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Phys. Status Solidi A 209, No. 5, 949952 (2012) / DOI 10.1002/pssa.201127549

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Raman scattering characterization of ZnSe/Zn0.6Cd0.4Se multilayers prepared by thermal vacuum evaporation

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applications and materials science

c epanovic , Zdravka Aneva , Zelma Levi , Zoran V. Popovic , and Ilko Miloushev Diana Nesheva* , Maja S
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Institute of Solid State Physics, Bulgarian Academy of Sciences, Blvd. Tzarigradsko Chaussee 72, 1784 Soa, Bulgaria Center for Solid State Physics and New Materials, Institute of Physics, University of Belgrade, Pregrevica 118, 11080 Belgrade, Serbia

Received 16 September 2011, revised 9 January 2012, accepted 18 January 2012 Published online 9 February 2012 Keywords multiple quantum wells, photoconductivity, Raman scattering, thermal evaporation, zink-cadmium-selenide
* Corresponding

author: e-mail nesheva@issp.bas.bg, Phone: 359 29795686, Fax: 359 29753632

Nanocrystalline multilayers from ZnSe/Zn0.6Cd0.4Se with three different layer thicknesses (3.5, 5.0, 10.0 nm) and, for comparison, 400 nm thick Zn0.6Cd0.4Se nanocrystalline single layers have been prepared by thermal evaporation of ZnSe and CdSe in vacuum. Raman scattering spectra have been measured in the range 1001000 cm1 under excitation with the 488 and 514.5 nm lines of an Ar laser. Series of four bands have been seen in the spectra of all samples. They have been related to replicas of the longitudinal optical LO-phonon in the ZnxCd1xSe layers and interpreted as an indication for

crystallinity of both kinds of samples. A blue shift of the 1 LO maximum has been observed, which has been connected with an increase of the compressive stress in the ternary layers when the layer thickness decreases. It has also been obtained that the ratio of the integrated intensity of the 1 LO band in the spectra taken with the 488 and 514.5 nm lines decreases with decreasing Zn0.6Cd0.4Se layer thickness. The result has been assigned to size-induced increase of the optical band gap of the layers. This conclusion has been conrmed by spectral photocurrent and optical transmission measurements.

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1 Introduction Ternary alloys of IIVI semiconductors included in zinc-selenide based quantum structures have demonstrated considerable promise as short-wavelength light sources, fast switching devices, etc. [13]. The interest in inclusion of such alloys (i.e. ZnCdSe, ZnSSe, etc.) in low-dimensional structures is high [48] since their lattice constant and optical properties can be changed by varying the composition which gives them advantages over binary compounds (ZnSe, CdSe, CdS). For preparation of multilayers (MLs) with good stability and periodicity, molecular beam epitaxy or metal-organic chemical vapour deposition (MOCVD) are most frequently applied. However, both techniques are quite expensive and, in addition, MOCVD normally uses dangerous gases. Besides, high quality crystalline ZnSe or GaAs substrates are necessary for the epitaxial growth. Therefore a considerable research activity has been addressed to preparation of low-dimensional structures by nonepitaxial lm growth and application of less expensive vapour deposition ([9] and references therein) or electrodeposition [10] techniques.

In several previous papers [9, 11, 12] we have reported on preparation of amorphous and amorphous/nanocrystalline multilayers with good articial periodicity and smooth interfaces in which carrier connement has been observed. In this study, preparation of ZnSe/ZnxCd1xSe periodic MLs by thermal evaporation of ZnSe and CdSe in high vacuum is reported. Raman scattering, spectral photocurrent, and optical transmission measurements are carried out to explore the lm microstructure and size induced changes in the electronic structure of the Zn0.6Cd0.4Se layers in MLs. 2 Experimental details Two kinds of samples: (i) multilayers of ZnSe/ZnxCd1xSe and (ii) single layers of ZnxCd1xSe, for comparison, were prepared by thermal evaporation of ZnSe and CdSe powder (Merck, Suprapure) loaded in two separate crucibles that can be independently heated. The crucibles were provided with cylindrical screens which were not intentionally heated. Thus each material was evaporated in a quasi-closed volume. When depositing ZnxCd1xSe layers the substrates, nominally at room temperature, were rotated and during each turn they passed
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D. Nesheva et al.: Raman scattering characterization of ZnSe/Zn0.6Cd0.4Se multilayers

over the two simultaneously heated crucibles spending 1/12 of the turn time above each crucible and 5/12 of the turn time between the two crucibles. The substrate rotation was started after achieving a deposition rate of 1.5 nm/s for both CdSe and ZnSe. The deposition rates and nominal layer thicknesses were controlled by two preliminary calibrated quartz microbalance systems MIKI FFV. Thus ZnxCd1xSe layers were prepared by alloying of CdSe and ZnSe sublayers with nominal thickness of $0.37 nm, deposited at each turn. The ZnSe layers of MLs were deposited at the same way but only the ZnSe crucible was heated. Both kind of layers in MLs had equal thickness of 3.5, 5.0 or 10 nm and the total thickness of all MLs was 200 nm; the thickness of the single layers was 400 nm. The ZnxCd1xSe composition was determined on single layers by Energy Dispersive Spectroscopy measurements using a JEOL Scanning Electron Microscope (JSM-6390) operating at an accelerating voltage of 25.00 kV. The samples were uncoated; the element used for optimization was Iron. A value of x 0.6 has been obtained. Raman scattering measurements were performed in pseudo-backscattering geometry using the 488 nm (2.54 eV) and 514.5 nm (2.41 eV) lines of an Ar laser with a power density of $0.3 W/cm2 at the sample surface). A Jobin-Yvon U1000 double monochromator and a photomultiplier as detector were used. All experiments were carried out at room temperature in air on layers deposited on crystalline p-Si substrate. Spectral photocurrent (PC) measurements were carried out at room temperature. The samples for these measurements were deposited on Corning 7059 glass substrates and provided with planar contacts of melted indium ($10 mm long and $1 mm spaced). They showed Ohmic-like current voltage characteristics at the applied elds of 102103 V/cm. The samples were illuminated by a chopped (2 Hz) monochromatic light from a diffraction grating monochromator MDR 2 at a spectral resolution of 4 nm. The measurements were carried out in the 0.41.0 mm spectral range. The samples on Corning 7059 glass substrates were also used in optical transmission measurements performed in the 4002500 nm spectral range at room temperature in air by means of a Perkin Elmer spectrophotometer, model Lamda 1050. 3 Results and discussion Raman scattering spectra of a Zn0.6Cd0.4Se single layer and three ZnSe/Zn0.6Cd0.4Se MLs with different layer thicknesses are shown in Fig. 1. A series of four longitudinal optical (LO) Raman peaks (at $240, $480, $720, $960 cm1) is observed in the spectra of all samples. This series originates from so-called LO-phonon replicas, well known in polar crystalline semiconductors. The observed LO-phonon replicas in the spectra of Zn0.6Cd0.4Se layers indicate that in both kinds of samples the Zn0.6Cd0.4Se layers are nanocrystalline rather than amorphous. Previous high resolution electron microscopy measurements on SiOx/CdSe MLs deposited in a similar way have indicated that the CdSe layers are
2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Figure 1 (online colour at: www.pss-a.com) Raman spectra of a Zn0.6Cd0.4Se single layer and ZnSe/Zn0.6Cd0.4Se MLs with layer thicknesses of 10, 5.0 and 3.5 nm taken under excitation with the 514.5 nm line. All spectra, recorded at identical experimental conditions, correspond to the same intensity scale with the top three of them vertically displaced for clarity.

nanocrystalline with nanocrystal size in direction perpendicular to the layer plane being equal to the layer thickness [9, 12]. Atomic force microscopy measurements performed using a Multimode V (Veeco, Santa Barbara, CA) microscope operating in tapping mode have revealed [13] that the Zn0.6Cd0.4Se single layers are nanocrystalline with a grain size around or less than 20 nm. Based on these observations we assume that the layers in ZnSe/Zn0.6Cd0.4Se MLs are nanocrystalline with a grain size which is close to the layer thickness. The LO phonons demonstrate a single phonon behaviour, expected for ZnxCd1xSe solid solutions [14] with the 1 LO maximum at $240 cm1. In the spectra of all samples it is disposed between the frequencies of the 1 LO modes in stoichiometric ZnSe (252 cm1) and CdSe (210 cm1). The LO band is asymmetric and has quite large FWHM ($17 cm1), which has been related [15] to lattice distortion due to the interfaces between nanocrystals and some variations in the lm composition on the nanoscale. The Raman spectra of Zn0.6Cd0.4Se layers were tted [15] to a sum of three Lorentzian bands: a band at 190 cm1 assigned to transverse optical (1 TO) phonons, a second band (at 225 cm1) related to 1 LO phonons in Cd-rich nanosized regions and a third band (at $239 cm1) related to scattering from 1 LO phonons in most of the lm volume. The formation of Cd-enriched regions in ZnxCd1xSe lms grown by MBE has been conrmed by several research groups [1618]. No appreciable scattering from the ZnSe layers of MLs (with 1 LO band expected at $252 cm1) is seen. This could be explained with the low total thickness of ZnSe (100 nm) and the larger Eo g of ZnSe single layers (2.6 eV) than the energy of the incident laser lines. As known the size reduction relaxes the Raman selection rules and therefore LO and TO Raman lines red shift and asymmetrically broaden to the low energy side. Relatively simple formulas can be found in the literature [19, 20], giving
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Original Paper
Phys. Status Solidi A 209, No. 5 (2012) 951

Figure 3 Ratio of the integrated intensity I of the 1 LO Raman band in the spectra measured under excitation by the 488 and 514.5 nm laser lines.

Figure 2 (online colour at: www.pss-a.com) Raman shift of the 1 LO maximum with decreasing Zn0.6Cd0.4Se layer thickness. Excitation by the 514.5 nm (a) and 488 nm (b) laser line was applied. All spectra in each gure correspond to the same intensity scale with the top three of them vertically displaced for clarity.

a relationship between the Raman shift/full width at half maximum of the Raman band and the crystal size. Experimental Raman spectra have been used to evaluate the average size of crystals in nanocrystalline Si and Ge lms as well as of CdS, CdSe nanocrystals embedded in various matrices. However, in the case of ZnxCd1xSe the existence of the second band at 225 cm1 strongly affects the shape of the main band at 239 cm1 and this makes impossible nanocrystal size estimation in our case. Figure 2(a) and (b) depicts the 1 LO maximum in the spectra of a single layer and three MLs with different layer thickness taken under excitation with the 514.5 and 488 nm laser lines, respectively. A gradual blue shift is observed with decreasing Zn0.6Cd0.4Se layer thickness. Since no appreciable compositional changes are expected, one can relate the blue shift to an increase of the internal strain in the Zn0.6Cd0.4Se layers with decreasing layer thickness. It is also seen from Fig. 2 that the intensity of the scattered light increases with decreasing layer thickness. The increase is by a factor of $3 and $5 for the 514.5 and 488 nm lines, respectively, were used when excitation. The observed effect is possibly a manifestation of resonance enhancement of the Raman scattering when the energy of incident light approaches the optical band gap energy, Eo g . This implies that
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the energies of the incident light (2.41 and 2.54 eV) are close to the optical band gap energy of the 5.0 nm ML and o especially to the Eo g of the 3.5 nm ML, but not to the Eg of the Zn0.6Cd0.4Se single layer and the layers in the 10 nm ML. Indeed, previous optical transmission investigations have shown [14] that the optical band gap of the Zn0.6Cd0.4Se single layer is Eo g % 2.1 eV. From the results shown in Fig. 2 one can assume that the Eo g of the 3.5 nm MLs lies in the 2.412.54 eV energy range while Eo g of the 5.0 nm ML is close but less than 2.41 eV. Figure 3 shows the ratio of the integrated intensity of the 1 LO Raman band in the spectra excited by the 488 and 514.5 nm lines. One can see that the intensity of the Raman scattering from the 3.5 nm ML excited by the 488 nm line (I488) is higher than that excited by the 514.5 nm line (I514). The situation is opposite for the other three samples, where the intensity ratio I488/I514 is lower than 1 and decreases with increasing layer thickness. This result supports the above assumption for the optical band gap energies of the samples. Based on the Raman data it can be concluded that a size induced increase of Eo g takes place in the MLs with the thinnest layers, which is in the range 0.30.4 eV. This is an indication of carrier connement in Zn0.6Cd0.4Se quantum wells. Experimental data related to the spectral photosensitivity of Zn0.6Cd0.4Se layers and 10 nm MLs are presented in Fig. 4. The photocurrent spectra of the 3.5 and 5.0 MLs are

Figure 4 (online colour at: www.pss-a.com) Photocurrent spectra of a Zn0.6Cd0.4Se single layer and a 10 nm ML.
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Acknowledgements This work has been partially supported by the Bulgarian Ministry of Education and Science under grant BM 1, the Serbian Ministry of Science and Technological Development under the Project No. 141047 and Bilateral project between BAS and SASA.

References
[1] M. A. Hines and P. Guyot-Sionnest, J. Phys. Chem. B 102, 3655 (1998). [2] I. Suemune, T. Tawara, T. Saitoh, and K. Uesugi, Appl. Phys. Lett. 71, 3886 (1997). [3] M. C. Harris Liao, Y. H. Chang, Y. F. Chen, J. W. Hsu, J. M. Lin, and W. C. Chou, Appl. Phys. Lett. 10, 2256 (1997). [4] N. N. Melnik, Yu. G. Sadofyev, T. N. Zavaritskaya, and K. L. Vodopyanov, Nanotechnology 11, 252 (2000). [5] H. Rho, L. M. Robonson, N. Mukolonwiez, L. M. Smith, H. E. Jackson, S. Lee, M. Dobrowolska, and J. K. Furdyna, Physica E 11, 5962 (2001). [6] A. Balocchi, A. Curran, T. C. M. Graham, C. Bradford, K. A. Prior, and R. J. Warburto, Appl. Phys. Lett. 86, 011915 (2005). [7] L. Gupta and S. C. Abbi, Mater. Sci. Eng. B 119, 171 (2005). [8] A. Sweiti, F. Medina, L. Martinez, and A. Lopez-Rivera, Semicond. Sci. Technol. 23, 035019 (2008). [9] D. Nesheva, in: Encyclopedia of Nanoscience and Nanotechnology, edited by H. S. Nalwa, Vol. 7 (American Scientic Publishers, California, 2004), p. 105. [10] J. A. Swizer, in: Electrochemistry of Nanomaterials, edited by G. Hodes (Wiley-VCH, Weinheim, 2001), chap. 3, p. 67. [11] R. Ionov and D. Nesheva, Thin Solid Films 213, 230 (1992). [12] D. Nesheva, in: Handbook of Surfaces and Interfaces of Materials, edited by H. S. Nalwa, Vol. 3 (Academic Press, San Diego, 2001), chap. 6, p. 239. c epanovic , I. Bineva, Z. Levi, [13] D. Nesheva, Z. Aneva, M. J. S , and B. Pejova, J. Phys.: Conf. Ser. 253, Z. V. Popovic 012035 (2010). [14] R. G. Alonso, E.-K. Suh, A. K. Ramdas, N. Samarth, H. Luo, and J. K. Furdyna, Phys. Rev. B 40, 3720 (1989). [15] D. Nesheva, Z. Aneva, M. J. Scepanovic, Z. Levi, I. Iordanova, and Z. V. Popovic, J. Phys. D, Appl. Phys. 44, 415305 (2011). [16] N. Peranio, A. Rosenauer, D. Gerthsen, S. V. Sorokin, I. V. Sedova, and S. V. Ivanov, Phys. Rev. B 61, 16015 (2000). [17] D. Schikora, S. Schwedhelm, D. J. As, K. Lischka, D. Litvinov, A. Rosenauer, D. Gerthsen, M. Strassburg, A. Hoffmann, and D. Bimberg, Appl. Phys. Lett. 76, 418 (2000). [18] S. Permogorov, A. Klochikhin, and A. Reznitsky, J. Lumin. 100, 243 (2002). [19] H. Richter, Z. P. Wang, and L. Ley, Solid State Commun. 39, 625 (1981). [20] I. H. Campbell and P. M. Fauchet, Solid State Commun. 58, 739 (1986).

Figure 5 (online colour at: www.pss-a.com) Optical transmission spectra of a Zn0.6Cd0.4Se single layer and three ZnSe/Zn0.6Cd0.4Se MLs with different layer thickness denoted in the gure.

not shown, because of low signal-to-noise ratio, which is due to a strong decrease of the photocurrent. Most likely, this increase is caused by the increase of the integrated interface area both between the layers in MLs and between the grains of the layers when the layer thickness decreases. One can see from the photocurrent spectra shown in Fig. 4 that the PC maximum of the ML is blue shifted by about 0.1 eV compared to the PC maximum of the Zn0.6Cd0.4Se single layer. This result conrms the above assumption for size induced increase of Eo g of the Zn0.6Cd0.4Se layers of MLs, which is due to carrier connement. In addition, it indicates that, indeed, Eo g of the 10 nm ML is rather far even from the energy of green laser line. Optical transmission spectra of the samples here studied are depicted in Fig. 5. They show a gradual blue shift with decreasing layer thickness that gives an additional evidence for the above assumed size induced increase of the optical band gap of the Zn0.6Cd0.4Se layers in MLs with decreasing thickness. 4 Conclusions A new technique for preparation of ZnSe/Zn0.6Cd0.4Se multilayers by thermal vacuum evaporation of ZnSe and CdSe has been reported. A blue shift of the 1 LO band related to the Raman scattering from the Zn0.6Cd0.4Se layers has been observed with decreasing layer thickness. The shift has been correlated with an increase of the compressive stress in these layers. Size-induced increase of the optical band gap of the Zn0.6Cd0.4Se layers has been assumed on the basis of Raman scattering results and conrmed by spectral photocurrent and optical transmission measurements. This conclusion shows that multiple quantum well structures from ZnSe/Zn0.6Cd0.4Se have been successfully produced by the developed technique.

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