Solar Energy Materials & Solar Cells 59 (1999) 75 } 84

Compositional and optoelectronic properties of CIS and CIGS thin "lms formed by electrodeposition
M.E. Calixto *, P.J. Sebastian , R.N. Bhattacharya , Rommel Nou"
Centro de Investigacio & n en Energn & a } UNAM, Solar-H2- Fuel Cell Area, Temixco, Morelos, 62580, Mexico NREL, Golden, Col., USA

Abstract CuInSe (CIS) and Cu(In,Ga)Se (CIGS) thin "lms were prepared by electrodeposition and   processing. The in#uence of "lm deposition parameters such as bath composition, pH, deposition potential and material purity on "lm properties was studied. The structural, morphological, compositional and opto-electronic properties of electrodeposited and selenized CIS and CIGS thin "lms were characterized using various techniques. As-deposited as well as selenized "lms exhibited a compact or a granular morphology depending on the composition. The "lm stoichiometry was improved after selenization at 5503C in a tubular furnace. The "lms are formed with a mixed phase composition of CuInSe and CuIn Se ternary phases. 1999     Elsevier Science B.V. All rights reserved.
Keywords: CIS; CIGS; Thin "lms; Film deposition

1. Introduction Cu(In,Ga)Se (CIGS) is one of the most important semiconductor materials that  can be used to make low-cost photovoltaic devices [1,2]. The co-electrodeposition technique, where Cu}In}Ga}Se species are present in the same chemical bath is one of the suitable techniques to prepare low cost thin "lms [3}12], because the deposition process does not require very sophisticated equipment and is easy to use it.

* Corresponding author. Fax:#52-7325-0018. 0927-0248/99/$ - see front matter 1999 Elsevier Science B.V. All rights reserved. PII: S 0 9 2 7 - 0 2 4 8 ( 9 9 ) 0 0 0 3 3 - 1

In the "rst case.0125 M CuCl . CIS and CIGS thin "lms were prepared by varying the electrodeposition parameters such as pH. the counter electrode a Pt mesh and the working electrode a Mo coated glass substrate. This semiconductor material can be prepared by di!erent deposition techniques like physical evaporation or electrodeposition of precursor "lms. XRD and opto-electronic characterization . To realize this.025 M InCl   and 0. 3. A potentiostat/galvanostat model PGP201 controlled the electrodeposition process. potential applied and bath composition. On the other hand. In a similar way. viz. chemical baths with the following compositions were prepared. deposition time"50 min and deposition temperature"243C. 0. (1) where the elements involved have almost the same order of electrode potential. adding HCl in di!erent quantities (drops in this case) can modify the pH of the chemical baths. Experimental details CIS and CIGS thin "lms were prepared by co-electrodeposition using a threeelectrode con"guration. 50 ml each of the following concentrations was used to prepare the   "nal bath. This fact is the principal reason for its use in thin "lm solar cells and also does not show evidence of any degradation. At this point. To realize CIGS thin "lm deposition 0.E. The goal of the present investigation is to prepare good quality CIS and CIGS thin "lms adopting only the co-electrodeposition technique and to avoid the PVD technique for adjusting the "nal composition.025 H SeO . It is possible to identify two types of co-deposition processes. This technique can be used as a co-deposition process or a multi-step process. the pH e!ect on the CIS and CIGS thin "lm formation was analyzed. Calixto et al. Finally. Results Electrodeposited CIS and CIGS thin "lms were characterized using inductivecoupled plasma (ICP) spectroscopy. the potential applied for the "lm deposition was varied to analyze the e!ect of this parameter on CIS and CIGS thin "lms growth. In the present study "lms were deposited under the following conditions. keeping other deposition parameters  constant. / Solar Energy Materials & Solar Cells 59 (1999) 75 } 84 Electrodeposition o!ers great advantages in terms of low cost of production and cells for large area photovoltaic applications. SEM.2839 M GaCl in su$cient quantity  was added to the chemical bath. 2.76 M. 0. In both cases the quasi-rest potential is measured to set up the experimental conditions to form the "lm. and (2) where the elements involved have di!erent electrode potentials. CIGS has a direct energy band gap and its extraordinarily high absorption coe$cient permits to use thin layers (1}2 m) of active material. thin "lms were prepared using di!erent chemical bath compositions keeping other variables constant to analyze the e!ect of bath composition on "lm properties. studies were also realized with InCl of low and high purity. where the reference electrode was a saturated calomel electrode (SCE).

E.50 } } In (at %) 19.025 0.025 0.46 14.18 43.99 43. / Solar Energy Materials & Solar Cells 59 (1999) 75 } 84 Table 1 Di!erent chemical bath compositions used to prepare the CIS and CIGS thin "lms Bath Cu> In> SeO\  Bath Cu (0.60 3.34 16.0 2.77 In (at %) 22.36 41.025 0.025 M) (ml) 50 40 25 50 } } 1 2 3 4 5 6 0.025 M) (ml) 50 70 100 40 } } Ga (0.012 0.21 43.69 34. Table 1 shows the compositions of the di!erent chemical baths that were used to prepare the CIS and the CIGS thin "lms.025 0.69 61.2 1.96 52.025 0.2 2.44 34.7 Thickness m Table 3 The chemical composition analysis results in atomic percentage for CIS thin "lms.14 16. These tables show an important variation of chemical composition between CIS thin "lms with and without thermal treatment.031 0.05 A B C D } } Table 2 The chemical composition analysis results in atomic percentage for as-deposited CIS thin "lms Bath ICP results Cu (at %) 1 2 3 4 5 6 30.2 5. respectively. This e!ect can be .65 3.025 0.90 62.3 3.64 12.05 0.025 0.012 0.52 Se (at %) 47.025 0.93 69.025 0.89 30.22 17. Calixto et al.012 M) (ml) 50 40 25 50 } } In (0.025 0. The composition analysis results of the electrodeposited CIS thin "lms before and after thermal treatment are given in Tables 2 and 3.028 M) (ml) 10 10 10 20 } } 77 Se (0.025 0.78 39.91 16.8 1.1 } } Thickness m methods.30 } } Se (at %) 55. the thermal treatment was done in a tubular furnace in Se atmosphere at 5503C.05 0.50 46.18 } } 3.025 0.85 40.44 39. Subjected to a thermal treatment in Se atmosphere Bath ICP Results Cu (at %) 1 2 3 4 5 6 24.15 13.1 3.3 3.69 3.M.

2 shows the optical characteristics (transmittance and re#ectance) for a CIS thin "lm prepared using bath 1 and deposited for 4 min on SnO . According to Fig. / Solar Energy Materials & Solar Cells 59 (1999) 75 } 84 Fig. In:25 and Se:50 in atomic percents. 3. remained constant during these studies. bath 1 has the best composition to grow CIS thin "lm with a composition near to the ideal one. Fig. which is a plot of photon energy versus } absorption coe$cient. Cu: 25. the optical band gap was calculated from an optoelectronic analysis using standard formula. attributed to the recrystallization phenomena at high temperatures and to the bath composition. re#ectance and absorption coe$cient.186 m. The results of the . Calixto et al. potential applied and also using InCl of di!erent purities on  "lm properties. After this. Fig. On the other hand. bath temperature. etc. The measurement was made  using air as reference and the "lm thickness was 0. 1 shows the XRD pictures for the electrodeposited CIS thin "lms prepared from di!erent chemical baths. 3. This "gure indicates that the CIS thin "lm has the chalcopyrite structure (tetragonal JCPDS 40-1487) as in the previous cases. In the same way a detailed analysis was done on the in#uence of the deposition parameters such as pH. The result is displayed in Fig.78 M. The other electrodeposition parameters such as bath composition. In    the same way. the band gap of the CIS thin "lm was calculated to be about 1.05 eV. According to the composition analysis results shown in these tables.E. This "gure indicates that the electrodeposited "lm has the chalcopyrite structure. 1. The XRD picture for CIS thin "lms grown from di!erent chemical baths. an XRD analysis was done to this sample and the result is shown in Fig. which contains CuInSe (tetragonal JCPDS 40-1487) and  CuIn Se (tetragonal JCPDS 35-1349) both having very similar di!raction peaks. 4. CIS thin "lm were deposited on SnO substrates to analyze their  optical properties like transmittance.

. / Solar Energy Materials & Solar Cells 59 (1999) 75 } 84 79 Fig. 3. Fig.M. The opto-electronic characteristics showing the band gap for an electrodeposited CIS thin "lm. Calixto et al. 2.E. The optical characteristics for an electrodeposited CIS thin "lm.

Calixto et al.8 2.84 .90 28. 4.09 20.05 26.2 pH"1. pot.80 M.2 Thickness m !375 !425 !500 26.44 51.33 25.40 In (at %) 18.E. (mV) !375 !425 !500 ICP Results Cu (at %) 26.77 Se (at %) 55.26 17.76 19.1 2. onto a SnO  substrate.02 25.81 1.2 1.30 49.61 19.52 !375 !425 !500 28. Table 4 Chemical composition analysis results in atomic percentage for as-deposited CIS thin "lms grown by changing the applied potential and the pH value of the chemical bath 1 shown in the Table 1 and prepared with InCl of high purity  pH"1.87 54.0 2.79 21.97 26.65 52.34 Appl.45 17. / Solar Energy Materials & Solar Cells 59 (1999) 75 } 84 Fig.05 54.48 2. The XRD pictures for a CIS thin "lm electrodeposited during 4 min from bath 1.36 20.83 19.18 54.1 pH"1.6 2.9 2.70 53.1 3.21 56.72 28.

72 43. pot.11 and applied potential"!600 mV vs.17 20.02 48. .999%).5%). (mV) !375 !425 !500 ICP Results Cu (at %) 28.89 29.73 Se (at %) 53.7 pH"1.3 Thickness mm !375 !425 !500 31. SCE is the following. Calixto et al.11 12. Figs. Cu: 28. Table 5 gives composition analysis results for "lms  deposited by varying pH and applied potential for the chemical bath 1 shown in Table 1 and using low purity InCl (98.95 1.8 1. 5 shows a SEM micrograph for a CIS thin "lm. by varying the InCl and GaCl quantities in the chemical bath.41 1. The  results shown in Tables 4 and 5 correspond to as-deposited "lms and without any thermal treatment.05 !375 !425 !500 42.40 44. This study was realized to know the e!ect of bath composition and hence Ga concentration in the "lm on opto-electronic properties.80 30.E. Ga: 1. Fig.40 19.66 18.36 48.8 1.   6 and 7 shows the opto-electronic characterization results for this case.73 22.31 Appl.03 54. Table 4 corresponds to the results of composition analysis for "lms deposited by varying pH and applied potential for the chemical bath 1 shown in Table 1 and using high purity InCl (99.29 37.34% before doing any thermal treatment.93 36.5 pH"1.13 26.18 44.71 45. CIS thin "lm with chemical composition nearer to that of CuInSe may be prepared by varying the pH value of  the chemical bath and potential applied and using InCl of high or low purity.5 1.5 1. The composition analysis results for a CIGS "lm grown from bath 1 with a pH"2.98 19.84% and Se: 48. / Solar Energy Materials & Solar Cells 59 (1999) 75 } 84 81 Table 5 Chemical composition analysis results in atomic percentage for as-deposited CIS thin "lms grown by changing the applied potential and the pH value of the chemical bath 1 shown in the Table 1 and prepared with InCl of low purity  pH"1.85 In (at %) 18.8 1.05%.45 54.70 chemical composition analysis for these "lms are shown in the Tables 4 and 5. On the other hand.2 1.M.23 23. which indicates  compact morphology for the "lm. It means that it is not really necessary to use another complementary deposition technique like PVD technique to adjust the "nal composition to CuInSe .4 1.77%.79 19.  According to the results shown in Tables 4 and 5.17 25. a CIGS thin "lm was deposited on SnO substrate using chemical baths  with di!erent compositions as shown in Table 1. In: 21.

morphological and opto -electronic properties using the electrodeposition technique. chemical bath composition. it is not really necessary to use another complementary deposition technique like PVD to adjust the "nal composition of CIS and CIGS thin "lms grown by electrodeposition. The present study indicates that it is possible to obtain thin "lms with good structural. According to the chemical composition analysis results. / Solar Energy Materials & Solar Cells 59 (1999) 75 } 84 Fig. deposition temperature and the applied potential owing to their in#uence on "lm properties and quality. Conclusion CIS and CIGS thin "lms were prepared adopting electrodeposition technique and a thermal treatment in Se atmosphere.magni"cation for an electrodeposited CIS thin "lm. 4. .82 M. 5. It may be suggested that the electrodeposition technique is one of the important techniques for growing CIS and CIGS thin "lms on large area at low cost. is important to mention that there is no signi"cant e!ect of InCl purity  on the "lm properties. is very important to control the deposition parameters like pH. deposition time. Calixto et al. The results presented in this work are of preliminary in nature and more detailed studies are in progress. The SEM picture with 15 000.E. On the other hand. Also.

. Fig. The optical characteristics for an electrodeposited CIGS thin "lm. The optoelectronic characteristics showing the band gap for electrodeposited CIGS thin "lms grown from di!erent baths. Calixto et al. 6. / Solar Energy Materials & Solar Cells 59 (1999) 75 } 84 83 Fig.M. 7.E.

Res. Mater. Tseng. / Solar Energy Materials & Solar Cells 59 (1999) 75 } 84 Acknowledgements The Authors would like to mention the help received from Mr. 69 (1991) 429. Gabor. Nou". Ramanathan. L. A. Ramamurthy. Photovoltaic Solar Energy Conference. Qui. 145 (1998) 3613. Thouin. Electrochem.K. [10] L. Contreras. References [1] A. Solar Cells 21 (1987) 65. Hawaii.F.A. J. J. R. Soc. [8] R. F.C. This work was carried out with partial "nancial support from DGAPA-UNAM through the project IN108198. Tennant. Herrero.S. [11] C. Basol. Bhattacharya. Franz. Guillemoles. Sco"eld. J. Lincot. Ortega. 1992. p. Proceedings of the First World Conference on Photovoltaic Energy Conversion. 29 (1994) 195. Electrochem. Vedel. M.F. [6] L. R. Sebastian. Soc. Vedel. J. 1994. Tuttle. Rouquette. J. Phys. Montreux. K. Rommel Nou". 1994. Calixto et al. Wang. Soc. Thouin. P. Campos in opto-electronic studies.84 M. 130 (1983) 2040. [7] D. J. Jeyakumar.X. J. K. A. Electrochem. J.M. 68. J. Thouin. 136. p. Thin Solid Films 237 (1994) 1. J. S. USA. Sanchez and Mr. Kapur.J. Phys. 142 (1995) 2996. Lincot. Guillen. [3] C. B.N. D. S. Cowache. P. Shih. [4] J. R. 142 (1995) 1834. [12] P. Asher. A. Rockett et al. E. . J. 866. [5] R. Proceedings of the 11th E. Boisivon. Proceedings of the First World Conference on Photovoltaic Energy Conversion. [2] M. Mr.. Y. Massaccesi. J. S. L.E. Oscar Gomez-Daza in "lm preparation. Herrero. Vedel. J. Fezzaa. Hawaii. S. A. Keane.E. Bull. Guillen. J. Switzerland. Calixto. Guillemoles. J. Bhattacharya. [9] V. Massaccesi. p. Electrochem. J.N. C. USA. Soc. Cowache. 67 (1989) 444.

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