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Study of 4the influence of annealing parameters on the optical and compositional properties of ZnS, ZnS:Mn and ZnS:Sm grown by Sol Gel

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XIX Latin American Symposium on Solid State Physics (SLAFES XIX) Journal of Physics: Conference Series 167 (2009) 012051

IOP Publishing doi:10.1088/1742-6596/167/1/012051

Study of 4the influence of annealing parameters on the optical and compositional properties of ZnS, ZnS:Mn and ZnS:Sm grown by Sol Gel
E. Gmez-Barojas1,4, E. Snchez-Mora2, T. Mendoza-Dorantes3, C. CastilloAbriz3 and R. Silva-Gonzlez2
1

CIDS-IC, BUAP. Ed. 103C, C.U. Col. San Manuel. Puebla, Pue. Mxico 72570 Instituto de Fsica, BUAP. Apdo. Postal J-48 Puebla, Pue. Mxico. 72570. FIQ, BUAP. Puebla, Pue. Mxico. 72570.

2 3

E-mail: egomez@sirio.ifuap.buap.mx

Abstract. Samples with 3 layers of ZnS were prepared on glass substrate by the Sol Gel method. The annealing parameters were varied as follows: each of the 3 constituent layers of sample 1 was annealed at 400 C for 12 hrs. For sample 2, the 1rst and 2nd layers were annealed at 300 C for 2hrs each and the 3rd one at 400 C for 12 hrs. For sample 3, the 1rst and 2nd layers were annealed at 200 C for 2hrs each and the 3rd at 400 C for 12 hrs. Furthermore, 2 samples: one with 3 layers of ZnS:Mn and the other with 3 layers of ZnS:Sm were prepared and annealed similarly to sample 2. AES depth profiles show a transversal diffusion of S in sample 1, a sulfur deficiency in sample 2, and a non distributed excess of S in sample 3. The absorption spectra of the 3 ZnS samples are very similar but the absorption edges shift to smaller energy values for the Mn and Sm doped ZnS samples. Sample 1 presents a PL spectrum with 2 bands at 441 and 537 nm while sample 2 presents a similar spectrum but the bands are 16 and 11 nm blue shifted.

1. Introduction The Zinc Sulfide (ZnS) is a II-VI semiconductor with a wide direct band gap in the near UV region. Its energy band gap is smaller in cubic ZnS (3.68 eV) [1] than in hexagonal ZnS (3.7 eV) [2]. It is an attractive material to be used as an antirreflecting coating in heterojunction solar cells, and as a phosphor in electroluminescent devices [3]. The object of this work was to prepare samples with three layers of ZnS on glass substrates by the solgel method and study the influence of the thermal treatments parameters on the composition and optical properties of the samples. These parameters were varied as follows: Each of the 3 layers of sample 1 was annealed at 400 C for 12 hrs; we label this annealing condition as (TT400C). Then, the 1rst and 2nd layers of sample 2 were annealed at 300 C for 2hrs each and the 3rd at 400 C for 12 hrs (TT300C) and for sample 3 the 1rst and 2nd films were annealed at 200 C for 2hrs and the 3rd at 400
4

To whom any correspondence should be addressed

c 2009 IOP Publishing Ltd

XIX Latin American Symposium on Solid State Physics (SLAFES XIX) Journal of Physics: Conference Series 167 (2009) 012051

IOP Publishing doi:10.1088/1742-6596/167/1/012051

C for 12 hrs (TT200C). All annealing processes were performed under N2 flux. Besides, two more samples were prepared: sample 4 with 3 layers of ZnS: Mn2+/glass and sample 5 with 3 layers of ZnS:Sm3+/glass by the same method using the (TT300C) annealing condition. 2. Experimental 2.1. Synthesis The ZnS layers were deposited on glass substrates by the Sol-Gel method. The ZnS base deposition solution contained 21.6 ml of metoxyethanol, 2.7970 g of 0.2 M zinc acetate dihydrate, 0.5749 g of 0.4 M thiourea and 0.4 ml of 3.6x10-4 M ethanolamine. The solution was heated to 60 C with constant agitation for 30 min and let aged for 2 days. Then, each of the constituent layers of a sample was deposited by dipping the glass substrate into the deposition solution for 5 min, slowly withdrawing it and let it dried in air. After each deposition an annealing process in N2 was carried out. Three ZnS samples were prepared with similar composition solution. However, sample 1 was annealed with the TT400 C condition. Sample 2 with the TT300 C condition and sample 3 with the TT200 C annealing condition. To prepare the ZnS:Mn and ZnS:Sm samples, manganese chloride tetrahydrate (20 wt %) and samarium nitrate hexahydrate (20 wt %) were added to base deposition solutions as sources of Mn and Sm ions, respectively and the layers were annealed with the TT300C condition. The samples were characterized by the techniques: Auger electron spectroscopy (JEOL, JAPM-7800) in combination with a Sputtering Ar ions system; UV-Visible Spectroscopy (Varian, Cary-100), and Photoluminescence spectroscopy (ARC-275 spectrometer, an R636-10 photomultiplier and UV light-excitation source). 3. Results 3.1. AES The spectra were recorded at Ep/Ip=5 keV/8 10-8 A and a base pressure of 1.7x10-7 Pa. Fig. 1 shows Auger depth profiles, relative intensity vs sputtering time, of the ZnS samples annealed with the conditions: (a) TT400C, (b) TT300C and (c) TT200C. In (a) the relative intensity of S is greater than that of Zn, (I(S) > I(Zn)), the shape of the S profile is not plane but curved, probably due to a transversal diffusion of S toward the sample surface. In b) the I(Zn) > I(S) through depth, except for the depression of the S profile which is very likely due to the different annealing temperature of the 3rd layer, it looks more homogeneous than that in (a). In c) the ZnS layer elemental composition is not homogeneous, since the S profile consists of 3 large peaks while the Zn profile is of very low intensity. The S profile in Fig. 1(a) could be due to the formation of SOx species in gas phase that migrate to the surface sample to be desorbed [4, 5]. A similar S transversal diffusion effect has been also observed in CdS/CdTe heterostructures [6]. It was not possible to perform this analysis in the doped ZnS samples because they present severe charging effects. 3.2. UV-Vis 3.2.1. ZnS samples Fig. 2) shows UV-Vis absorption and transmission spectra. The lower part of the absorption spectrum in Fig. 2a is slightly shifted to larger wavelengths as the annealing temperature is increased. The spectrum corresponding to the sample with the (TT300 C) annealing condition shows some oscillations in the lower part (see the inset) due to the combination of annealing temperatures used. In 2 (b) transmittance spectra are shown. The sample with TT300 C annealing condition shows well defined interference fringes. The fringes are associated with the uniformity of a film thickness, when the thickness is not uniform or it is slightly tapered the interference effects are destroyed and the transmission is a smooth curve as the spectrum of the sample with TT400 C annealing condition.

XIX Latin American Symposium on Solid State Physics (SLAFES XIX) Journal of Physics: Conference Series 167 (2009) 012051

IOP Publishing doi:10.1088/1742-6596/167/1/012051

Since UV-Vis spectra were recorded from each constituent layer, the thickness, t, refraction index, n; absorption coefficient, ; and energy band gap, Eg were calculated using the transmittance spectra and the Swanepoel method [7]. The estimated data are listed in Table 1.

30000

S O Zn

10000

S O Zn

25000

8000

Intensity (a.u.)

20000

Intensity (a.u.)

6000

Zn

15000

4000
S

10000

Zn
2000

5000 O
0

20

40

60

Sputtering time (min)

Sputtering time (min)

Fig. 1. (a) Auger depth profile of the ZnS sample with TT400C annealing condition.
14000
S

Fig. 1. (b) Auger depth profile of the ZnS sample with TT300C annealing condition.

12000

Intensity (a.u.)

10000

S O Zn

8000

6000

4000

2000
Zn

0 0 2 4 6 8 10

Sputtering time (min)

Fig. 1. (c) Auger depth profile of the ZnS sample with TT200C annealing condition Table 1. Calculated optical parameters of the ZnS samples with different annealing conditions.

Sample, annealing condition ZnS, TT400oC ZnS, TT300oC ZnS, TT200oC

Eg (eV) 3.65 3.67 3.70 1.83 1.67 1.52

n
=497 nm =540 nm =561 nm

t (nm) 425.4 572.7 502.6

(cm-1)

1.3x108 5.5x107 1.7x107

XIX Latin American Symposium on Solid State Physics (SLAFES XIX) Journal of Physics: Conference Series 167 (2009) 012051
100
0.15
0

IOP Publishing doi:10.1088/1742-6596/167/1/012051

1.0

ZnS TT200 C 0 ZnS TT300 C 0 ZnS TT400 C

80

0.8

0.10

Transmittance %

Absorbance (a.u.)

0.6
0.05

60

0.4
0.00

40

0.2

300

400

500

600

700

800

20
0.0

ZnS TT200 C 0 ZnS TT300 C 0 ZnS TT400 C

0
300 400 500 600 700 800

300

400

500

600

700

800

Walvelength (nm)

Walvelength (nm)

Fig. 2 (a). Absorbance spectra of the ZnS samples with TT200 C, TT300 C and TT400 C annealing conditions:

Fig. 2 (b) Transmittance spectra of the ZnS samples with TT200 C, TT300 C and TT400 C. annealing conditions

3.2.2. Samples with 3 layers of ZnS:Mn and ZnS:Sm Fig. 3 shows UV-Vis spectra of the ZnS:Mn and ZnS:Sm samples (a) absorbance and (b) transmittance spectra. Correspondent ZnS spectra are included for comparison. In (a) the absorption threshold of the doped ZnS samples are shifted to smaller energy values (3.26 eV for ZnS:Mn and 3.06 eV for ZnS:Sm) with respect to the one of the undoped ZnS. In b) the transmittance percentages of ZnS:Mn and ZnS:Sm are smaller than the one of the undoped ZnS.
ZnS:Mn 20 % W TT300 C 0 ZnS:Sm 20 % W TT300 C 0 ZnS TT300 C 1.0
0

100 90 80

ZnS:Mn 20 % W TT300 C 0 ZnS:Sm 20 % W TT300 C 0 ZnS TT300 C

0.8

70

Transmittance %

Absorbance (a.u.)

60 50 40 30 20

0.6

0.4

0.2

10
0.0 300 400 500 600 700 800

0 300 400 500 600 700 800

Walvelength (nm)

Walvelength (nm)

Fig. 3. (a) Absorbance vs wavelength spectra of the ZnS:Mn, ZnS:Sm and ZnS samples:

Fig. 3. (b) Transmittance vs wavelength spectra of the ZnS:Mn, ZnS:Sm and ZnS samples.

3.3. Photoluminescence Fig. 4 shows luminescence spectra of the ZnS samples whose annealing conditions were: a) TT400C and b) TT300C. In a) the emission band with maximum at 441 nm (2.81 eV) in the blue range is assigned to Zn vacancies and the emission band at 537 nm (2.31 eV) is assigned to vacancies located near the ZnS valence band [8,9] that act as acceptors in the semiconductor terminology. In b), the PL spectrum shows 2 broad shoulders at 425 nm (2.91 eV), and 526 nm (2.36 eV). These bands are similar to the ones in a) but blue shifted due to the change in the thermal treatment condition. The doped ZnS samples presented similar spectra to the above (not shown)

XIX Latin American Symposium on Solid State Physics (SLAFES XIX) Journal of Physics: Conference Series 167 (2009) 012051
537 nm
3.0

IOP Publishing doi:10.1088/1742-6596/167/1/012051

525.97 nm

2.5
0.8

Intensity x 10 (a.u.)

0.6

Intensity * 10 (a.u.)

2.0

425 nm

-4

-4

441 nm
0.4

1.5

1.0

0.2

0.5

0.0 350 400 450 500 550 600

0.0 350 400 450 500 550 600

Walvelength (nm)

Walvelength (nm)

Fig. 4. (a) Photoluminescence spectrum of the ZnS sample with TT400C annealing condition.

Fig. 4. (b) Photoluminescence spectrum of the ZnS sample with TT300C annealing condition.

4. Conclusion From UV-Vis characterization results, it is observed that having used a new solution with 2 days of age for each constituent ZnS layer a large and equal amplitude of the absorption edges of the three samples were obtained. The absorbance borders of the doped ZnS are shifted to larger wave lengths with respect to that of ZnS. The ZnS sample annealed at the TT300 C condition presents better features for example: good absorbance amplitude and a large transmittance percentage. The AES depth profiles show that the S transversal diffusion can be avoided by performing the annealing at TT300 C condition. The ZnS sample with TT300 C annealing condition presents greater PL intensity and and the bands are 16 and 11 nm blue shifted with respect to the one with TT400oC annealing condition. The ZnS:Mn and ZnS:Sm samples require further investigation since no great change in the PL spectra was observed. 5. Acknowledgment Work partially supported by VIEP, BUAP trough projects Nos. 11/EXC/07/G. 6. References Landolt, H.; Bomstein, R. Numerical data and functional relationships in science and technology, New Series. Springer-Verlag.; Berlin, 1999 [2] Q. Xion. Nano Letters. 4, 9 (2004) 1663. [3] B. Su and K. L. Choy. J. Mater. Chem. 10 (2000) 949 [4] E. Gmez-Barojas, R. Silva-Gonzlez, J. Pantoja- Enriquez. Solar Energy Materials & Solar Cells 90 (2006) 2235 [5] X. Q. Wang, D. Xu, S. G. Li, J. Huang, and W. Du. Crys. Res. Technol. 41,1,55 (2006) 55 [6] X. Q. Wang, D. Xu, X. F. Cheng, M. K. Lu, D. R. Yuan, J. Huang, G. W. Lu, H. X. Ning, X. L. Duan, Z. M. Wang, G. T. Lu, S. G. Li, Y. Chen, and Y. Q. Zhou. Mater. Res. Bull. 37 (2002) 1859. [7] Monjoy Sreemany, Suchitra Sen, J. Matter. Chem. and Phys. 83 (2004)169 [8] W. Chen, R. Sammynaiken, Yining Huang, J. Olle Malm, R. Wallenberg, J. Olor Bovin., V. Zwiller and N. A. Kotov. J. Appl. Phys. 89, 2 (2001) 1120 [9] H. C. Warad, S. C. Ghosh, B. Hetmtanon, C. Thanachayanont and J. Dutta, J. Sci and Tech. of Adv. Materials. 6 (2005) 296 [1]