International Journal of Smart and Nano Materials

Date Submitted by the Author: Complete List of Authors:

rP Fo
Journal: Manuscript ID: Manuscript Type: n/a Keywords:

Electronic structures of ZnO short nanorods: Experiment and Theory

URL: http://mc.manuscriptcentral.com/ijsnm Email: ijsnm@hit.edu.cn.

ee
Draft

International Journal of Smart and Nano Materials

Original Article

Mustaffa, Dzulkhairi; Universti Teknologi MARA, Centre for Nanomaterials Research Kamarulzaman, Norlida; Universti Teknologi MARA, Centre for Nanomaterials Research M. A. Ibrahim, Abdel Baset; Universti Teknologi MARA, Faculty of Applied Sciences Kasim, Muhd Firdaus; Universti Teknologi MARA, Centre for Nanomaterials zinc oxide, first principle, band gap, density of states, density functional theory

rR ev ie w On ly

Page 1 of 20

International Journal of Smart and Nano Materials

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Electronic structures of ZnO short nanorods: Experiment and Theory D. T. Mustaffa 1,2, N. Kamarulzaman* 1,2, A.B. Ibrahim 2 M.F. Kasim 1,2
1

Centre for Nanomaterials Research, Institute of Science, Level 3 Block C, Universiti

Teknologi MARA, 40450 Shah Alam, Selangor, Malaysia

2

Faculty of Applied Sciences, Universiti Teknologi MARA, 40450 Shah Alam Malaysia

rP Fo

Corresponding author email address: norlyk@salam.uitm.edu.my,

norly003@yahoo.co.uk, Tel.: +6 019 3115359, +6 03 55444481; Fax: +6 03 55443870

Biographical notes: Dzulkhairi Tajuddin Bin Mustaffa is a Ms.c student in in Universiti Teknologi MARA (UiTM). He is working on the first principles study of MgO nanostructures with different crystal lattice. He has done calculation on numerous samples of metal oxides and compared them with their experimental band gaps. He is currently calculating the electronic properties such as band structures ans density of states of nanostructured ZnO. Norlida Kamarulzaman is a professor and also an academic staff of Universiti Teknologi MARA (UiTM). She is a physicist and has been teaching physics in UiTM for more than 20 years. Her research interests are Li-ion cathode materials and other metal oxides, in the bulk as well as nanostructures. She is also interested in characterization methods such as XRD, Electron Microscopy, XPS, and spectroscopy as well as thermal characterization methods. She has investigated the behaviour of electrochemical, electrical and optical properties of nanostructures and is continuously searching for answers to explain the unique behaviour of nanostructure metal oxides. She has also used neutron diffraction methods to elucidate structural parameters of Li based materials in order to obtain better accuracy for structural analysis. Her findings include improved electrochemical performance of nanostructure battery cathodes, band gap widening of nanostructured ZnO, MgO and doped metal oxides compounds. Her effort in research is to contribute towards the better understanding of phenomena observed in nanostructured materials. She has published more than 80 papers to major international journals such as Journal of Power Sources, Powder Technology, J. Cryst. Growth, Advanced Materials Research, and etc.

URL: http://mc.manuscriptcentral.com/ijsnm Email: ijsnm@hit.edu.cn.

ee

rR

ev

ie

On

ly

International Journal of Smart and Nano Materials

Page 2 of 20

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Abdel-Baset Ibrahim is currently holds the position of a Senior Lecturer at the school of physics and material studies, Faculty of Applied Sciences. His research interests are focused on modelling and simulation of novel phenomena and devices physics. This includes areas such as nonlinear and quantum optics, Theoretical condensed matter physics, waveguide theory and fiber optics, electromagnetic waves and propagation, Optical properties of materials, Interaction of light with matter, Liquid crystals. Dr Ibrahim has more than fifteen years of experience in both Research and Development (R&D) and in academia. Muhd Firdaus Kasim is a Ph.D student in Universiti Teknologi MARA (UiTM). He is working on the preparation of ZnO and ZnO doped nanostructures using a wet chemistry method without the use of any chelating agents. He has synthesized a number of compounds and have obtained their optical band gaps. He is currently analyzing structural characteristics of the compounds and trying to correlate them with the optical behaviour and band gap values that have been obtained. M.F.Kasim hopes to contribute scientific knowledge regarding nanostructure ZnO and

doped ZnO materials.

rP Fo

URL: http://mc.manuscriptcentral.com/ijsnm Email: ijsnm@hit.edu.cn.

ee

rR ev ie w On ly

Page 3 of 20

International Journal of Smart and Nano Materials

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Electronic structures of ZnO short nanorods: Experiment and Theory

Nanostructured ZnO was synthesized using a sol-gel method without a chelating agent. The band gap of the nanostructured ZnO was experimentally determined using UV spectroscopy and found to be smaller than bulk values. To understand this phenomenon exhibited by the nanostructures, electronic structure studies of

Introduction

ZnO forms many nanostructures such as nanorods, nano flowers, etc. [1-4]. These nanostructures exhibit characteristics different from the bulk. Not much work has been done to theoretically explain the observed phenomena. The first principle calculation using density functional theory (DFT) were introduced by Hohenberg and Kohn [5] for the study of the many body problem. DFT has been used by numerous researchers in studying materials in terms of electronic properties, optical properties and several other properties [6-8]. In DFT, we use the electron density distribution n(r), instead of the the many electron wavefunction (r1, r2... rN) which simplifies the calculations for investigating the electronic structure of

many-body systems [5].

groups of scientists such as Xiang et al. [9] and Mao et al. [10]. In the work done by Mao, they studied the band structures of single walled ZnO nanotubes by performing

rP Fo
experimental results. functional theory

the ZnO via first principles density functional theory was done. From the results

of the calculations, the band gap of ZnO nanorods was in good agreement with

Keywords: zinc oxide; first principles; density of states; band gap; density

First principle study of nanostructured ZnO band gaps have been done by a few

URL: http://mc.manuscriptcentral.com/ijsnm Email: ijsnm@hit.edu.cn.

ee rR ev ie w On ly

International Journal of Smart and Nano Materials

Page 4 of 20

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

calculations on bulk ZnO and use the same information of plane wave basis set to optimize the ZnO nanotubes. In our work, the synthesis and characterization of ZnO nanostructures are done and a spectroscopic method is used to obtain the band gap experimentally. A theoretical approach to explain the narrowing of the band gap observed from experiment has been attempted. The calculations are done using the structural parameters of the nanostructures elucidated from X-Ray powder diffraction, input into the computer programme, modeled and finally, the band gap of the ZnO nanomaterial is calculated using the functional called the Revised Perdew-Burke-Ernzerhof (RBPE).

Experimental

Materials synthesis and characterization

using any chelating agents. The starting material used was zinc acetate dihydrate (R & M chemicals, 99.5% purity). This material was first dissolved in absolute ethanol and then stirred for about 1 hour. The pH of the material was about 5.5. The material was slow dried and a white precursor was obtained. The samples were then grinded using an agate mortar to obtain fine powders of ZnO. The precursor was annealed at 500 C for 24 h. The annealed precursor were characterized by using X-Ray Diffraction (XRD) using the PANalytical Xpert Pro MPD diffractometer. The XRD measurements were done using a Bragg-Brentano optical configuration with Cu k radiation. The XRD dataset was collected using settings suitable for quantitative analysis. The analysis was done using the Rietveld method via the Xpert Highscore plus software. The morphology and crystallite size of the materials were then examined by using Field Emission

rP Fo

The synthesis of ZnO powders was prepared by using a sol-gel method without

URL: http://mc.manuscriptcentral.com/ijsnm Email: ijsnm@hit.edu.cn.

ee rR ev ie w On ly

Page 5 of 20

International Journal of Smart and Nano Materials

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Scanning Electron Microscopy (FESEM - JEOL JSM-7600F). The band gap energies of the materials were obtained using a UV-Vis spectrophotometer, the Perkin Elmer Lambda 950 UV-Vis-NIR. The measurements were done in reflection mode and in ambient conditions

Computational Details

Zn atoms and two O atoms in each unit cell [11] illustrated in Figure 1.

(Figure 1)

environment. The Crystal Builder module was used to build and simulate the crystal structure. The cell parameters of ZnO nanostructure were obtained from Rietveld refinements of the X-ray Diffraction (XRD) results obtained experimentally. The cell parameters used in these calculations are as shown in Table 1. The electronic calculations were performed on the ZnO nanostructure using the CASTEP module [12] with generalized gradient approximation (GGA) and using the Revised Perdew-BurkeErnzerhof (RPBE) exchange-correlation functional [13]. Calculations were also done for bulk ZnO for comparisons where the crystal structural parameters were obtained from the Inorganic Crsystal Structure Database (ICSD). For the plane wave basis set of the calculation, the energy cut-off was set at 340 eV and the ultrasoft pseudopotential was used to describe the electron-ion interaction. Both the band structure and density of states of the bulk and nano ZnO are calculated

rP Fo

ZnO has a hexagonal wurtzite structure with the space group P63mc, with two

The structure simulation was done using the Material Studio 5.0 software

URL: http://mc.manuscriptcentral.com/ijsnm Email: ijsnm@hit.edu.cn.

ee

rR

ev

ie

On

ly

International Journal of Smart and Nano Materials

Page 6 of 20

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Results and discussions Figure 2 shows the indexed XRD results of the nanorods. It is clear that the ZnO nanomaterial crystallizes in the hexagonal crystal structure with the space group P63MC. The sample is pure with no impurity peaks present. (Figure 2) SEM result show that the morphology of the ZnO nanomaterial has mixed shapes of short rods, hexagonal crystals, polyhedral and spherical shapes as illustrated in Figure 3. All the shapes show that at least one dimension is less than 100 nm, that is, they can be considered as nanostructures. The low dimensions of the crystallites are believed to be responsible for the observed change in band gap as discussed later.

(Figure 3)

absorption edge is observed to begin at 380 nm. The corresponding band gap of the nanostructured ZnO obtained by the Tauc plot as detailed elsewhere [14] is 3.29 eV. This is lower than the band gap of the ZnO bulk material which is 3.37 eV.

(Figure 4)

It can be seen that for this sample, the lowest conduction band and highest valence band are at the same k-point set (G) This finding proves that the nanostructured ZnO is a direct band gap semi-conductor [15]. The value for the nanostructured ZnO is 0.873 eV. This is much too low compared to the experimental value obtained by UV spectroscopy. For the bulk ZnO, the same strategy is used in the calculations and the band gap obtained is 0.945eV which is also too low compared to known bulk ZnO band gap obtained experimentally which has the value of 3.37 eV [16, 17]. Our calculation, even though smaller than experimental values, agrees with the result of other researchers such as Mao et al., 1.0 eV [10] using the local density approximation (LDA) and Li et

rP Fo

The reflection spectrum of the ZnO nanostructure is shown in Figure 4. The

Figure 5 shows the results of the calculated band structure of the ZnO material.

URL: http://mc.manuscriptcentral.com/ijsnm Email: ijsnm@hit.edu.cn.

ee

rR

ev

ie

On

ly

Page 7 of 20

International Journal of Smart and Nano Materials

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

al. who obtained a value of 1.05 eV [11] using the generalized gradient approximation (GGA). (Figure 5) It is well known that most first principle calculations underestimated the band gap values. The underestimation of the calculated band gaps is related to the DFT limitation where the excitation state is neglected during the calculation of the band structures lowering the conduction band [18]. To overcome the DFT limitation the so called scissor operator is introduced which eliminates the underestimated band gaps [19]. In our case, the value of the scissor operator was 2.425, obtained for the bulk ZnO calculations. Using this scissor operator value, a new calculation was done for the nanostructured ZnO obtaining a value of 3.30 eV. As can be seen, the calculation yields a value closer to the experimental value. This showed that the scissor operator value is suitable for the ZnO materials under consideration. With the result obtained for bulk ZnO, we can thus eliminate the DFT limitation on our ZnO nanostructure calculation. The theoretical result can be said to support the phenomena of the band gap narrowing

of ZnO observed from experiment.

bulk ZnO. The sharp PDOS peak of ZnO appears at about -17.5 eV, which is mainly from O-s state. The valence band above -6.2 eV of ZnO can be divided into two regions: the lower part from -6.2 to -4.3eV and the upper part from -4.3 to about 0 eV, of which the lower valence band is contributed by a mixture of 3d states of Zn and 2p states of O, while the upper part comes mainly from 2p states of O. The conduction band of ZnO is mainly composed of the 4s state of Zn and 2p state of O. The results above are in good agreement with other reports [20, 21]. (Figure 6)

rP Fo

Figure 6 shows the partial density of states (PDOS) of ZnO nanostructures and

URL: http://mc.manuscriptcentral.com/ijsnm Email: ijsnm@hit.edu.cn.

ee

rR

ev

ie

On

ly

International Journal of Smart and Nano Materials

Page 8 of 20

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Figure 7 shows the conduction band part of DOS for both ZnO nanostructure and bulk ZnO. As we can see, the conduction band of ZnO nanostructure is slightly lower compared to the bulk ZnO. Therefore the conduction band of ZnO nanostructure is shifting downwards as shown in Figure 2(a). This effect explain the band gap narrowing of the ZnO nanostructure. (Figure 7)

Conclusion

what is happening to the energy bands of nanostructured materials. After adjustments made using the scissor operator, it was found that the ZnO nanomaterial band gap calculated from the viewpoint of theory is 3.30 eV which is very close to the experimental value of 3.29 eV. The downward shifting of the conduction band is the reason of the band gap narrowing of the ZnO nanostructure as observed from experiment. The DOS of ZnO nanostructure as studied by using the first-principles shows contributions of the s, p and d states in the valence band but only the s and p

states are present in the conduction band.

Acknowledgements,

The authors would like to thank the Institutes of Science, Universiti Teknologi MARA (UiTM) for the internal fund used in this research work. The authors would also grateful for the support from Faculty of Applied Sciences, UiTM.

rP Fo

The theoretical calculations presented in this paper have given insight about

URL: http://mc.manuscriptcentral.com/ijsnm Email: ijsnm@hit.edu.cn.

ee

rR

ev

ie

w On ly

Page 9 of 20

International Journal of Smart and Nano Materials

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

References [1] Ge M.Y., Wu H.P., Niu L., Liu J.F., Chen S.Y., Shen P.Y., Zeng Y.W., Wang Y.W., Zhang G.Q. and Jiang J.Z., Journal of Crystal Growth 305 (2007) 162 166. [2] Yao C.W., Wu H.P., Ge M.Y., Yang L., Zeng Y.W., Wang Y.W., Jiang J.Z., Materials Letters 61 (2007) 34163420 [3] [4] Phuruangrat A., Thongten T., Thongtem S., Mater. Lett. 63, (2009) 1224-1226

rP Fo
(2007), pp. 6905. (2006);

Wang X.B., Song C., Geng K.W., Zeng F., Pan F., Applied Surface Science 253

[5] [6] [7] [8]

Hohenberg, P.; Kohn, W., Phys. Rev. B, 136, (1964) 864-871 Zhu Y. Z., Chen G. D., and Ye H., Physical Rev. B 77, (2008) 245-209 Rodriguez J. A. and Maiti A., J. Phys. Chem. B 2000, 104, 3630-3638 Rasmussen D. B., Janssens T. V.W., Temel B., Bligaard T., Hinnemann B., Helveg S., Sehested J., J. of Catalysis 293 (2012) 205214

ee

rR

[9]

Xiang H. J., Jinlong Y., Hou J. G., and Zhu Q., App. Phys. Lett. 89, 223111

ev

[10] [11]

Mao Y., Zhong J., and Chen Y., Physica E-40 (2008) 499502 Li P., Deng S.H., Zhang L., Li Y.B., Zhang X.Y. and Xu J.R., Computational

ie

Materials Science 50 (2010) 153157 [12]

Clark S. J., Segall M. D, Pickard C. J., Hasnip P. J., Probert M. I. J., Refson K., Payne M. C., Z. Kristallogr. 220 (2005) 567570.

On

[13] [14]

Hammer B., Hansen L. B. and Norskov J. K., J Phys. Rev. B 59 (1999) 11 Rusdi R., Rahman A.A, Mohamed N.S., Kamarudin N. and Kamarulzaman N., Preparation of 2011 Powder Technology 210 1822.

ly

[15] [16]

Pandaley R., Jaffe J. E. and Kunz A. B., Phys. Rev. B, 43 (1991) 9228-9237 Li X., He G., Xiao G., Liu H., and Wang M., J. of Coll. and Interface Science 333 (2009) 465473

[17] [18]

Lee J., Ko K., and Park B., J. of Crystal Growth 247 (2003) 119125 Xie H., Zeng Y., Huang W., Peng L., Peng P. and Wang T., Int. J. of the Phy. Sciences Vol. 5(17) (2010) pp. 2672-2678

URL: http://mc.manuscriptcentral.com/ijsnm Email: ijsnm@hit.edu.cn.

International Journal of Smart and Nano Materials

Page 10 of 20

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

[19] [20]

Brik M.G., J. Phys. Condens. Matter 21 (2009) 485502 (8pp) Xu P.S., Sun Y.M., Shi C.S., Xu F.Q. and Pan H.B., Nuclear Instruments and Methods in Physics Research B199 (2003) 286290

[21]

Peng W., Zeng Y., Zhang C., Yan Y. and Hu W., Int. J. of the Phy. Sciences Vol. 7(14) (2012) pp. 2174 2180

rP Fo
URL: http://mc.manuscriptcentral.com/ijsnm Email: ijsnm@hit.edu.cn.

ee rR ev ie w On ly

Page 11 of 20

International Journal of Smart and Nano Materials

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Table 1. Lattice parameters and band gaps of bulk ZnO and ZnO nanostructure

Sample Bulk ZnO Nano ZnO

a=b [] 3.2500 3.2498

c [] 5.20600 5.20609

s.o.f of Zn s.o.f of O 1.0000 0.9588 1.0000 1.0000

Experimental Band Gap [eV] 3.370 3.290

rP Fo
URL: http://mc.manuscriptcentral.com/ijsnm Email: ijsnm@hit.edu.cn.

ee rR ev ie w On ly

International Journal of Smart and Nano Materials

Page 12 of 20

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Table 1. Lattice parameters and band gaps of bulk ZnO and ZnO nanostructure Figure 1. Single Unit Cell of ZnO Figure 2. XRD pattern of ZnO nanostructure Figure 3. SEM images of ZnO nanostructure Figure 4. UV-Vis of ZnO nanostructure Figure 5. Band Structure of (a) ZnO nanostructure (b) Bulk ZnO Figure 6. DOS of (a) ZnO nanostructure (b) Bulk ZnO Figure 7. Conduction band DOS of (a) ZnO nanostructure (b) Bulk ZnO

rP Fo

URL: http://mc.manuscriptcentral.com/ijsnm Email: ijsnm@hit.edu.cn.

ee rR ev ie w On ly

Page 13 of 20

International Journal of Smart and Nano Materials

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

rP Fo
URL: http://mc.manuscriptcentral.com/ijsnm Email: ijsnm@hit.edu.cn.

ee
XRD pattern of ZnO nanostructure 56x39mm (600 x 600 DPI)

rR

ev

ie w On ly

International Journal of Smart and Nano Materials

Page 14 of 20

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

rP Fo
URL: http://mc.manuscriptcentral.com/ijsnm Email: ijsnm@hit.edu.cn.

ee
SEM images of ZnO nanostructure 96x76mm (300 x 300 DPI)

rR ev ie w On ly

Page 15 of 20

International Journal of Smart and Nano Materials

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

rP Fo
URL: http://mc.manuscriptcentral.com/ijsnm Email: ijsnm@hit.edu.cn.

ee rR
Single Unit Cell of ZnO 199x193mm (300 x 300 DPI)

ev ie w On ly

International Journal of Smart and Nano Materials

Page 16 of 20

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

rP Fo
URL: http://mc.manuscriptcentral.com/ijsnm Email: ijsnm@hit.edu.cn.

ee rR
UV-Vis of ZnO nanostructure 58x42mm (600 x 600 DPI)

ev

ie w On ly

Page 17 of 20

International Journal of Smart and Nano Materials

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

rP Fo
URL: http://mc.manuscriptcentral.com/ijsnm Email: ijsnm@hit.edu.cn.

ee
DOS of (a) ZnO nanostructure (b) Bulk ZnO 29x41mm (600 x 600 DPI)

rR ev ie w On ly

International Journal of Smart and Nano Materials

Page 18 of 20

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

rP Fo
Band Structure of (a) ZnO nanostructure (b) Bulk ZnO 28x36mm (600 x 600 DPI)

URL: http://mc.manuscriptcentral.com/ijsnm Email: ijsnm@hit.edu.cn.

ee rR ev ie w On ly

Page 19 of 20

International Journal of Smart and Nano Materials

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

rP Fo
Conduction band DOS of (a) ZnO nanostructure (b) Bulk ZnO 29x34mm (600 x 600 DPI)

URL: http://mc.manuscriptcentral.com/ijsnm Email: ijsnm@hit.edu.cn.

ee rR ev ie w On ly

International Journal of Smart and Nano Materials

Page 20 of 20

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Table 1. Lattice parameters and band gaps of bulk ZnO and ZnO nanostructure

Sample Bulk ZnO Nano ZnO

a=b [] 3.2500 3.2498

c [] 5.20600 5.20609

s.o.f of Zn 1.0000 0.9588

s.o.f of O 1.0000 1.0000

Experimental Band Gap [eV] 3.370 3.290

rP Fo
URL: http://mc.manuscriptcentral.com/ijsnm Email: ijsnm@hit.edu.cn.

ee rR ev ie w On ly