International Journal of Application or Innovation in Engineering & Management (IJAIEM)

Web Site: www.ijaiem.org Email: editor@ijaiem.org, editorijaiem@gmail.com Volume 2, Issue 9, September 2013 ISSN 2319 - 4847

Synthesis of Aluminum and Boron co-doped ZnO nanostructure films on Glass Substrate
Anwar Hussein Ali1, Rashid HashimJabbar2,Abdulhussein K. Elttayef 2
1

Dept. of Physics, College of Science, Al-Mustansiriyah University, Baghdad, Iraq. 2 Center of Applied Physics, Ministry of Science and Technology, Baghdad, Iraq.

Abstract
In this study, undoped and Aluminum and Boron co-doped ZnO(AZB)thin films were deposited at 450 oCon glass substrates by Spray Pyrolysis methodin (1505 nm). Characterization techniques of XRD, SEM and UV-visible spectra measurements were performed to investigate the effects of Aluminum and Boron co-doping on the structural and optical properties of ZnO thin films.The structure of AZB nanostructure films hasbeen found to exhibit the hexagonal wurtzite structure. The increase of AZB concentration caused to decrease the grain size, bandgapfor AZB(2 at %) and increase the transmittance for AZB(2, 4, 6 at %) in a visible region .The structural details and microstructurewere obtained from X-ray diffraction and scanning electron microscope(SEM).

Keywords:ZnOnanostructures, boron and aluminum co-doped, Synthesis.

1. Introduction
Semiconductor ZnO has been the subject of research for many applications for the past several years, because the material is nontoxic, biosafe, chemically stable, and biocompatible. ZnO has a direct wide bandgapof around 3.2-3.37eV at room temperature 300K[1,2], where the bottom of the conduction band is formed from the 4s levels of Zn2+ and the top of the valence band is built from the 2p orbitals of O2-. It has strong ionic bonding and exciton binding energy of 60 meV. low resistivity and high transparency in the visible range and high light trapping characteristics [3]. [4]ZnO has attracted increasing attention as a potential material for optoelectronic devices such as low threshold blue/UV lasers, solar cells, LEDs, sensors, display devices and photodetectors[5-7].The synthesis of nanoparticleshas become a highly developed _eld owing to thescienti_c and technological interest due to the structuralpeculiarities and unusual physical and chemical propertiesthey may lead to [4]. In recent years, it has beenfound that ZnO can be synthesized by various routessuch as electron beam evaporation technique [5], chemicalspray pyrolysis technique [1], RF thermal plasmaevaporation [6], sol_gel method [3, 7], and precipitation[1, 7] methods. Among these methods, precipitation hasmany advantages over the other methods, for example,it is unsophisticated and a low cost method[2,4,8].Zinc oxide (ZnO) has been used in a wide range of products for many years, including, amongothers, varistors, surface acoustic wave devices and cosmetics. Besides these established applications,ZnO and its ternary alloys are now also being considered as potential materials foroptoelectronic applications, such as light emitting diodes, photovoltaics, sensors, displays, etc[9].

2. Experimental
Nanostructure films of AZB (0.0, 2, 4, 6, 8 at %) i.e.[ZnO pure, ZnO:(B 1%+Al 1%),ZnO:(B 2%+ Al 2%),ZnO:(B 3%,Al 3%),ZnO:(B 4%,Al 4%)]prepared by spray pyrolysis deposition (SPD) technique in air from zinc nitrate (Zn(NO3)2.6H2O) diluted with distilled water to concentration of molarities equal 0.075 M, (Zn(NO3)2.6H2O) is a solid material which has a white color and its molecular weight (297.4 g/mole). The deposition method involves the decomposition of an aqueous solution of zinc nitrate. The spray solution is sprayed onto heated substrates held at 450oC. The time of the deposition is 3 sec. each 42 sec., Compressed air is used as a gas carrier and it is fed with the solution into a spray nozzle at a preadjusted constant atomization pressure. Film thickness(t=1505 nm) was determined by(TFProbeTM Spectroscopic Reflectometer film thickness measurement system). Diffraction studies are carried out using X- Ray Shemadz XRD Diffractrometer (operated at 40 kV an accelerating potential and 30 mA with filtered CuK radiation 0.15406 nm wavelengths) was performed to identify the crystalline phases present in the deposited films. The size and morphology of the AZB nanostructuresamples were observed with a scanning electron microscope (SEM).

3. Result and discussion

3.1. Structural analysis:The XRD graphs of AZB nanostructure films are shown in fig.1. It is obvious the nanostructurefilm is polycrystalline and all the samples have hexagonal wurtzite structure. the intensity of ZnO pure nanostructure film is more than the intensity of AZB nanostructure for (002) plane.

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International Journal of Application or Innovation in Engineering & Management (IJAIEM)

Web Site: www.ijaiem.org Email: editor@ijaiem.org, editorijaiem@gmail.com Volume 2, Issue 9, September 2013 ISSN 2319 - 4847

Figure 1. X-ray diffraction pattern ofAZB nanostructure with concentration: 0.0 to 8 at.%.

The crystallite size and strain dependon the 2 peak position which enables us to determinethe effect of peak broadening using the Williamson-Hall(W-H) method: .. (1) The plot of 4 sin versus cos taking (100), (002), and (101) lattice planes correspondingto the wurtzite phase of ZnO are shown in Figure 2.From the linear fit to the data, the crystallite size wasextracted from the y-intercept and the micro strain from theslope of the straight line. The strain is due to the incorporationof a dopant in the periodic lattice. The W-Hplots show a negative strain for AZB nanoparticles which is an indication of latticeShrinkage[10].
0.025 0.024 0.023 0.022 0.021 0.02 0.019 0.018 0.017 0.016 0.015 0.014 0.013 0.012 0.011 0.01 0.009 0.008 0.007 0.006 0.005 0.004 0.003 0.002 0.001 0

ZnO pure AZB 6%

AZB 2% AZB 8%

AZB 4%

FWHM COS()

1.05

1.1

1.15

1.2

1.25

1.3

4SIN()
Figure 2. W-H plots of AZBnanostructure with concentration: 0.0 to 8 at.%.

The obtained crystallite size (DW-H)and microstrain () calculated by William-Hall method, crystallite size measured by scanning electron microscope(DSEM (nm)) and energy gap for different samples are summarized in Table 1. Table 1. W-H crystallite size (DW-H), DSEM, strain () and optical gap (Eo) for AZB nanostructure with concentration: 0.0 to 8 at.%. Doping( D SEM Eg(eV (x10DW-H (nm) 3 %) (nm) ) ) 0 60.3 31 9 3.25 2 14.5 20 3.7 3.22 4 9.5 15 5.5 3.30 6 8.0 12 9 3.31 8 7.6 8 3.3 3.25 3.2.Optical properties: The transmittance spectra of AZB nanostructure films in thewavelength range of 3001100 nm are shown in Fig. 4(a).where the transmittance at 550 nm is increase with increase the concentration 0.0 to 6 at % then decrease for the concentration 8 at %.

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Web Site: www.ijaiem.org Email: editor@ijaiem.org, editorijaiem@gmail.com Volume 2, Issue 9, September 2013 ISSN 2319 - 4847

Figure 3.Transmittance of AZB nanostructure with concentration: 0.0 to 8 at.%. Optical absorption coefficient ( ) is calculated using Lambert'slaws using following equation [11]. .. (2) Where T is the transmittance and is the thickness of film.The optical bandgap of AZB nanostructure films is estimated by the extrapolation of the linear portion of vs plots. For the allowed direct transition, the variation of a with photon energy ( ) obeyTaucs plot method[11] .

where A is a constant, is optical bandgap, is plank constantand is the absorption coefficient. The plot of versus for AZB nanostructure films at different concentration is shown in Fig. 4(a).A plot of versus often 2 yields a reasonably goodstraight line fit to the absorption edge of the glass and theextrapolation at which = 0, provides a convenient experimentalbenchmark for optical bandgap.Figure 3 shows the UV-visible absorption spectra of AZB nanostructure with concentration: 0.0 to 8 at.%.For the direct-band-gap semiconductorof ZnO, the band gap energy can be expressed by thefollowing equation [3]: where is the absorption coefficient, his the photonenergy, is the edge-width parameter and is the band-gap energy for direct transitions as indicated inFigure 4.[12].

Fig. 4. (a) Taucs plots of AZB nanostructure films at different Al and B with fixed concentration. (b) Absorptance spectra of AZB nanostructure filmsat different Al and B with fixed concentration. (c) Effect of Al and B concentration on the bandgap of AZB nanostructure films.

3.3. Surface morphology:The surface morphology of the AZB nanostructures is observed using scanning electron microscope (SEM).The change in the morphology of AZB nanostructure films is due to the difference in ionic radiusbetween B3+ (0.041 nm) and Al3+ (0.054 nm) with Zn2+ (0.074 nm)[13].The surface morphology usingscanning electron

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International Journal of Application or Innovation in Engineering & Management (IJAIEM)

Web Site: www.ijaiem.org Email: editor@ijaiem.org, editorijaiem@gmail.com Volume 2, Issue 9, September 2013 ISSN 2319 - 4847
microscope (SEM) of the AZB nanostructures is observed to be drastically influenced with variation in Al and B doping concentration as shown in figure(4).

0.0

2%

4%

6%

8%

Figure.4. SEM image of AZB nanostructure with concentration: 0.0 to 8 at.%.

4. Conclusions
The crystallite size calculated by W-H and by scanning electron microscope is decrease with increase of concentration of boron and aluminum co-doped ZnO.It wasfound that the increase of concentration of Al and B due to decrease of grain size. The increase of AZB concentration caused to decrease the bandgap for AZB(2 at %) and increase the transmittance for AZB(2, 4, 6 at %) andthe absorptance was in the minimum value for AZB( 4, 6 at %) in a visible region .

References
[1] P. Mitra and S. Mondal,"Structural and Morphological Characterization of ZnOthin Films Synthesized by SILAR",Progress in Theoretical and Applied Physics, Vol. 1, 2013, 17-31(2013) [2] ErsinKayahan,"White lightluminescencefromannealedthinZnOdepositedporous silicon",Journal of Luminescence, 130 (2010) 12951299 [3] Svetlana Spitsina,"Growth, Doping, and Characterization of ZnO Nanowires: Application in a Miniaturized Gas Ionization Sensor",phd. Thesis In the Department of Electrical and Computer Engineering,Concordia University, Canada, (2013) [4] D. Gltekin, M. Alaf and H. Akbulut,"Synthesis and Characterization of ZnONanopowdersand ZnO-CNT NanocompositesPrepared by Chemical Precipitation Route",Vol. 123 (2013). [5] V. K. Dwivedi, P. Srivastava, and G. VijayaPrakash,"Photoconductivity and surface chemical analysis of ZnO thin films depositedby solution-processing techniques for nano and microstructure fabrication",Vol. 34, No. 3 Journal of Semiconductors March 2013 [6] Josef W. Spalenka, Padma Gopalan, Howard E. Katz, and Paul G. Evans,"Electron mobility enhancement in ZnO thin films via surface modification bycarboxylic acids APPLIED PHYSICS LETTERS 102, 041602 (2013). [7] T.O. Berestok, D.I. Kurbatov, N.M. Opanasyuk, A.D. Pogrebnjak1,"Structural Properties of ZnO Thin Films Obtained by Chemical Bath Deposition Technique, JOURNAL OF NANO- AND ELECTRONIC PHYSICS,Vol. 5 No 1, 01009(4pp) (2013) [8] MohitAgarwal, PankajModi, R.O. Dusane,"Study of Electrical, Optical and Structural Properties of Al- Doped ZnO Thin Filmson PEN Substrates" JOURNAL OF NANO- AND ELECTRONIC PHYSICS,Vol. 5 No 2, 02027(4pp) (2013) [9] Firoz Khan, Abdul Mobin, M. Husain," Formation of ZnO by Annealing of Thermally Evaporated Zinc in Oxygen Ambient for Solar CellApplication",ISSN- 2277-1956. [10] JasmeetKaur, Praveen Kumar, Thangaiah Stephen Sathiaraj and RengasamyThangaraj,"Structural, optical and fluorescence properties ofwet chemically synthesized ZnO:Pd2+nanocrystals", Kaur et al. International Nano Letters 2013, 3:4 [11] Vinod Kumar, R.G. Singh, Neetu Singh , AvinashiKapoor, R.M. Mehra, L.P. Purohit, "Synthesis and characterization of aluminumboron co-doped ZnO nanostructures",Materials Research Bulletin 48 (2013) 362366

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Web Site: www.ijaiem.org Email: editor@ijaiem.org, editorijaiem@gmail.com Volume 2, Issue 9, September 2013 ISSN 2319 - 4847
[12] Jun Zhang, Su-Qing Zhao, Kun Zhang, Jian-Qing Zhou and Yan-FeiCai, "A study of photoluminescence properties andperformance improvement of Cd-doped ZnOquantum dots prepared by the solgel method", Zhang et al. Nanoscale Research Letters 2012, 7:405 [13] VinodKumarb, R.G. Singh, Neetu Singh, AvinashiKapoor, R.M. Mehra, L.P. Purohit," Synthesis and characterization of aluminumboron co-doped ZnO nanostructures", Materials Research Bulletin 48 (2013) 362366

Author
Anwar H. Al-fouadi, Ph.DAl-Mustansiriyah University,College of Science, Dept. of Physics, Msc. Aston university in Birmingham U.K. 1983, Bsc. Al-Mustansiriyah University, College of Science, Dept. of Physics. Assistant proff. science Al-Mustansiriyah University in field of solid state material science. Rashid HashimJabbar, Ph.D student. Presently,M.Sc. in Physics Science degree in 2009,Al-Mustansiriyah University,College of Science, Dept. of Physics,and BSc. in Department of Physics College of sciencein 1989,from University of Baghdad, a researcher at the Applied Physics Center and member of thin films application Department, Ministry of Science and Technology, Baghdad, Iraq AbdulhusseinK.Elttayef is currently a professor of physics At the Applied physics center, Baghdad, Iraq. He received his Ph.D Degree from Heriot Watt University (U.K) in 1990. His currently research Interests include the preparation of nano films (semiconductors and polymers) by different methods for applications of gas sensors, solar cells and optical detectors. He has written 40 scientific publications in this area.

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