Elsevier Editorial System(tm) for Thin Solid Films Manuscript Draft Manuscript Number: TSF-D-11-00200R2 Title: Growth and

characterization of ZnO and Mg(x)Zn(1-x)O thin films by aerosol assisted chemical vapor deposition technique Article Type: Full Length Section/Category: A. Synthesis and Characterization Keywords: ZnO, MgxZn{1-x}O; Polycrystalline; AACVD; Thin films. Corresponding Author: Mr. VIPIN KUMAR KAUSHIK, M.Tech. Corresponding Author's Institution: Shri GS Institute of technology and Science First Author: VIPIN KUMAR KAUSHIK, M.Tech. Order of Authors: VIPIN KUMAR KAUSHIK, M.Tech.; TAPAS GANGULI, PhD; CHANDRCHUR MUKHARJI, PhD; PRANAY K SEN, PhD; RAVI KUMAR, M.Sc. Abstract: Poly crystalline thin films of ZnO and MgxZn1xO have been deposited on glass substrates with varying Mg-content under constant growth parameters. Aerosol assisted chemical vapor deposition technique has been adopted for the deposition of thin films in which we use the solution of zinc acetyl acetonate and magnesium acetate in isopropyl alcohol and O2 is used as the carrier gas. The depositions have been carried out at 480 oC. The films were found to exhibit high transmittance (>90 %), low absorbance and low reflectance in the visible regions. Absorption coefficient and thickness of the films have been determined from transmittance spectra in the ultraviolet-visible-near infrared regions by applying widely used envelope method. The energy band gap of the deposited samples increases from 3.25 to 3.75 eV, with increasing Mg content in the films. The crystallographic structure of these films was analyzed by using x-ray diffraction method. The films were polycrystalline in nature with preferred (0001) orientation perpendicular to substrate surface. A systematic change in surface morphology is observed with increasing Mg content in the films.

Cover Letter

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*Reply to Editor and Referees

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*Highlights

Bullet Points
As asked by the editorial office, a short collection of bullet points that convey the core findings of the article is given below. Design an aerosol assisted chemical vapour deposition (AACVD) system for the growth of thin films. ZnO and MgxZn1-xO thin films have been deposited on glass substrate using the above AACVD system. The MgxZn1-xO thin films were pollycristalline and single phase up to x = 0.2. The films are optically transparent with low absorbance. The variation of lattice parameters (a and c) of MgxZn1-xO films follow Vegards law upto x = 0.2.

*Manuscript Click here to view linked References

Growth and characterization of ZnO and Mgx Zn1x O thin lms by aerosol assisted chemical vapor deposition technique
Vipin K. Kaushika , Tapas Gangulib , Ravi Kumarb , C. Mukherjeeb , P. K. Sena
a Department

of Applied Physics, Shri G.S. Institute of Technology and Science, Indore-452 003, India. E-mail: vip08007@gmail.com b Raja Ramanna Centre for Advanced Technology, Indore-452 013, India.

Abstract Poly crystalline thin lms of ZnO and Mgx Zn1x O have been deposited on glass substrates with varying Mg-content under constant growth parameters. Aerosol assisted chemical vapor deposition technique has been adopted for the deposition of thin lms in which we use the solution of zinc acetyl acetonate and magnesium acetate in isopropyl alcohol and O2 is used as the carrier gas. The depositions have been carried out at 480 o C. The lms were found to exhibit high transmittance (>90 %), low absorbance and low reectance in the visible regions. Absorption coecient and thickness of the lms have been determined from transmittance spectra in the ultraviolet-visible-near infrared regions by applying widely used envelope method. The energy band gap of the deposited samples increases from 3.25 to 3.75 eV, with increasing Mg content in the lms. The crystallographic structure of these lms was analyzed by using xray diraction method. The lms were polycrystalline in nature with preferred (00 orientation perpendicular to substrate surface. A systematic change in 01) surface morphology is observed with increasing Mg content in the lms. Keywords: ZnO, Mgx Zn1x O, Polycrystalline, AACVD, Thin lms

1. Introduction The growth and characterization of ZnO and ZnO based alloys e.g. Mx Zn1x O (M=Mg, Cd and Mn etc.). has become an active research eld due to the wide ranging applications of the above materials in the fabrication of light emitting diodes, UV-photo detectors, UV-blue semiconductor lasers, at panel displays, solar cells, gas sensors, photo-voltaic cells and transparent electrodes [1-3]. Since the oscillator strength of excitons is typically much larger than that of direct electron-hole transitions in direct band gap semiconductors, the large exciton binding energy of ZnO (60 meV) compared to GaN (25 meV) makes it a promising material for optical devices utilising excitonic eects. Optically pumped lasing has been reported in ZnO platelets, thin lms, clusters
Preprint submitted to Elsevier December 22, 2011

consisting of ZnO nano-crystals and ZnO nano wires [4-6]. Recently, several near ultraviolet diode sources have been reported that utilize the GaN material system [7]. As an alternative to the GaN material system, ZnO alloys are of great interest. Alloying ZnO lms with MgO or CdO permits the band gap to be tailored between 2.8 and 4 eV, which facilitates band gap engineering [8]. This also suggests the possibility of hybrid optoelectronic devices comprising lattice-matched MgZnO/AlGaN heterojunctions. Although the crystal structure of ZnO is hexagonal, whereas that of MgO is cubic, the near equality of ionic radii of Mg++ (1.36 ) and Zn++ (1.25 ) allows some replacement in A A either structure [9]. According to the phase diagram, MgO allows a maximum of 56 wt. % ZnO at 1600 o C and maintains its NaCl structure with the lattice constant remaning close to that of pure MgO (4.208 ) [10]. A In the case of bulk ZnO, the bulk solid solubility of Mg is limited to only maximum 2%, and the unit cell retains its hexagonal structure [11]. However, the solubility of Mg in ZnO thin lms has been reported to have dierent values, e.g. Ryoken et. al. [12] have reported the stable wurtzite formation upto x = 0.18 by pulsed laser deposition (PLD) technique. Kang et.al. [13] have reported the solubility limit to be upto x = 0.4 by magnetron sputturing technique. Ohtomo et. al. [14] have reported this limit to be upto x = 0.36 by PLD technique. Besides the above reports, Mgx Zn1x O lms have also been deposited by metalorganic chemical vapor deposition [15], molecular beam epitaxy [16], sputtering [13, 17], spray pyrolysis [18], etc. In the present work, we have employed the aerosol assisted chemical vapor deposition (AACVD) technique for the growth of Mgx Zn1x O lms on soda lime glass substrates. AACVD is an attractive technique due to its low cost, simplicity, minimal waste production and the possibility of injecting liquid precursor or solid precursor dissolved in suitable solvents in the CVD reactor for growth of thin lms. This technique becomes specically benecial for liquid/solid precursors with very low vapor pressure. There are a few reports on the use of AACVD technique for the deposition of ZnO, ZrC, F:SnO2 , -Fe2 O3 thin lm electrodes, yttria stabilized zirconia [1923] etc. In this technique, a nozzle of extremely ne dimensions is used to inject the solution of the precursor directly onto the heated substrate. Using AACVD technique, we have been able to incorporate up to 20 wt. % Mg in ZnO while maintaining the wurtzite hexagonal structure. The crystalline structure and the surface morphology of ZnO lms were investigated using X-ray diraction (XRD) and atomic force microscopy (AFM) respectively. The optical properties of the lms were studied via optical spectrophotometery. In this paper, we report the deposition of single phase wurtzite Mx Zn1x O thin lms upto x = 0.2. 2. Experimental Technique In the present work, we have used an indigenously developed aerosol assisted chemical vapor deposition (AACVD) system for the growth of thin lms of ZnO and Mgx Zn1x O. The schematic of the AACVD system is shown in g.1. The 2

system consists of a horizontal SS-304 cylindrical reactor, where the growth is carried out at atmospheric pressure. The precursor was dissolved in a suitable solvent and used as the source of the depositing material. This liquid precursor was injected into the reactor through a ne nozzle having an orice of 500 m diameter the schematic of which is also shown in the same gure. Oxygen gas

Figure 1: Schematic of indigenously designed AACVD system.

was used as the carrier gas for the injection of the liquid precursor in the form of an aerosol inside the reactor. The ow rate of the precursor was controlled by varying the ow of carrier gas (O2 ). The precursor, in the form of aerosol, ows close to the horizontally placed heated substrate and cracks homogeneously to form the required thin lm. The temperature of the substrate is monitored by a thermocouple and the temperature was maintained within 1 o C. The substrate surface is placed at an angle 10o to the horizontal planes to ensure the deposition of uniform lms. For the growth of Mgx Zn1x O, dierent mass proportions of Mg acetate (Mg(CH3 COO)2 ) and zinc acetyl acetonate (Zn(C5 H7 O2 )2 .H2 O) were dissolved in isopropyl alcohol (IPA) and are used as precursors. For dissolving the solute, IPA was heated to its boiling point and the solution was stirred for about 15 min. The mass ratio of Mg to Zn in the precursor solution is henceforth referred to as xliquid . This prepared precursor solution was transported through a ne nozzle with the help of oxygen gas at a constant ow rate of 0.5 lpm. The growth temperature was kept at 480 o C. Before growth, the deposition chamber was purged with oxygen gas for 10 minutes at a ow rate of 0.5 lpm. Soda lime glass substrates (1 1 ) were used for the deposition of the lms. The substrates were cleaned by boiling in trichlorothylene, acetone and methanol for 2 minutes each, prior to deposition. Transmission spectra of the lms were obtained using a UV-Visible-NIR spectrophotometer (Shimadzu 1700UV) in the range of 250 nm to 900 nm. The crystalline structure of the various lms were determined from the 2 patterns obtained using a Panalytial X-Pert PRO MRD system. The system uses a 2.2 kW X-ray generator and the measurement were carried out with copper K source. AFM measurements were carried out in a SOLVER-PRO setup (NT-MDT) using Si cantilever tips of radius of curvature 20 nm and resonant frequency 190 kHz in non-contact mode of 3

measurement. Variation of Surface morphology and roughness of the lms with respect to Mg content were determined. 3. Results and Discussions I. Optical Characterization: The transmittance spectra of the deposited thin lms of ZnO and Mgx Zn1x O are shown in g. 2. Transmittance of the substrate is also shown in the same gure. The presence of interference fringes and a sharp absorption edge can be seen in all the lms. Absorption edges have been highlighted in the inset shown in g. 2. Good optical quality of Mgx Zn1x O lms are grown irrespective its Mg content. As expected, the sharp band edge absorption feature shifts to lower wavelengths (blue shift) with increasing Mg concentration [24]. The thickness of the deposited lms were evaluated from the transmission data by using envelope method [25] and the respective values are given in Table-1. It appears worthy to note that the error bars for the measured thickness is only a few percent and depends upon the degree of accuracy of the measured refractive index. The absorption edge has been determined for all the lms by the well established Tauc plot method, which are shown in g. 3 and used to calculate the band gap of lms. The band gaps obtained for all the lms have been compared with those available in literature [11] for the estimation of Mg/Zn ratio in the lms (referred as xsolid ). The observed values of xsolid for all the lms are also mentioned in Table-1. II. Structural Characterization: The X-ray diraction patterns of all the lms obtained in the conventional Bragg-Brentano geometry. The obtained data indicates that all the Mgx Zn1x O lms are polycrystalline. Respective (hkil) values for all the peaks are indicated in g. 4. It is important to note that no extra peaks corresponding to the MgO phase is observed in the measured 2 range that conform the deposition of single phase polycrystalline Mgx Zn1x O ternary in the range of xsolid studied in this work. Although the growth of ZnO thin lms mainly occurs along the c-axis (00 01). However, in our case, possibly due to the low deposition temperature and the polycrystalline nature of the substrate, the lms are quit randomly oriented as observed by the presence of other reection in XRD pattern. With the incorporation of Mg in the lattice site of Zn, the situation gets altered mainly due to the fact that the MgO have cubic structure and not the hexagonal structure, like ZnO. Thus altered texture in Mgx Zn1x O for xsolid > 0 is observed. Further analysis of the texture is beyond the scope of this work as polycrystalline substrates are used. Fig. 5a shows the XRD data in 2 range of 30o to 36o where the two major reections,(10 and (00 are observed. A systematic shift in the position of 10) 02) these two peaks with xsolid is observed as shown by the arrows in g. 5a. The c and a values of the lms are evaluated from the reection plane (10 (00 10), 02),

Table 1: Experimentally measured and calculated parameters of Mgx Zn1x O thin lms.

Film No. 020409 080409a 080409b 190809a 230909 240909

xliquid

Thickness t(m) 1.31 1.99 0.82 1.69 0.80 0.80

Abs. edge ab (eV) 3.25 3.44 3.51 3.59 3.64 3.74

xsolid

0.00 0.04 0.11 0.14 0.18 0.21

0.00 0.04 0.09 0.14 0.16 0.20

Average Roughness (nm) 2.7 7.6 6.8

rms Roughness (nm) 3.6 10.1 8.6

(1011), (10 and (11 using the eqn.: 12) 22) 1/d2 = 4/3((h2 + k 2 + hk)/a2 ) + l2 /c2 . (1)

The variation of c and a with xsolid are plotted in gs. 5b and 5c, respectively. We nd that there is a linear variation in the values of both c and a up to xsolid = 0.2 (the range of studied in this work). Interestingly, their trends are opposite: c decreases, while a increases with increasing Mg content in the lm. The linear t of the data are also shown in gs. 5b and 5c. The respective equations for c(x) and a(x) for x 0.2 are as follows (in ): A c(x) = 5.21 0.20x; and a(x) = 3.25 + 0.09x. (2)

The above relations enable us to evaluate the c/a values for Mgx Zn1x O lms for the variation of Mg composition up to xsolid 0.2. In g. 6, we plot c/a vales with xsolid and observe that the ratio c/a decrease with xsolid , which is similar to the observation for Alx Ga1x N systems [26]. In both the cases, the substitution is with a smaller sized atom, namely, Mg at Zn site and Al at Ga sites and hence the observed results of a decrease in c/a values with xsolid , is consistent with a similar wurtzite material system. The observation of a linear variation of c and a values with xsolid upto x 0.2 appears nontrivial. This is because in a recent report on sol-gel Mgx Zn1x O lms growth [11] Vegards law was shown to be varing only up to xsolid = 0.05. Beyond 0.05, signicant phase segregation was observed and the lattice parameter does not follow Vegards law and varies irregularly. This can be explained by the possible presence of compositional inhomogeneity of Mg incorporation in ZnO for the xsolid , ranging from 0.05 to 0.20. However, such inhomogeneities are ruled out in our lms up to xsolid = 0.2, as we do not see any noticeable deviation from Vegards law in this range for a and c values. Figures 7(a), 7(b) and 7(c) show two dimensional AFM images (55 m) of pure ZnO, Mg0.09 Zn0.91 O and Mg0.20 Zn0.80 O, respectively. Roughness of the pure ZnO lm is low (2.7 nm) and is much less than the measured values of the roughness of the Mgx Zn1x O lms. It appears that with increasing Mg content initially roughness increases nearly three fold (7.6 nm at xsolid = 0.09) and with 5

further increase of Mg content roughness decreases (6.8 nm at xsolid = 0.2). It is apparent from the gure that there is a systematic change in the surface morphology with increasing xsolid from 0 to 0.2. Initially at low Mg content (0.09) very small grains (few tens of nanometer) are formed and these grains are closely packed. Further, when Mg content is doubled much larger grains are form ( 100 nm). These grains are smoother, less closely packed and they are nearly rectangular in shape. Average roughness and rms roughness of the lms are included in Table-1. 4. Conclusions We have deposited good optical quality poly-crystalline Mgx Zn1x O thin lms using an indigenously developed AACVD system. The transmission data clearly shows a shift in the band edge to lower wavelengths with increasing Mg-content in the lms. This information has been used to determine the Mgcontent in the lms and the Mg incorporation eciency for an AACVD system has been determined. XRD data shows that in the range of Mg compositions (0 x 0.2) studied in this work, there is no phase segregation. The variations in the values of the lattice constants a and c for the dierent values of x (0 x 0.2) have been determined for the deposited lms. A systematic change in surface morphology is observed with increasing Mg content in the lms. 5. Acknowledgment The authors acknowledge Dr. Meena Tiwari of SGSITS, Indore for the UVVIS measurement. Authors VK, TG and RK thank Dr. S. M. Oak of RRCAT, Indore for encouragement and support during the course of the work. References [1] Z. L. Wang, J. Phys.: Condens. Matter 16 (2004) R829. u [2] U. Ozgr, Ya. I. Alivov, C. Liu, A. Teke, M. A. Reshchikov, S. Doan, V. g Avrutin, S. J. Cho, H. Morko, J. Appl. Phys. 98 (2005) 041301. c [3] A. Janotti, C. G. Van de Walle, Rep. Prog. Phys. 72 (2009) 126501. [4] C. L. Hsu, S. J. Chang, H. C. Hung, Y. R. Lin, C. J. Huang, Y. K. Tseng, I. C. Chen, IEEE Trans. Nanotechnol. 4 (2005) 649. [5] S. F. Yu, C. Yuen, S. P. Lau, H. W. Lee, Appl. Phys. Lett. 84 (2004) 3244. [6] L. Y. L. Wu, A. I. Y. Tok, F. Y. C. Boey, X. T. Zeng, X. H. Zhang, IEEE Trans. Nanotechnol. 6 (2007) 497. [7] R. Dahal, B. Pantha, J. Li, J. Y. Lin, H. X. Jiang, Appl. Phys. Lett. 94 (2009) 063505. 6

[8] T. Makino, Y. Segawa, M. Kawasaki, A. Ohtomo, R. Shiroki, K. Tamura T. Yasuda, H. Koinuma, Appl. Phys. Lett. 78 (2001) 1237. [9] S. Choopun, R. D. Vispute, W. Yang, R. P. Sharma, T. Venkatesan, Appl. Phys. Lett. 80 (2002) 1529. [10] C. Kim, S. J. Leem, I. K. Robinson, W. I. Park, D. H. Kim, G. C. Yi, Phys. Rev. B 66 (2002) 113404. [11] R. Ghosh, D. Basaka, J. Appl. Phys. 101 (2007) 023507. [12] H. Ryoken, N. Ohashi, I. Sakaguchi, Y. Adachi, S. Hishita, H. Haneda, J. Cryst. Growth 287 (2006) 134. [13] S. W. Kang, Y. Y. Kim, C. H. Ahn, S. K. Mohanta, H. K. Cho, J. Mater. Sci.: Mater Electron 19 (2008) 755. [14] A. Ohtomo, M. Kawasaki, T. Koida, K. Masubuchi, H. Koinumab Y. Sakurai, Y. Yoshida, T. Yasuda, Y. Segawa, Appl. Phys. Lett. 72 (1998) 2466. [15] S. T. Tan, B. J. Chen, X. W. Sun, W. J. Fan, H. S. Kwok, X. H. Zhang, S. J. Chua, J. Appl. Phys., 98 (2005) 013505. [16] Z. Ji, Y. Song, Y. Xiang, K. Liu, C. Wang, Z. Ye, J. Cryst. Growth 265 (2004) 537. [17] J. L. Zhao, X. M. Li, A. Krtschil, A. Krost, W. D. Yu, Y. W. Zhang, Y. F. Gu, X. D. Gao, Appl. Phys. Lett. 90 (2007) 062118. u u [18] N. Kilin, L. Arda, S. Oztrk, Z. Z. Oztrk, Cryst. Res. Technol. 45 (2010) c 529. [19] M. R. Waugh, G. Hyett, I. P. Parkin, Chem. Vap. Deposition 14 (2008) 366. [20] Y. S. Won, Y. S. Kim, V. G. Varanasi, O. Kryliouk, T. J. Anderson, C. T. Sirimanne, L. M. White, J. Cryst. Growth 304 (2007) 324. [21] D. S. Bhachu, M. R. Waugh, K. Zeissler, W. R. Branford, I. P. Parkin, Chem.Eur. J. 17 (2011) 11613. [22] A. Tahir, K. G. U. Wijayantha, S. S. Yarahmadi, M. Mazhar, V. McKee, Chem. Mat. 21 (2009) 3763. [23] H. B. Wang, C. R. Xia, G. Y. Meng , D. K. Peng, Mater. Lett. 44 (2000) 23. [24] Y. Y. Kim, B. H. Kong, M. K. Choi, H. K. Cho, Mater. Sci. Eng. B 165 (2009) 80. [25] R. Swanepoel, J. Phys. E: Sci. Instrum. 16 (1983) 1214. [26] Z. Dridi, B. Bouhafs, P. Ruterana, Semicond. Sci. Technol. 18 (2003) 850. 7

100

80

Transmittance ( %)

60
Transmittance (%)

75 60 45 30 15 0

40

x=0.00 x=0.04 x=0.09 x=0.14 x=0.16 x=0.20 Bare

20

300

330

360

390

420

450

Wavelength (nm)

300

400

500 600 700 Wavelength (nm)

800

900

Figure 2: Transmittance spectra of Mgx Zn1x O thin lms with varying Mg content (xsolid ). Inset shows the range close to the band edge of the thin lms.

20
x=0.00 x=0.04 x=0.09 x=0.14 x=0.16 x=0.20
Eg = 3.25 eV Eg = 3.44 eV

(h) X 1012 (eV/m)2

2

15

10

Eg = 3.51 eV Eg = 3.59 eV Eg = 3.64 eV Eg = 3.74 eV

0 2.9 3.0 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8

h (eV)
Figure 3: Blue shift of band gap in Mgx Zn1x O lms with varying Mg content (xsolid ).

1500

Intensity (arb. units)

(1010)

(0002)

(1011)

1800

(1120)

(1013)

x=0.20

900

x=0.16 x=0.09

600

x=0.04 x=0.00

300

40

50

60

(1122)

1200

(1012)

70

2 (Degree)

Figure 4: X-Ray diraction spectra of Mgx Zn1x O thin lms for varying Mg content (xsolid ).

5.22

(1010)

1500

(0002)

(a)
x=0.20

(b)
5.21 3.26

(c)

Intensity (arb. units)

c ( )

Lattice parameter

Lattice parameter
0.0 0.1 0.2

5.20

a ( )
3.26 5.19 3.25 5.18 5.17 3.25 5.16

1000

x=0.16 x=0.09 x=0.04

500

x=0.00
30 31 32 33 34 35
0.0 0.1 0.2

2 (Degree)

xsolid

xsolid

Figure 5: Shifting of c and a values of Mgx Zn1x O lms as a function of xsolid .

1.605

c/a Values

1.600

c/a Values

1.595

1.590

1.585

1.580 0.00 0.05 0.10 0.15 0.20

xsolid

Figure 6: Variation of c/a values of Mgx Zn1x O lms as a function of xsolid .

10

Figure 7: 2D AFM micrography of Mgx Zn1x O lms (a) for xsolid = 0.00 (pure ZnO), (b) for xsolid = 0.09 and (c) for xsolid = 0.20. All the lms are deposited on glass substrate at temperature 480 0 C.

11

Additional Material

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