Progress in Natural Science: Materials International 2013;23(1):64–69 Chinese Materials Research Society
Progress in Natural Science: Materials International www.elsevier.com/locate/pnsmi www.sciencedirect.com
ORIGINAL RESEARCH
Structural and optical properties of Cr doped ZnO crystalline thin films deposited by reactive electron beam evaporation technique Amjid Iqbala,n, Arshad Mahmooda, Taj Muhammad Khana, Ejaz Ahmedb a
National Institute of Laser and Optronics (NILOP), P.O. Nilore, Islamabad 45650, Pakistan Physics Division PINSTECH, P.O. Nilore, Islamabad 45650, Pakistan
b
Received 28 July 2012; accepted 27 November 2012 Available online 23 February 2013
KEYWORDS Cr doping; Thin film; ZnO thin films; Roughness; Ellipsometry; Optical constants
Abstract ZnO and Cr-doped ZnO thin films are grown on to glass substrates using reactive electron beam (e-beam) evaporation technique. Variation of structural, morphological, and optical properties with Cr doping is investigated. X-ray diffraction (XRD) studies show that the films are polycrystalline in nature with single phase. Energy dispersive spectroscopy (EDS) results demonstrate that Cr ions are substitutionally incorporated into ZnO. Atomic force microscopy (AFM) reveals that the films present a compact surface and root mean squared (RMS) roughness increased with Cr contents. The optical band gap energy Eg of the films has been determined using Transmission data by spectrophotometer and ellipsometry. The band gap energy found to be decreased with increasing Cr doping concentration. The optical constants (refractive index, extinction coefficient) are calculated using ellipsometry and found to increase with Cr doping concentration. & 2013 Chinese Materials Research Society. Production and hosting by Elsevier B.V. All rights reserved.
1.
Introduction
n
Corresponding author. Tel.: þ92 51 9290231, þ92 34 59503007; fax: þ92 51 2208051. E-mail address:
[email protected] (A. Iqbal). Peer review under responsibility of Chinese Materials Research Society.
Zinc oxide which is group II–IV semiconductor material with a wide direct band gap of 3.37 eV and large exciton binding energy of 60 meV has numerous applications in the fields of ultraviolet light emitting devices, ultraviolet laser diodes, transparent conducting films and solar cell [1,2]. ZnO nano crystalline structures are attractive due to its fantastic electronic, optical and magnetic properties [3]. It is highly desired to prepare ZnO nano materials to finely tune its electrical, optical
1002-0071 & 2013 Chinese Materials Research Society. Production and hosting by Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.pnsc.2013.01.010
Structural and optical properties of Cr doped ZnO crystalline thin films and magnetic properties for its potential applications in spinoptoelectronics devices. Doping with proper elements is an effective method to tune surface state, energy levels and transport performance of carriers in semiconductors, enhancing their electrical, optical and magnetic properties [4–7]. The doping of transition metal elements in ZnO offers a feasible means of fine tuning the band gap to make use as UV detector and light emitters [8]. Cr is a typical transition metal element with special abundant electron shell structure and close ionic radius of Cr3þ (0.063 nm) to that of Zn2þ (0.074 nm), which means that Cr3þ can easily substitute into ZnO lattice [9]. However, Cr doped ZnO thin films has received little experimental attention, in spite of, favorable for doping, chemical stability against etching and existence of ferromagnetism at room temperature [9–11]. Another important feature of this material is that it has magnetic, semiconducting and optical properties. The samples can be synthesized in the bulk and thin film forms and a wide range of magnetic properties including room temperature ferromagnetism have been reported and can be applied to short-wave magneto-optical devices. Cr-doped ZnO is a promising material for spintronics applications and can be made a room temperature transparent ferromagnetic semiconductor. The control tuning of the optical band-gap with Cr doping in ZnO can be applied in the fabrication of devices such as detector and light emitters. Much effort has been placed on the fabrication of ZnO based dilute magnetic semiconductor materials, their structural and magnetic characterization. There are no so many reports about the influences of Cr doped ZnO thin films on the lattice structure and optical properties. Nevertheless, the optical properties like optical constants (n, k) and transmittance in UV regions for this material is less reported, despite of its essential importance for applications in spin-optoelectronic devices. Cr doped ZnO thin films have been prepared by a variety of techniques such as, RF magnetron sputtering, co sputtering [12,13], and pulse laser deposition [14]. To our knowledge, none of the report has mentioned the growth of Cr doped ZnO by electron beam (e-beam) technique. In this work we have reported the influence of Cr doping on structural, optical and morphological properties of Cr doped ZnO thin films using reactive (e-beam) evaporation technique. In addition to this, we achieved tunebility in physical properties with Cr doping using (e-beam) technique.
2.
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Discover X-ray diffractometer with a CuKa-radiation ˚ as an X-ray source and 2y range from 251 to (l¼ 1.54186 A) 701. Concentrations of Cr, Zn and O were determined by EDS installed with leo440i SEM. Surface morphology of thin films was investigated by atomic force microscope (AFM) (Quesant Universal SPM, Ambios Technology, USA) (QScopeTM 350) in non contact mode. The optical transmittance measurements were carried out using UV-NIR Spectrophotometer (Hitachi U-4001) in the spectral range from 300 to 900 nm. Film thickness and optical constants (e.g. refractive index, extinction coefficient) were carried out using Jawoolam 200VI Ellipsometer. C and D spectra were measured at the incidence angle 701 in the spectral wavelength range from 370 to 900 nm.
3.
Results and discussion
3.1.
XRD study
The deposited polycrystalline thin films were subjected to XRD analysis for phase and structural identification as shown in Fig. 1. The characteristic peaks with high intensities corresponding to the planes (1 0 0), (0 0 2), (1 0 1) and lower intensities at (1 0 2), (1 1 0), (1 0 3) and (1 1 2) indicate the films is of high quality of hexogonal ZnO wurtzite structure. It is evident from the XRD data that there are no extra peaks due to chromium, other oxides or any zinc chromium phase, indicating that as synthesized samples are single phase. The peaks of diffraction patterns of doped samples are shifted to right as compared to the undoped ZnO. This shows that small variation in lattice parameters occur as Cr concentration in sample increase. The lattice constant C was calculated using the following equation for thin films [15]: 1 4 h2 þ hk þ k2 l2 þ 2 ¼ ð1Þ 2 2 d 3 a c C values are presented in Table 1. As can be seen, with increase of Cr doping lattice constant C decrease from 0.526 nm to 0.521 nm. A decrease in the lattice parameters can be expected when Zn2þ ions are replaced by Cr3þ ions because of the smaller radius of Cr3þ ions (0.063 nm) than Zn2þ ions (0.074 nm) [9], so the substitutional incorporation
Experimental detail
The targets of ZnO and Cr doped ZnO were prepared by the conventional solid state reaction route method. The desired amount of highly pure ZnO and Cr2O3 (0, 3, 6 mol%) powder was taken and mixed for 3 h by pestle and mortar and made its pellets using pellet presser. Then, the pellets were sintered at the temperature of 950 1C for 6 h. The sintered pellets were used as targets for the deposition of the films. The rotary and diffusion pumps were used to evacuate the vacuum chamber of e-beam system up to 2 105 mbar. The substrate to target distance was 35 cm and to gain homogeneous films, the substrates were rotating continuously with speed 15 cycles/ min. Deposition process was carried out for 6 min at 300 1C substrate temperature in oxygen environment. Structural and phase identification of the thin films were carried out by grazing angle X-ray diffraction technique using Bruker D-8
Fig. 1 XRD pattern of (a) pure ZnO, (b) 3.3 at% Cr and (c) 7.7 at% Cr doped ZnO thin films.
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Table 1
Calculated parameters for ZnO and Cr doped ZnO thin films using XRD analysis.
Sl. No.
Cr composition (at%)
Grain size (nm)
Lattice constant C (nm)
1 2 3
0 3.3 7.7
28.47 40.13 42.26
0.526 0.523 0.521
Fig. 2 EDX spectrum of (a) 3.3 at% Cr and (b) 7.7 at% Cr doped ZnO films.
Fig. 3 AFM micrographs of (a) ZnO, (b) 3.3 at% Cr and (c) 7.7 at% Cr doped ZnO thin films.
Structural and optical properties of Cr doped ZnO crystalline thin films
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Fig. 4 (a) Transmission spectra of pure and Cr doped ZnO films and (b) band gap of pure and Cr doped ZnO thin films.
Fig. 5 Schematic diagram of Cauchy and EMA layer model.
Fig. 6 Experimental and modeled values of C and D (a) ZnO, (b) 3.3 at% Cr doped ZnO and (c) 7.7 at% Cr doped ZnO.
of Cr dopant results in modification of the lattice constant C. The contraction in lattice constant C and slight shift in XRD peaks of different concentrations could be attributed to Cr incorporation and is indicative of Cr doping in to the ZnO matrix.
The average crystallite size (D) of the first three major peaks was calculated using the Scherer’s formula [16]. The calculated grain size is listed in Table 1. The table reveals that the moderate amount of Cr doping in ZnO thin films reinforce the grain growth.
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Fig. 7 (a) Variation of optical constants (a) refractive index and (b) extinction coefficient in Cr-doped ZnO thin films.
Table 2
3.2.
Comparison of optical band gaps calculated by ellipsometry and spectrophotometry.
Sl. No.
at% of Cr
Band gap (eV) ellipsometry
Band gap (eV) spectrophotometry
1 2 3
0 3.3 7.7
3.32 3.28 3.19
3.35 3.31 3.26
EDS analysis
The amount of Cr-doping was examined by EDS. Fig. 2(a) and (b) shows the EDS spectrum of 3.3 at% Cr and 7.7 at% Cr doped ZnO thin films respectively. From the figures it is well evident that the deposited thin films consist of Cr, Zn and O compositions. The presence of Si peak is due to glass substrate. Therefore, the EDS results further indicate that Cr is incorporated in to ZnO, which is also, consistent with XRD results.. 3.3.
AFM study
Fig. 3(a–c) shows the AFM micrographs with scanning area of 1 mm 1 mm for pure ZnO and Cr doped ZnO thin films, respectively. All the samples have smooth morphologies with root mean squared (RMS) roughness ranging from 5.06 nm to 24.04 nm. Similar results are observed by Ren-Chuan Chang et al. in Mg doped ZnO thin films [17]. It is observed that the RMS roughness increases with Cr doping which means the surface becomes rough and grain size increases. The observed increase in RMS with Cr doping may be due to no proper agglomeration of crystallites.. 4. 4.1.
Optical study Spectrophotometry
Optical transmission spectra of the films were taken in the wavelength of 300–900 nm using UV-NIR Spectrophotometer. Fig. 4(a) displays the transmittance of pure and Cr doped ZnO thin films. Transmission spectra of the samples divulge that the transmittance decreases with Cr concentration which may be due to the thickness of the films and doping effect. The optical band gap energy (Eg) was determined from transmission measurements by analyzing the optical data with the expression for the optical absorption coefficient, and the photon energy hn using the following equation for direct band
gap materials [18]: ðahnÞ2 ¼ AðhnEg Þ
ð2Þ
where a is the absorption coefficient, h is the Planck’s constant, A is a constant and Eg is the optical band gap energy. The optical band gap was obtained by extrapolating the linear portion of the plots of (ahv)2 versus hn to a ¼0. For pure ZnO optical band gap was found to be 3.35 eV. We observed the tuneability of the optical band gap from 3.35 eV to 3.26 eV with Cr contents in ZnO material. Similar results have also been reported for cobalt and Ni doped ZnO thin films [19,20]. The decrease in the optical band gap in transition metal doped II–IV semiconductor compounds has been observed and can be best interpreted in terms of sp–d spin exchange interaction between band electrons and the localized d electrons of the transition metal ions substituting the cations [19,21].
5.
Spectroscopic ellipsometry
Film thickness and optical constants (e.g. refractive index, extinction coefficient) were measured using spectroscopic ellipsometry. C and D spectra were measured at the incidence angle 701 in the spectral wavelength range of 370–900 nm. Cauchy layer model was used for ZnO thin film to calculate thickness and optical constants. Cauchy dispersion relation for this model is given by the equation [22]: Bn Cn þ ð3Þ l2 l4 The A, B, C parameters are variable fitted parameters that determine the index dispersion. For Cr doped ZnO films effective medium approximation (EMA) layer model was used to calculate film thickness and optical constants. Fig. 5 shows the layer models used for fitting experimental and theoretical data. Fig. 6 shows the curve fitting for theoretical and experimental data. The film
nðlÞ ¼ An þ
Structural and optical properties of Cr doped ZnO crystalline thin films thickness was found to 62 nm for ZnO, 105 nm for 3.3 at% Cr and 125 nm for 7.7 at% Cr doped ZnO. Fig. 7(a) and (b) shows the refractive index and extinction coefficient of pure and Cr doped ZnO, which manifests an increasing trend in optical constants with respect to increasing Cr contents. This may be attributed to the increased surface roughness which is clearly seen from AFM micrographs in Fig. 3. Because of the surface roughness, the optical scattering will increase and results in increase of optical constants. In this study, besides the Cr incorporation, the film thickness size plays an important role in the high refractive index value. That is, it can be clearly seen that the refractive index increase with increasing film thickness. A comparison of the optical band gaps was made calculated by two different techniques, ellipsometry and spectrophotometry. The comparison is shown in Table 2. From Table 2 we can predict that the optical band gaps calculated from the transmission data (3.35 eV) is much close to the actual value than calculated from ellipsometry data. This discrepancy in the calculated values and experimental results from ellipsometry and spectrophotometry respectively is due to the fact that ellipsometry data models based on assumptions for data fitting between experimental and theoretical data. Moreover the values calculated by ellipsometry are close to others experimental reported data [23,24].
6.
Conclusion
ZnO and Cr doped ZnO crystalline thin films were prepared on glass substrate using e-beam evaporation technique at 300 1C of substrate temperature. Moreover effect of Cr concentration on band gaps modulation, film roughness, strain and optical constants (n, k) was discussed. We observed that Cr doping have great impact on the structural and optical properties of ZnO thin film. XRD confirmed single phase, polycrystalline thin films. Grain size and surface roughness increases with Cr concentration as observed from XRD and AFM. Transmittance spectra showed that thin films are transparent which decreases with increase in Cr contents. The band gaps modulation from 3.35 eV to 3.26 eV was observed and reflects the sp–d exchange in ZnO with Cr. A comparison of band gaps was made by spectrophotometry and ellipsometry. The band gaps energy calculated from transmission data and ellipsometry are closely matched. Refractive index and extinction coefficient increases with Cr contents. AFM study shows the formation of thin film and also confirmed the increase in surface roughness with increase in Cr contents.
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Acknowledgments The authors gratefully acknowledge the assistance from National Institute of Laser and Optronics (NILOP), Pakistan and Optics Laboratory Pakistan. References [1] D.C. Look, B. Claflin, Materials Science and Engineering B 80 (2001) 383–387. [2] Wei Jin, In-Kyum Lee, Alexander Kompch, Journal of European Ceramic Society 27 (2007) 4333–4337. [3] Baiqi Wang, Javed Iqbal, Xudong Shan, Guowei Huang, Material Chemistry and Physics 113 (2009) 103–106. [4] M. Sun, Q.F. Zhang, J.L. Wu, Journal of Physics D 40 (2007) 3798. [5] C.K. Xu, J. Chun, D.E. Kim, J.J. Kim, B. Chon, T. Joo, Applied Physics Letters 90 (2007) 083113. [6] J.B. Cui, U.J. Gibson, Applied Physics Letters 87 (2005) 133108. [7] H. Zhang, D. Yang, X. Ma, N. Du, J. Wu, D. Que, Journal of Physical Chemistry B 110 (2006) 827. [8] S. Senthilkumaar, K. Rajendran, S. Banerjee, Materials Science in Semiconductor Processing 11 (2008) 6–12. [9] Yang Liua, Jinghai Yang, Journal of Alloys and Compounds 486 (2009) 835–838. [10] M.D. Olvera, A. Maldonado, R. Asomoza, M.M. Lira, Journal of Materials Science: Materials in Electronics 11 (2000) 1–5. [11] K. Sato, H.K. Yoshida, Japanese Journal of Applied Physics Part 2 40 (2001) L334. [12] J. Elanchezhiyan, K.P. Bhuvana, N. Gopalakrishnan, Journal of Alloys and Compounds 468 (2009) 7–10. [13] Y.M. Hu, Y.T. Chen, Z.X. Zhong, C.C. Yu, Applied Surface Science 254 (2007) 3873–3878. [14] Issei Satoh, Takeshi Kobayashi, Journal of Applied Surface Science 216 (2003) 603–606. [15] B.D. Cullity, S.R. Stock, Elements of X-Ray Diffraction, 3rd ed. Addison Wesley Publishing Company, Inc., USA, 2001. [16] B.D. Cullity, Elements of X-ray Diffractions, Addition-Wesley, Reading, MA, 1978, p. 102. [17] Ren-Chuan Chang, Sheng-Yuan Chua, Po-Wen Yeh, Sensors and Actuators B 132 (2008) 290–295. [18] E.J.I. Pankove, Optical Processes in Semiconductors, Dover Publications, New York, 1976. [19] C.B. Fitzgerald, Applied Surface Science 247 (2005) 493–496. [20] Y.R. Lee, A.K. Ramdas, R.L. Aggarwal, Physical Review B 38 (1988) 10600. [21] R.B. Bylsma, W.M. Becker, J. Kossut, U. Debska, D.Y. Short, Physical Review B 33 (1986) 8207. [22] R. Capan, N.B. Chaure, A.K. Hassan, A.K. Ray, Semiconductor Science and Technology 19 (2004) 198–202. [23] F.K. Shan, Y.S. Yu, Journal of European Ceramic Society 24 (2004) 1869–1872. [24] Jianguo Lv, Kai Huang, Xuemei Chen, Optics Communications 284 (2011) 2905–2908.
