Skip to main content

The effects of postdeposition annealing conditions on structure and created defects in Zn0.90Co0.10O thin films deposited on Si(100) substrate

  • Musa Mutlu Can (a1), Tezer Fırat (a2), S.Ismat Shah (a3), Feray Bakan (a4) and Ahmet Oral (a4)...

We analyze the effect of postdeposition annealing conditions on both the structure and the created defects in Zn0.90Co0.10O thin films, which deposited on the Si(100) substrates by the radio frequency magnetron sputtering technique using a homemade target. The dependence of the number and distribution of defects in homogeneously substituted Co+2 for Zn+2 ions in ZnO lattice on the annealing conditions is investigated. Orientations of thin films are in the [0002] direction with a surface roughness changing from 67 ± 2 nm to 25.8 ± 0.6 nm by annealing. The Co+2 ion substitution, changing from 7.5% ± 0.3% to 8.8 ± 0.3%, leads to the formation of Zn–O–Co bonds instead of Zn–O–Zn bonds and splitting of the Co 2p energy level to Co 2p1/2 and Co 2p3/2 with an energy difference of 15.67 ± 0.06 eV. The defects in the lattice are revealed from the correlations between Zn–O–Co bonds and intensity of the Raman peak at around 691 cm−1. In addition, the asymmetry changes of O 1s peak positions in the x-ray photoelectron spectra are in agreement with the Raman results.

Corresponding author
a)Address all correspondence to this author. e-mail:
Hide All
1.Fukumura, T., Yamada, Y., Toyosaki, H., Hasegawa, T., Koinuma, H., and Kawasaki, M.: Exploration of oxide-based diluted magnetic semiconductors toward transparent spintronics. Appl. Surf. Sci. 223, 6267 (2004).
2.Fitzgerald, C.B., Venkatesan, M., Dorneles, L.S., Gunning, R., Stamenov, P., Coey, J.M.D., Stampe, P.A., Kennedy, R.J., Moreira, E.C., and Sias, U.S.: Magnetism in dilute magnetic oxide thin films based on SnO2. Phys. Rev. B 74, 115307 (2006).
3.Calderon, M.J. and Das Sarma, S.: Theory of carrier mediated ferromagnetism in dilute magnetic oxides. Ann. Phys. 322, 26182634 (2007).
4.Matsukura, F., Ohno, H., and Dietl, T.: In Handbook of Magnetic Materials, edited by Buschow, K.H.J. (Elsevier Science, Amsterdam, Netherlands, 2002).
5.Pearton, S.J., Heo, W.H., Ivill, M., Norton, D.P., and Steiner, T.: Dilute magnetic semiconducting oxides. Semicond. Sci. Technol. 19, R59R74 (2004).
6.Risbud, A.S., Spaldin, N.A., Chen, Z.Q., Stemmer, S., and Seshadri, R.: Magnetism in polycrystalline cobalt-substituted zinc oxide. Phys. Rev. B 68, 205202 (2003).
7.Peng, Y.Z., Liew, T., Song, W.D., An, C.W., Teo, K.L., and Chong, T.C.: Structural and optical properties of Co-doped ZnO thin film. J. Supercond. 18(1), 97103 (2005).
8.Park, J.H., Kim, M.G., Jang, H.M., Ryu, S., and Kim, Y.M.: Co-metal clustering as the origin of ferromagnetism in Co-doped ZnO thin films. Appl. Phys. Lett. 84(8), 13381340 (2004).
9.Norton, D.P., Overberg, M.E., Pearton, S.J., Pruessner, K., Budai, J.D., Boatner, L.A., Chisholm, M.F., Lee, J.S., Khim, Z.G., Park, Y.D., and Wilson, R.G.: Ferromagnetism in cobalt-implanted ZnO. Appl. Phys. Lett. 83(26), 54885490 (2003).
10.Sati, P., Hayn, R., Kuzian, R., Regnier, S., Schafer, S., Stepanov, A., Morhain, C., Deparis, C., Laugt, M., Goiran, M., and Golacki, Z.: Magnetic Anisotropy of Co2+ as Signature of Intrinsic Ferromagnetism in ZnO:Co. Phys. Rev. Lett. 96, 017203 (2003).
11.Naeem, M., Hasanain, S.K., Kobayashi, M., Ishida, Y., Fujimori, A., Buzby, S., and Shah, S.I.: Effect of reducing atmosphere on the magnetism of Zn1−xCoxO (0 ≤ x ≤ 0.10) nanoparticles. Nanotechnology 17, 26752680 (2006).
12.Hays, J., Reddy, K.M., Graces, N.Y., Engelhard, M.H., Shutthanandan, V., Luo, M., Xu, C., Giles, N.C., Wang, C., Thevuthasan, S., and Punnoose, A.: Effect of Co doping on the structural, optical and magnetic properties of ZnO nanoparticles. J. Phys. Condens. Matter 19, 266203 (2007).
13.Fitzgerald, C.B., Venkatesan, M., Lunney, J.G., Dorneles, L.S., and Coey, J.M.D.: Cobalt-doped ZnO–a room temperature dilute magnetic semiconductor. Appl. Surf. Sci. 247, 493496 (2005).
14.Thota, S., Dutta, T., and Kumar, J.: On the sol–gel synthesis and thermal, structural, and magnetic studies of transition metal (Ni, Co, Mn) containing ZnO powders. J. Phys. Condens. Matter 18, 24732486 (2006).
15.Mandal, S.K., Das, A.K., Nath, T.K., Karmakar, D., and Satpati, B.: Microstructural and magnetic properties of ZnO:TM (TM = Co, Mn) diluted magnetic semiconducting nanoparticles. J. Appl. Phys. 100, 104315 (2006).
16.Kittilstved, K.R., Liu, W.K., and Gamelin, D.R.: Electronic structure origins of polarity-dependent high-TC ferromagnetism in oxide-diluted magnetic semiconductors. Nat. Mater. 5, 291297 (2006).
17.Wang, Q., Sun, Q., Chen, G., Kawazoe, Y., and Jena, P.: Vacancy-induced magnetism in ZnO thin films and nanowires. Phys. Rev. B 77, 205411 (2008).
18.Khare, N., Kappers, M. J., Wei, M., Blamire, M. G., and MacManus-Driscoll, J. L.: Defect-induced ferromagnetism in Co-doped ZnO. Adv. Mater. 18(11), 14491452 (2006).
19.Song, C., Pan, S.N., Liu, X.J., Li, X.W., Zeng, F., Yan, W.S., He, B., and Pan, F.: Evidence of structural defect enhanced room-temperature ferromagnetism in Co-doped ZnO. J. Phys. Condens. Matter 19, 176229 (2007).
20.Pemmaraju, C.D., Hanafin, R., Archer, T., Braun, H.B., and Sanvito, S.: Impurity-ion pair induced high-temperature ferromagnetism in Co-doped ZnO. Phys. Rev. B 78, 054428 (2008).
21.Berciu, M. and Bhatt, R.N.: Effects of disorder on ferromagnetism in diluted magnetic semiconductors. Phys. Rev. Lett. 87, 107203 (2001).
22.Coey, J.M.D., Stamenov, P., Gunning, R.D., Venkatesan, M., and Paul, K.: Ferromagnetism in defect-ridden oxides and related materials. New J. Phys. 12, 053025 (2010).
23.Chakraborti, D., Trichy, G.R., Prater, J.T., and Narayan, J.: The effect of oxygen annealing on ZnO:Cu and ZnO:(Cu, Al) diluted magnetic semiconductors. J. Phys. D: Appl. Phys. 40, 76067613 (2007).
24.Bang, S., Lee, S., Park, J., Park, S., Ko, Y., Choi, C., Chang, H., Park, H., and Jeon, H.: The effects of post-annealing on the performance of ZnO thin film transistors. Thin Solid Films 519, 81098113 (2011).
25.Wang, T., Liu, Y., Fang, Q., Xuc, Y., Li, G., Sun, Z., Wu, M., Li, J., and He, H.: Morphology and optical properties of Co doped ZnO textured thin films. J. Alloys Compd. 509, 91169122 (2011).
26.Can, M.M., Shah, S.I., Doty, M.F., Haughn, C.R., and Fırat, T.: Electrical and optical properties of point defects in ZnO thin films. J. Phys. D: Appl. Phys. 45, 195104 (2012).
27.Al-Kuhaili, M.F., Durrani, S.M.A., Bakhtiari, I.A., and Saleem, M.: Optical constants of vacuum annealed radio frequency (RF) magnetron sputtered zinc oxide thin films. Opt. Commun. 285, 44054412 (2012).
28.Guillen, C. and Herrero, J.: Transparent films on polymers for photovoltaic applications. Vacuum 84, 924929 (2010).
29.Srivastava, A.K., Praveen, , Arora, M., Gupta, S.K., Chakraborty, B.R., Chandra, S., Toyoda, S., and Bahadur, H.: Nanostructural features and optical performance of RF magnetron sputtered ZnO thin films. J. Mater. Sci. Technol. 26(11), 986990 (2010).
30.Zhu, Y.F., Zhou, G.H., Ding, H.Y., Liu, A.H., Lin, Y.B., and Dong, Y.W.: Synthesis and characterization of highly-ordered ZnO/PbS core/shell heterostructures. Superlattices Microstruct. 50, 549556 (2011).
31.Layek, A., Manna, B., and Chowdhury, A.: Carrier recombination dynamics through defect states of ZnO nanocrystals: From nanoparticles to nanorods. Chem. Phys. Lett. 539540, 133138 (2012).
32.Ahn, M-W., Park, K-S., Heo, J-H., Park, J-G., Kim, D-W., Choi, K.J., Lee, J-H., Hong, S-H.: Gas sensing properties of defect-controlled ZnO-nanowire gas sensor. Appl. Phys. Lett. 93, 263103 (2008).
33.Jiang, H., Wang, H., and Wang, X.: Facile and mild preparation of fluorescent ZnO nanosheets and their bioimaging applications. Appl. Surf. Sci. 257, 69916995 (2011).
34.Lee, H-J., Jeong, S-Y., Cho, C.R., and Park, C.H.: Study of diluted magnetic semiconductor: Co-doped ZnO. Appl. Phys. Lett. 81, 40204022 (2002).
35.Jin, Z., Fukumura, T., Kawasaki, M., Ando, K., Saito, H., Sekiguchi, T., Yoo, Y.Z., Murakami, M., Matsumoto, Y., Hasegawa, T., and Koinuma, H.: High throughput fabrication of transition-metal-doped epitaxial ZnO thin films: A series of oxide-diluted magnetic semiconductors and their properties. Appl. Phys. Lett. 78, 38243826 (2001).
36.Zhang, Y.B., Liu, Q., Sritharan, T., Gan, C.L., and Li, S.: Pulsed laser ablation of preferentially orientated ZnO:Co diluted magnetic semiconducting thin films on Si substrates. Appl. Phys. Lett. 89, 042510 (2006).
37.Shon, Y., Kwon, Y.H., Yuldashev, S.U., Park, Y.S., Fu, D.J., Kim, D.Y., Kim, H.S., and Kang, T.W.: Diluted magnetic semiconductor of p-type GaN epilayers implanted with Mn+ ions. J. Appl. Phys. 93, 15461548 (2003).
38.Kim, K.J. and Park, Y.R.: Spectroscopic ellipsometry study of optical transitions in Zn1−xCoxO alloys. Appl. Phys. Lett. 81, 14201422 (2002).
39.Zhang, S.B., Wei, S-H., and Zunger, A.: Intrinsic n-type versus p-type doping asymmetry and the defect physics of ZnO. Phys. Rev. B 63, 075205 (2001).
40.Ravichandran, C., Srinivasan, G., Lennon, C., Sivananthan, S., and Kumar, J.: Influence of post-deposition annealing on the structural, optical and electrical properties of Li and Mg co-doped ZnO thin films deposited by sol–gel technique. Superlattices Microstruct. 49, 527536 (2011).
41.Straumal, B.B., Protasova, S.G., Mazilkin, A.A., Myatiev, A.A., Straumal, P.B., Schütz, G., Goering, E., and Baretzky, B.: Ferromagnetic properties of the Mn-doped nanograined ZnO films. J. Appl. Phys. 108, 073923 (2010).
42.Subramanian, M., Tanemura, M., Hihara, T., Ganesan, V., Soga, T., and Jimbo, T.: Magnetic anisotropy in nanocrystalline Co-doped ZnO thin films. Chem. Phys. Lett. 487, 97100 (2010).
43.Can, M.M., Fırat, T., and Özcan, Ş.: Dominancy of antiferromagnetism in Zn1–xCoxO diluted magnetic semiconductors. J. Mater. Sci. 46, 18301838 (2011).
44.Can, M.M., Fırat, T., and Özcan, Ş.: Structural, optic, and magnetic investigation of the synthesized ZnO and Zn0.99Co0.01O semiconductors via solid state reaction. IEEE Trans. Magn. 46(6), 18091812 (2010).
45.Reimer, L.: Scanning Electron Microscopy: Physics of Image Formation and Microanalysis (Springer, Berlin, Germany, 1998); pp. 208218.
46.Husna, J., Aliyu, M.M., Islam, M.A., Chelvanathan, P., Hamzah, N.R., Hossain, M.S., Karim, M.R., and Amin, N.: Influence of annealing temperature on the properties of ZnO thin films grown by sputtering. Energy Procedia 25, 5561 (2012).
47.Hsieh, P.T., Chen, Y.C., Lee, M.S., Kao, K.S., Kao, M.C., and Houng, M.P.: The effects of oxygen concentration on ultraviolet luminescence of ZnO films by sol-gel technology and annealing. J. Sol-Gel Sci. Technol. 47, 16 (2008).
48.Khairnar, A.G. and Mahajan, A.M.: Effect of post-deposition annealing temperature on RF-sputtered HfO2 thin film for advanced CMOS technology. Solid State Sci. 15, 24–28 (2013).
49.Sahu, D.R. and Huang, J-L.: The properties of ZnO/Cu/ZnO multilayer films before and after annealing in the different atmosphere. Thin Solid Films 516, 208211 (2007).
50.Wagner, C.D., Riggs, W.M., Davis, L.E., and Moulder, J.F.: Handbook of X-ray Photoelectron Spectroscopy, G.E. Muilenberg, ed. (Perkin-Elmer, Minnesota, 1979); pp. 82–83, 88–89, 172–173.
51.Lai, L-W. and Lee, C-T.: Investigation of optical and electrical properties of ZnO thin films. Mater. Chem. Phys. 110, 393396 (2008).
52.Hsieh, P-T., Chen, Y-C., Kao, K-S., and Wang, C-M.: Luminescence mechanism of ZnO thin film investigated by XPS measurement. Appl. Phys. A 90, 317321 (2008).
53.Sun, S-Y., Huang, J-L., and Lii, D-F.: Effects of oxygen contents on the electrical and optical properties of indium molybdenum oxide films fabricated by high density plasma evaporation. J Vac: Sci. Technol. 22, 1235 (2004).
54.Fernandes, A.J., Chen, P.P-T., Wintrebert-Fouquet, M., Timmers, H., Shrestha, S.K., Hirshy, H., and Perks, R.M., and Usher, B.F.: The nature of nitrogen related point defects in common forms of InN. J. Appl. Phys. 101, 123702 (2007).
55.Lennon, C., Tapia, R.B., Kodama, R., Chang, Y., Sivananthan, S., and Deshpande, M.: Effects of annealing in a partially reducing atmosphere on sputtered Al-doped ZnO thin films. J. Electron. Mater. 38(8), 15681573 (2009).
56.Xu, X.L., Lau, S.P., Chen, J.S., Chen, G.Y., and Tay, B.K.: Polycrystalline ZnO thin films on Si (100) deposited by filtered cathodic vacuum arc. J. Cryst. Growth 223, 201205 (2001).
57.Zeng, J.N., Low, J.K., Ren, Z.M., Liew, T., and Lu, Y.F.: Effect of deposition conditions on optical and electrical properties of ZnO films prepared by pulsed laser deposition. Appl. Surf. Sci. 197198, 362367 (2002).
58.Sudakar, C., Kharel, P., Lawes, G., Suryanarayanan, R., Naik, R., and Naik, V.M.: Raman spectroscopic studies of oxygen defects in Co-doped ZnO films exhibiting room-temperature ferromagnetism. J. Phys. Condens. Mater. 19 026212 (2007).
Recommend this journal

Email your librarian or administrator to recommend adding this journal to your organisation's collection.

Journal of Materials Research
  • ISSN: 0884-2914
  • EISSN: 2044-5326
  • URL: /core/journals/journal-of-materials-research
Please enter your name
Please enter a valid email address
Who would you like to send this to? *



Full text views

Total number of HTML views: 0
Total number of PDF views: 0 *
Loading metrics...

Abstract views

Total abstract views: 0 *
Loading metrics...

* Views captured on Cambridge Core between <date>. This data will be updated every 24 hours.

Usage data cannot currently be displayed