Raman Spectroscopy of Optical Properties In Cds Thin Films - doiSerbia

Science of Sintering, 47 (2015) 145-152 ________________________________________________________________________

doi: 10.2298/SOS1502145T UDK 677.017.5; 543.42

Raman Spectroscopy of Optical Properties In Cds Thin Films J. Trajić1*), M. Gilić1, N. Romčević1, M. Romčević1, G. Stanišić1, B. Hadžić1, M. Petrović1, Y.S. Yahia2 1

Institute of Physics, P.O. Box 68, University of Belgrade, 11080 Belgrade, Serbia Nano–Science& Semiconductor Labs., Department of Physics, Faculty of Education, Ain Shams University, Roxy, Cairo, Egypt 2

Abstract: Properties of CdS thin films were investigated applying atomic force microscopy (AFM) and Raman spectroscopy. CdS thin films were prepared by using thermal evaporation technique under base pressure 2 x 10-5 torr. The quality of these films was investigated by AFM spectroscopy. We apply Raman scattering to investigate optical properties of CdS thin films, and reveal existence of surface optical phonon (SOP) mode at 297 cm-1. Effective permittivity of mixture were modeled by Maxwell – Garnet approximation. Keywords: Thin films, Crystal growth, Phonons, Atomic force microscopy, Raman spectroscopy

1. Introduction Thin film polycrystalline semiconductors have attracted great interest in an expanding variety of applications in various electronic and optoelectronic devices. Thin films now occupy a prominent place in basic research and solid state technology. The technological interest in polycrystalline based devices is mainly caused by their very low production costs. Among the II – VI semiconductors, CdS polycrystalline thin film is a representative material. Cadmium sulphide (CdS) is a very useful optoelectronic [1, 2], piezo – electronic [3] and semiconducting material. It has a wide direct band gap (2.42 eV) so has been used as a window material together with several semiconductors such as CdTe, Cu2S and CuInSe2 [4]. The deposition of CdS films has been explored by different techniques: sputtering, thermal evaporation, chemical bath deposition, and molecular beam epitaxy [5 – 9] in each of these methods polycrystalline, uniform and hard films are obtained, and their electrical properties are very sensitive to the method of preparation. In the case of crystal with relatively small dimension, in the frequency range between bulk longitudinal optical phonon frequency (ωLO) and transversal optical phonon frequency (ωTO), a new mode known as a surface phonon mode appears. It is well established that for the case of real crystal, when their dimension is relatively small, surface modes and effects of dimension will be also manifested in addition to the normal mode of infinite lattice. When dimension become extremely small, only the surface mode persist [10]. _____________________________

*)

Corresponding author: [email protected]

146

J. Trajić et al. /Science of Sintering, 47 (2015) 145-152

___________________________________________________________________________ Surface modes play an important role in deciding the different physical properties of nanocrystals. For a plane wave propagating in the x – direction in a bulk crystal, the temporal and spatial variation of the wave is described by the factor exp[i(kx − ωt)], where the wavevector k = (ω c ) ε (ω ) and ε(ω) is the dielectric constant of the crystal. In the frequency range between bulk longitudinal (ωLO) and transverse optical mode frequency (ωTO), ε(ω) has negative value, and accordingly k is imaginary. Therefore, in this frequency range the wave decays exponentially in the medium, i.e. it cannot propagate in bulk crystals and only surface modes exist [11]. In this work we report experimental studies of CdS thin films evaporated by thermal evaporation technique properties. Thickness of the films we analyzed was 1.6, 1.8, 2.0 and 2.2 μm. Samples characterization was performed using atomic force microscopy (AFM) while optical properties were analyzed using Raman spectra measurements.

2. Samples preparation and characterization CdS powder was purchased from Sigma – Aldrich Company with high purity. CdS thin films of different thicknesses were deposited onto highly pre–cleaned glass substrates using the thermal evaporation at room temperature. A high vacuum coating unit (Edwards, E – 306 A) was used under base pressure 2 x 10-5 torr. The distance between the evaporation source (molybdenum boat) and the substrate holder was about 21 cm to avoid the heating flow from the heating source to the substrates. The rate of deposition was 10 nm/s and the film thickness was controlled using a quartz crystal thickness monitor (FTM4, Edwards). The morphology of CdS thin films was investigated by atomic force microscopy (AFM). An atomic force microscopy (AFM) was used to determine the general cell wall structure together with the assembly of particular components into the wall structure as a whole. AFM images for investigated CdS samples were presented in Fig. 1. For all samples hillocks having the height at about 30 nm were observed (Tab. I).

(a)

(b)

J. Trajić et al./Science of Sintering, 47 (2015) 145-152

147

___________________________________________________________________________

(c)

(d)

Fig. 1. AFM surface image of CdS thin films of different thicknesses on glass substrate: a) d = 1.6 μm, b) d = 1.8 μm, c) d = 2.0 μm and d) d = 2.2 μm. b) Surface topology and values of average roughness (Ra) and root mean squared (RMS) roughness was analyzed. According to obtained results which are presented in table 1, the employed surfaces at micro scale are relatively smooth and uniform (with the exception of a few scratches). AFM images showed that all CdS samples present well defined nanosized grains, having relatively small roughness values, ranging from 3.84 nm to 5.84 nm, as shown in Tab. I. Tab. I. Average height, average roughness (Ra) and root mean squared (RMS) roughness for different CdS thin films thicknesses Average height d [μm] Ra [nm] RMS [nm] [nm]

1.6

30.09

3.87

5.4

1.8

25.14

3.84

4.76

2.0

28.67

5.84

7.27

2.2

30.07

5.56

6.99

3. Results and discussion The micro – Raman spectra were taken in the backscattering configuration and analyzed by Jobin Yvon T64000 spectrometer, equipped with nitrogen cooled charge – coupled – device detector. As an excitation source we used the 514.5 nm line of an Ar – iron laser. The measurements were performed at different laser power. Spectra were taken at room temperature.


148

___________________________________________________________________________ Cadmium sulfide has wurtzite crystal structure. It has C6v symmetry with 4 atoms per unit cell. Group theory predicts, at zone center that of 9 optical branches there is one A1 and one doubly degenerate E1, which are both Raman and infrared active, two doubly degenerate E2 branches which are Raman active only, and two inactive B1 branches [12]. As opposite to E2 phonons, both A1 and E1 are polar modes and split into transverse (TO) and longitudinal (LO) phonons with different frequencies due to macroscopic electric fields associated with LO phonons. As we have emphasized, dimensions of our samples belongs to nanoscale. As it has been mentioned many times [13–18] reduction of the particles dimensions to nanoscale results in breakdown of phonon momentum selection rule and allows phonons with l ≠ 0 to contribute to Raman scattering. Hence some new forbidden vibration modes (acoustic modes – in low frequency region and surface optical modes – in high frequency region) will emerge due to imperfections, impurity, valence band mixing and/or nonspherical geometry of the nanostructures. The typical Raman spectra of the bulk CdS crystal is presented in Fig. 2. The modes we observe are characteristic for wurtzite structure CdS [19–21]. Those are the mode at 212 cm-1 with B2 symmetry, mode at 234 cm-1 which is transversal mode with A1 symmetry, E1 symmetry mode at 245 cm-1 and mode at 252 cm-1 with E2 symmetry. Dominant structure in these spectra is longitudinal mode at 305 cm-1 and its first overtone at 611 cm-1 (Inset in Fig. 2), which is consistent with the fact that the one of the striking features of the Raman spectra CdS is the remarkable overtones series of the longitudinal optical phonons [10].

Α1(tran) Ε1(tran)

ωLO

Intensity (arb. unit.)

Intensity (arb. unit.)

B2

200

300

Α1 (long) Ε1 (long)

E2

2ωLO

400

500

600

700

-1

Raman shift (cm )

200

250

300

350

-1

Raman shift (cm )

Fig. 2. Raman spectra of bulk CdS single crystal.

Raman spectra of CdS thin films (d = 1.6, 1.8, 2.0 and 2.2 μm) at room temperature are presented in Fig. 3. The observed Raman spectra for all those samples besides characteristic CdS modes and their multiphonon combinations, show the LO frequency shift from 305 cm-1 to 297 cm-1, and 611 cm-1 to 594 cm-1. The LO phonon shift of CdS crystal is attributed to the surface optical phonon (SOP) mode effect [10, 22–27]. Surface phonon modes are observed for particles sizes smaller then the wavelength of exciting laser light inside the particles. Usually these modes of small particles appear in polar crystals [28]. The dielectric function for the case of polar semiinsulating semiconductor: ω 2 − ω 2 − iωγ i ε (ω ) = ε ∞ ∏in=1 LOi (1) 2 ωTOi − ω 2 − iωγ i


149

___________________________________________________________________________ describe its optical properties in the IR region. Here, ωTO and ωLO are the frequencies of the transverse and longitudinal optical bulk phonons, respectively; ε∞ is the dielectric constant at high frequencies, and γ is the damping constant. The bulk phonons in small particles have properties similar to those of the corresponding phonons in infinite crystals; however their wave functions are adapted to the geometry of small particle.

Intensity (arb. units)

d=2.2μm

E1TO

3E1TO

2E1TO E1TO+E1LO

SOP

d=2.0μm

2SOP 3SOP

d=1.8μm

d= 1.6μm

200

400

600

800

1000

-1

Raman shift (cm )

Fig. 3. Raman spectra of CdS thin film with thickness of d = 1.6, 1.8, 2.0 and 2.2 μm at room temperature.

When visible light interacting with semiconducting nanoparticles (characteristic size L, dielectric function ε2) which are distributed in a medium with the dielectric constant ε1 in the limit λ >> L, the heterogeneous composite can be treated as a homogeneous medium, and so – called effective medium theory applies. There are many mixing models for the effective dielectric permittivity of such a mixture [29]. Since all our samples are well defined and separated nanosized grains we decided to use Maxwell – Garnet model for present case. For the spherical inclusions case, the prediction of the effective permittivity of mixture εeff according to the Maxwell – Garnet mixing rule is [30, 31]: ε 2 − ε1 ε ff = ε 1 + 3 fε 1 (2) ε 2 + 2ε 1 − f (ε 1 − ε 2 ) Here, spheres of permittivity ε2 are located randomly in homogeneous environment ε1 and occupy a volume fraction f. In the area of interest for the appearance of surface optical phonons, we have two phonons ωA1TO = 233.5 cm-1, ωA1LO = 305 cm-1 and ωE1TO = 242 cm-1, ωE1LO = 308 cm-1 [12]. Low mobility and low free carriers concentration allow us to neglect the plasmon – phonon interaction influence. Our nanoparticles are randomly distributed in space, and accordingly, to the incident ligh. As one can see, the E1 symmetry phonon is registered in the Raman spectra, while there is no A1 symmetry phonon, so we concluded that A1 symmetry phonon participate in the creating SOP.


150

___________________________________________________________________________ In order to demonstrate the influence of various parameters on the SOP, the appearance of Raman line for the dielectric function (equation (1)) with n = 1 and phonon with A1 symetry, whereby the nanoparticles are situated in air (ε1 = 1) is shown on Fig. 4. In this case Raman intensity due to the excitation of dominant extraordinary phonons is given with: ⎛ ⎞ (3) I ∼ Im ⎜ − 1 ⎟ ε eff ⎠ ⎝ Such calculation predicts appearance of one asymmetric peak with wavenumbers below ωA1(LO) in the area of Maxwell – Garnet formula applicability. Therefore, the difference in the intensity and line shape of simulated SOP modes is mainly the results of variation in main volume fraction and damping rate, as demonstrated in Fig. 4. In our case, the position of the SOP mode maximum directly follows the change of filling factor (Fig. 4a). As one can see from Fig.4b, changes in damping leads only to a change in mode shape while its position remains unchanged.


f=0.8 f=0.7 f=0.6 f=0.5 f=0.4 f=0.3 f=0.2 f=0.1 γ=20

200

250

300

350

400


γ=90 γ=80 γ=70 γ=60 γ=50 γ=40 γ=30 γ=20

f=0.5

200

250

300

350

400

-1

Raman shift (cm )

Fig. 4. Surface optical modes position vs. (a) filing factor f and (b) phonon damping.

Raman spectra usually are analyzed with the help of Lorentzian and Gaussian curvers [32]. In this work we have assumed that all phonon lines are of Lorentzian type. SOP lines are calculated by Eq.(2 – 3), with ε1 = 1 and n = 1 in Eq.1 (A1 phonon). Main volume fractions f obtained as the best fit parameter estimation, are presented in Tab. II. Tab. II. Main volume factor for different CdS thin films thicknesses.

CdS thin films

d = 1.6µm

d = 1.8µm

d = 2.0 µm

d = 2.2 µm

F

0.75

0.73

0.71

0.71


151

___________________________________________________________________________

4. Conclusions In this paper, we present results of investigation CdS thin films with different thicknesses. We determined that all samples surfaces are relatively smooth and uniform, having well defined nanosized grains with relatively small roughness values. Raman spectra measurements reveal, besides characteristic CdS modes and their multiphonon combinations, existence of surface optical phonon modes. We threat the CdS thin film as a mixture of homogenous spherical inclusion in air modeled by Maxwell – Garnet formula. Besides characteristic cadmium sulphide modes we registered the existence of SOP modes.

Acknowledgements This research was financially supported by the Serbian Ministry of Education, Science and Technological Development (Project 45003).

5. References 1. Y. Iyechika, G. Wigner, D. Jager, A. Witt, C.Klingshirn, SPIE Opt. Comput. 88 (1988) 103. 2. S.V. Bogdanov, V.G. Lyssenko, Phys. Status Solidi B150 (1988) 593. 3. V.V. Stefko, Sov. J. Commun. Technol. Electron. 36 (1991) 13. 4. M.A. Mahdi, S.J. Kasem, J.J. Hassen, A.A. Swadi, J. Al–Ani, Int. J. Nanoelectronics and Materials 2 (2009) 163. 5. J.G. V´azquez, A. Zehe, O. Zelaya, Cryst. Res. Technol. 34 (1999) 949. 6. B. Su , K.L. Choy, Thin Solid Films 359 (2000) 160. 7. A. Ashour, N. El–Kadry, S.A. Mahmoud, Thin Solid Films 269 (1995)117. 8. S.A. Mahmoud, A.A. Ibrahim, A.S. Riad, Thin Solid Films 372 (2000) 144. 9. A.I. Oliva, O. Solis–Canto, R. Castro–Rodr´ıguez, P. Quintana, Thin Solid Films 391 (2001) 28. 10. D.S. Chuu, C.M. Dai, W.F. Hsieh, C.T. Tsai, J. Appl. Phys. 69 (1991) 12. 11. A. Singha, B. Satpati, P.V. Satyam, Roy Anushree, J. Phys.: Condens. Matter 17 (2005) 5697. 12. B. Tell, T.C. Damen , S.P.S. Porto, Phys. Rew. 144 (1966) 2. 13. H. Zeng, W. Cai, B. Cao, J. Hu, Y. Li Y, P. Liu, Appl. Phys. Lett. 88 (2006) 181905. 14. A. Ghosh, R.N.P.J. Choudhary, Phys. D: Appl. Phys. 42 (2009) 075416. 15. F. Friedrich, N.H. Nickel, Appl. Phys. Lett. 91 (2007) 111903. 16. J. Xu, W. Ji, X.B.Wang, H. Shu, Z.X.Shen, S.H. Tang, J. Raman Spectrosc. 29 (1998) 613. 17. Z. Ž. Lazarević, Č. Jovalekić, D. Sekulić, M. Slankamenac, M. Romčević, A. Milutinović, N. Ž. Romčević, Science of Sintering, 44 (2012) 331-339. 18. D. L. Sekulić, Z. Ž. Lazarević, Č. Jovalekić, A. Rečnik, M. Romčević, B. Hadžić, N. Ž. Romčević, Science of Sintering, 46 (2014) 235-245. 19. M.A. Nusimovici, M. Balkanski, Phys. Rev. B, 1 (1970) 595. 20. M.A. Nusimovici, J.L. Birman, Phys. Rev. 156 (1967) 925. 21. R. Marshal, S.S. Mitra, Phys. Rev. 134 (1964) A1019. 22. J.F. Scott, T.C. Damem, Opt. Commun. 5 (1972) 410. 23. R. Rossetti, S. Nakahara, L.E. Brus, J. Chem. Phys.79 (1983) 1086. 24. B.F. Variano, N.E.Schlotter, D.M.Hwang, C.J. Sandroff, J. Chem. Phys. 88 (1988) 2848.

152


___________________________________________________________________________ 25. A.V. Baranov, Y.S. Bobovich, N.I. Grebenshchikova, V.I. Petrov, M.Y. Tsenter, Opt. Spectrosc. 60 (1986) 685. 26. H. Jerominek, M. Pigeon, S. Patela, Z. Jakubczk, C. Delisle, R.J. Tremblay, Appl. Phys. 63 (1988) 957. 27. E.F. Hilinski, P.A. Lucas, J. Chem. Phys. 89 (1988) 3435. 28. G. Irmer, J. Raman Spectrosc. 38 (2007) 634. 29. K. Karkkainen, A.Saviola, K. Nikoskinen, IEEE Transaction on geosciences and remote sensors 39 (5) (2001) 1013. 30. J.C.M. Garnett, Trans. R. Soc. CCIII (1904) 385420. 31. A. Saviola, I. Lindell, Dielectric Properties of Heterogeneous Materials PIER 6 Progres in Electromagnetic Research ed A Priou, (Amsterdam: Elsevier) (1992) 101. 32. H. Idink, V. Srikanth, W.B. White, E.C. Subbarao, J. Appl. Phys. 76 (1994) 1819 .

Садржај: Особине танких филмова CdS су испитиване применом микроскопије атомских сила и Раман спектроскопије. Танки филмови CdS су добијени методом термалног напаравања. Квалитет филмова је испитиван микроскопијом атомских сила. Проучавање оптичких својстава танких филмова CdS је извршено применом Рамановог расејања. Установљено је постојање површинских оптичких фононских модова на 297 cm-1. Диелектрична функција је моделована применом Максвел Гарнетове формуле. Кључне речи: Танки филмови, раст кристала, фонони, микроскопија атомских сила, Раман спектроскопија.