtering starting from a metal Zn target with 4 N purity. The used ZnO lm has a resistivity of about 10 3 cm measured by four probe method and helps to reduce shunts caused by holes from CdS thin lm and enhance the open-circuit voltage (Voc) and the FF [5]. Zinc oxide has been identied by Romeo et al. [14] and Matin et al. [15] as a potential candidate for buffer layer into CdTe cells, some researches like Mazzamuto et al. [16] and Perrenoud et al. [17] have used successfully ZnO as a buffer layer. In general the use of this material semi-insulating has allowed us to improve the reproducibility and performance of our solar cells. Our investigation on the benets of ZnO as buffer layer is underway and will soon be published. CdS lms (160 nm) were grown by RF sputtering also with a target of CdS with 4 N purity. CdTe lms (8 to 10 m thick) are grown by CSS using two rectangular graphite blocks (9 9 0.5 cm), heated by special halogen lamps (they do not produce contamination). The separation between graphite blocks is 35 mm and the atmosphere during the growth was of 0.1 mbar of O2 and 0.4 mbar of Ar. The source and substrate temperature were 590 C and 520 C, respectively. The rate of deposition of CdTe lm is about 1 m/min. The chlorination is performed using Freon gas that contains chlorine in its composition, those one decomposes at 400 C, it allows chlorine releasing. This method was developed by Romeo [16,18]. The treatment is done at 400 C in a quartz ampoule in a mixture of Freon argon with to a total pressure in the range of 400800 mbar. Freon pressure is varied between 20 and 50 mbar. After 5 min treatment the Freonargon mixture is removed and high vacuum is restored in order to remove surface residues of Cl, which can inuence the next step of the back contact. The ohmic contact on CdTe lms was performed by etching the CdTe surface with Br2:CH3OH solution followed by the

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deposition of two lms, Cu (5 nm) and Mo (0.75 m), grown by RF sputtering in Ar atmosphere. After, the device is annealed at 200 C for 20 min in an Ar atmosphere. Once completed, the cells were delimited by mechanical scribing by using a stainless steel tip in a square form, with area = L 2 (L is the side length). In our fabrication method a light soaking of the cells is included. This is performed for 20 min with the cell put under a halogen lamp. The light intensity on the cell is about 900 mW/cm 2 and its temperature rises to 100 C. With this light soaking we can optimize the cell performance, achieving increases in both Voc and short-circuit current density (Jsc). We will discuss about this in more detail below. The thickness of different deposited lms for cell fabrication was measured using a Vecco Dektak-8 Stylus Proler. Finally, the current densityvoltage (JV) measurements were determined using a SourceMeter from Keithley 2420. Specic LabVIEW software was used to collect the JV data. The Rs and shunt resistance (Rsh) were determinate by the slope of JV characteristics at I 40 mA in forward and 0.2 V in reverse, respectively [19]. 3. Results and discussion Fig. 1 shows the current densityvoltage JV characteristics of cells on the same substrate with areas from 1 cm 2 to 0.08 cm 2. Table 1 shows the parameters of these four cells and the ones for a cell with a small area (0.034 cm 2) optimized by light soaking. Note that in all JV characteristics, there is no presence of rollover [12]. From Fig. 1 we see that these cells have close values of Jsc and Voc, but different values of Rs. We correlated uctuations in Jsc and Voc to local variations in the properties of the cell. Fig. 2 shows the JV characteristics of an array of 3 3, cut on the same substrate, from a 1 cm 2 cell, this gure shows a fairly good homogeneity, with little uctuations in Jsc and Voc as observed in Fig. 1. This result supports the idea that uctuations in Jsc and Voc of Fig. 1 are determined by spatial inhomogeneities in the cell. Fig. 3 shows simulated JV characteristics with a diode simple model, where Rs was varied, considering Rsh sufciently high to not inuence the FF (our Rsh experimental values are sufciently high to have an important inuence in this parameter). This classical gure shows the effect of Rs in solar cells [2] and makes clear the fact that Jsc is not affected by Rs up to 25 cm 2, but not the FF. As it is seen from Fig. 1, the experimental curve of the cell with 1 cm 2 is qualitatively similar to the theoretical curve with 10 cm 2. From the above considerations, we can see that these cells are limited primarily by the value of Rs. In order to know the quality of the diode in our cells, we estimated

Table 1 Parameters of cells with different areas and for a cell with a small area (0.034 cm2) optimized by light soaking. Rsh is the shunt (parallel) resistance. L (mm) 10 8 5 2.8 1.85 Jsc (mA/cm2) 14.4 13.8 11.9 13.5 22.4 Voc (V) 0.751 0.742 0.769 0.751 0.73 FF (%) 48 57 69 72 69.7 Efciency (%) 5.2 5.9 6.3 7.3 11.4 Rs ( cm2) 22.6 16.2 8.0 5.1 3.7 Rsh ( cm2) 472.6 702.9 631 1023 554 Area (cm2) 1 0.64 0.25 0.078 0.034

reverse saturation diode current (J0), and diode ideality factor (n) for the smallest cell (to reduce the Rs effect in forward dark JV characteristic). This estimation was performed through ln (J) versus V curves in darkness [1,20]. A J0 10 11 A/cm 2 and n = 1.7 are obtained in forward [19], and J0 10 10 A/cm 2 in reverse. The results conrm a good quality of the cell diode. In addition, these cells do not show the JV curve crossing between dark and light, another feature for well behaved cells [16]. There are reports in literature of cells with Voc and Jsc with good values but low FF, determined by a high value of Rs, due to a non-optimized back contact [2]. Fig. 4 shows the experimental dependence of Rs with the L dimension of the cells. This is clearly a parabolic dependence of the type a + b L 2, according to models developed for thin lm solar cells, which take into account the distributed resistance of the TCO [21]. We arrive at this type of relationship, in which the rst term corresponds to the contribution of the absorber and the second to the contacts. According to this model, the result in the gure would indicate a contribution of CdTe on the order of 104 cm which corresponds well with what we measured by four-point lighting conditions and with those reported in literature [8,22]. Fig. 4 shows that FF versus Rs dependence is linear, which corresponds to the Formula FFs = FF0 (1 Rs/Rch) where Rch = Voc/Jsc [23]. FF0 is the ll factor that provides the quality of the cell junction and it is interesting to note that extrapolation of the line in Fig. 4, gives 78%, which corresponds to the value reported for cells of the state of the art [5]. This result proves that the optimized Rs value in our cells, leads to an achievable efciency over 11% in 1 cm2 area. In the case of the CdS/CdTe cells there are reports of the effect of light soaking in aging [24], but in our knowledge, not on the benecial effect of soaking for short times of minutes. In the case of amorphous Si cells in Ref. [25] reported that Voc increases with soaking, but it is unclear whether the mechanism is the reduction of recombination in the junction or in the bulk of the absorber. Anyway, our results show

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Fig. 2. JV characteristics of an array of 3 3, cut on the same substrate, from a cell with an area of 1 cm2.

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Fig. 1. JV characteristics of cells with different areas.

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Fig. 5. JV characteristics of an optimized small cell by using light soaking.

simultaneous increases of Jsc and Voc, which has to be related to a decrease in the rate of recombination in the cell. This presumably could be determined by an ion-assisted redistribution in internal electric elds produced by lighting and a temperature of about 100 C. Fig. 5 shows the JV characteristic of a cell of small area where the light soaking treatment has been optimized. As seen in Table 1, this cell has very good properties (more than 11% efciency) but still the Rs value is higher than that reported by Wu [5]. In larger areas, Rs limits the efciency due to the fact that it tends to a value close to 25 cm 2. In Ref. [12] it is demonstrated that the carrier concentration, in the case of Cu/Mo contacts, is lower than that of the Sb2Te3/Mo, however the barrier height is low enough to create a quasi-ohmic contact. However, this low carrier density in the back contact zone, can be explained through relatively high Rs observed in our work with Cu/Mo contacts. XRD studies performed to our cells after the Br2: CH3OH treatment, followed by Cu deposition by RF sputtering, show that the Cu1.4Te alloy is formed in the surface of CdTe lm, when the Cu lm is very thin (5 nm). This is the best alloy for back contact containing Cu [26]. It is important to comment that the Mo/Cu has provided to our cells more stability and robustness Cu/Au contacts

used in Ref. [8] allowed to obtain values of Rs of about 3 cm 2 in 1 cm 2 area, but with bad reproducibility and fast degradation of cell properties. 4. Conclusion Square solar cells (of side L) obtained in this work show a quadratic behavior in L for the series resistance. This behavior was reported previously for distributed resistance models, which consider the contribution to Rs of transparent front contact. Extrapolating the linear dependence of FF as a function of Rs we got a FF of 78% as for the cells of the state of the art. This corresponds to the good properties of our diode cells with a J0 of the order of 10 10 A/cm 2 in dark. The high value of series resistance of our cells with Cu/Mo back contact (23 cm 2 for cell with 1 cm 2 and 4 cm 2 for cell with 0.03 cm 2) could be related to a low carrier density characteristic of this contact. However this carrier concentration is sufcient to have a barrier height low enough to create a quasi-ohmic contact without the presence of rollover in JV characteristics. Through a procedure of light soaking for several minutes and low temperatures (100 C) we reach 11.4% efciency, which may be related with ionic redistribution in the junction region that improves the quality of the cell. Acknowledgment This work has been supported by CONACYT-Mxico under contract FORDECYT-116157. J. L. Pea acknowledges CONACYT-Mxico by nancial sabbatical support received under contract of Estancias Sabaticas No-128592. A. Rios-Flores acknowledges CONACYT-Mxico by scholarship to study in the Applied Physics Department of CINVESTAV-IPN Unidad Mrida. The authors acknowledge Oswaldo Gmez, Willian Cahuich and Roberto Sanchez by technical support and Lourdes Pinelo by secretarial assistance. References
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Fig. 4. a) Series resistance dependence with the square cell side length dimensions and b) ll factor versus series resistance values measured in the cells.

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