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

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Electrodeposition o!ers great advantages in terms of low cost of production and cells for large area photovoltaic applications. This technique can be used as a co-deposition process or a multi-step process. It is possible to identify two types of co-deposition processes, viz. (1) where the elements involved have almost the same order of electrode potential, and (2) where the elements involved have di!erent electrode potentials. In both cases the quasi-rest potential is measured to set up the experimental conditions to form the "lm. 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. This fact is the principal reason for its use in thin "lm solar cells and also does not show evidence of any degradation. This semiconductor material can be prepared by di!erent deposition techniques like physical evaporation or electrodeposition of precursor "lms. 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.

2. Experimental details CIS and CIGS thin "lms were prepared by co-electrodeposition using a threeelectrode con"guration, where the reference electrode was a saturated calomel electrode (SCE), the counter electrode a Pt mesh and the working electrode a Mo coated glass substrate. A potentiostat/galvanostat model PGP201 controlled the electrodeposition process. CIS and CIGS thin "lms were prepared by varying the electrodeposition parameters such as pH, potential applied and bath composition. In the "rst case, the pH e!ect on the CIS and CIGS thin "lm formation was analyzed. To realize this, chemical baths with the following compositions were prepared; 0.0125 M CuCl , 0.025 M InCl   and 0.025 H SeO . 50 ml each of the following concentrations was used to prepare the   "nal bath. To realize CIGS thin "lm deposition 0.2839 M GaCl in su$cient quantity  was added to the chemical bath. At this point, adding HCl in di!erent quantities (drops in this case) can modify the pH of the chemical baths. In a similar way, the potential applied for the "lm deposition was varied to analyze the e!ect of this parameter on CIS and CIGS thin "lms growth. Finally, 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. On the other hand, studies were also realized with InCl of low and high purity, keeping other deposition parameters  constant. In the present study "lms were deposited under the following conditions; deposition time"50 min and deposition temperature"243C.

3. Results Electrodeposited CIS and CIGS thin "lms were characterized using inductivecoupled plasma (ICP) spectroscopy, SEM, XRD and opto-electronic characterization

M.E. Calixto et al. / 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 (0.012 M) (ml) 50 40 25 50 } } In (0.025 M) (ml) 50 70 100 40 } } Ga (0.028 M) (ml) 10 10 10 20 } }

77

Se (0.025 M) (ml) 50 40 25 50 } }

1 2 3 4 5 6

0.012 0.025 0.031 0.05 0.012 0.025

0.025 0.025 0.025 0.025 0.025 0.025

0.025 0.025 0.025 0.025 0.05 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 30.44 39.50 46.69 61.91 16.89 30.77 In (at %) 22.34 16.64 12.60 3.15 13.14 16.52 Se (at %) 47.21 43.85 40.69 34.93 69.96 52.69 3.1 3.2 2.8 1.0 2.2 5.7 Thickness m

Table 3 The chemical composition analysis results in atomic percentage for CIS thin "lms. Subjected to a thermal treatment in Se atmosphere Bath ICP Results Cu (at %) 1 2 3 4 5 6 24.78 39.18 43.90 62.50 } } In (at %) 19.22 17.46 14.65 3.30 } } Se (at %) 55.99 43.36 41.44 34.18 } } 3.3 3.3 3.2 1.1 } } Thickness m

methods. Table 1 shows the compositions of the di!erent chemical baths that were used to prepare the CIS and the CIGS thin "lms. The composition analysis results of the electrodeposited CIS thin "lms before and after thermal treatment are given in Tables 2 and 3, respectively; the thermal treatment was done in a tubular furnace in Se atmosphere at 5503C. These tables show an important variation of chemical composition between CIS thin "lms with and without thermal treatment. This e!ect can be

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Fig. 1. The XRD picture for CIS thin "lms grown from di!erent chemical baths.

attributed to the recrystallization phenomena at high temperatures and to the bath composition. According to the composition analysis results shown in these tables, bath 1 has the best composition to grow CIS thin "lm with a composition near to the ideal one; Cu: 25, In:25 and Se:50 in atomic percents. Fig. 1 shows the XRD pictures for the electrodeposited CIS thin "lms prepared from di!erent chemical baths. This "gure indicates that the electrodeposited "lm has the chalcopyrite structure, which contains CuInSe (tetragonal JCPDS 40-1487) and  CuIn Se (tetragonal JCPDS 35-1349) both having very similar di!raction peaks. In    the same way, CIS thin "lm were deposited on SnO substrates to analyze their  optical properties like transmittance, re#ectance and absorption coe$cient. Fig. 2 shows the optical characteristics (transmittance and re#ectance) for a CIS thin "lm prepared using bath 1 and deposited for 4 min on SnO . The measurement was made  using air as reference and the "lm thickness was 0.186 m. After this, the optical band gap was calculated from an optoelectronic analysis using standard formula. The result is displayed in Fig. 3, which is a plot of photon energy versus } absorption coe$cient. According to Fig. 3, the band gap of the CIS thin "lm was calculated to be about 1.05 eV. On the other hand, an XRD analysis was done to this sample and the result is shown in Fig. 4. 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, potential applied and also using InCl of di!erent purities on  "lm properties. The other electrodeposition parameters such as bath composition, bath temperature, etc. remained constant during these studies. The results of the

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Fig. 2. The optical characteristics for an electrodeposited CIS thin "lm.

Fig. 3. The opto-electronic characteristics showing the band gap for an electrodeposited CIS thin "lm.

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Fig. 4. The XRD pictures for a CIS thin "lm electrodeposited during 4 min from bath 1, onto a SnO  substrate. 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"1.34 Appl. pot. (mV) !375 !425 !500 ICP Results Cu (at %) 26.33 25.97 26.40 In (at %) 18.61 19.36 20.77 Se (at %) 55.05 54.65 52.81 1.9 2.0 2.2 pH"1.48 2.1 3.1 2.1 pH"1.6 2.2 1.8 2.2 Thickness m

!375 !425 !500

26.05 26.02 25.26

17.76 19.09 20.21

56.18 54.87 54.52

!375 !425 !500

28.72 28.90 28.45

17.83 19.79 21.70

53.44 51.30 49.84

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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"1.31 Appl. pot. (mV) !375 !425 !500 ICP Results Cu (at %) 28.13 26.17 25.85 In (at %) 18.40 19.79 19.73 Se (at %) 53.45 54.03 54.41 1.8 1.8 1.7 pH"1.5 1.4 1.5 1.5 pH"1.95 1.2 1.8 1.3 Thickness mm

!375 !425 !500

31.80 30.89 29.23

23.17 20.73 22.71

45.02 48.36 48.05

!375 !425 !500

42.93 36.29 37.11

12.66 18.98 19.18

44.40 44.72 43.70

chemical composition analysis for these "lms are shown in the Tables 4 and 5. 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 (99.999%). 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 (98.5%).  According to the results shown in Tables 4 and 5, 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. The  results shown in Tables 4 and 5 correspond to as-deposited "lms and without any thermal treatment. It means that it is not really necessary to use another complementary deposition technique like PVD technique to adjust the "nal composition to CuInSe . Fig. 5 shows a SEM micrograph for a CIS thin "lm, which indicates  compact morphology for the "lm. The composition analysis results for a CIGS "lm grown from bath 1 with a pH"2.11 and applied potential"!600 mV vs. SCE is the following; Cu: 28.77%, In: 21.05%, Ga: 1.84% and Se: 48.34% before doing any thermal treatment. On the other hand, a CIGS thin "lm was deposited on SnO substrate using chemical baths  with di!erent compositions as shown in Table 1. This study was realized to know the e!ect of bath composition and hence Ga concentration in the "lm on opto-electronic properties. by varying the InCl and GaCl quantities in the chemical bath. Figs.   6 and 7 shows the opto-electronic characterization results for this case.

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Fig. 5. The SEM picture with 15 000;magni"cation for an electrodeposited CIS thin "lm.

4. Conclusion CIS and CIGS thin "lms were prepared adopting electrodeposition technique and a thermal treatment in Se atmosphere. According to the chemical composition analysis results, 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, morphological and opto -electronic properties using the electrodeposition technique. On the other hand, is very important to control the deposition parameters like pH, chemical bath composition, deposition time, deposition temperature and the applied potential owing to their in#uence on "lm properties and quality. Also, is important to mention that there is no signi"cant e!ect of InCl purity  on the "lm properties. 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. The results presented in this work are of preliminary in nature and more detailed studies are in progress.

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Fig. 6. The optical characteristics for an electrodeposited CIGS thin "lm.

Fig. 7. The optoelectronic characteristics showing the band gap for electrodeposited CIGS thin "lms grown from di!erent baths.

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Acknowledgements The Authors would like to mention the help received from Mr. Oscar Gomez-Daza in "lm preparation, Mr. A. Sanchez and Mr. J. Campos in opto-electronic studies. This work was carried out with partial "nancial support from DGAPA-UNAM through the project IN108198.

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