Skip to main content Accessibility help

Defects in three-dimensional spherical assemblies of Ni-doped ZnO nanocrystals

  • K.C. Barick (a1), M. Aslam (a2), Jinsong Wu, Vinayak P. Dravid (a3) and D. Bahadur (a1)...


Three-dimensional spherical assemblies of Ni-doped ZnO nanocrystals have been prepared by the solution phase synthesis process. It has been observed that transition metal ions (Zn, Ni) are uniformly distributed in the sample and exist in the +2 oxidation state. Detailed investigation of structural defects formed during the formation of spherical assemblies by oriented attachment of nanocrystals was carried out by high-resolution transmission electron microscope (HRTEM), Raman and photoluminescence (PL) spectroscopy. HRTEM analysis revealed the existence of various crystal defects, such as stacking faults, dislocations, etc. The incorporation of Ni2+ into ZnO structure strongly influences the vibrational and optical properties of the sample due to the increment of defect densities. Compared to the optical phonons of ZnO, additional mode observed at 538 cm−1 in Raman spectra of Ni-doped ZnO could be associated with the incorporation of Ni2+ in Zn2+ site. The increase in PL intensity of green emission with Ni2+ doping indicates the formation of a higher concentration of oxygen vacancy in doped nanostructures.


Corresponding author

Address all correspondence to these authors.


Hide All
1.Wu, L.Y.L., Tok, A.I.Y., Boey, F.Y.C., Zeng, X.T., and Zhang, X.H.: Chemical synthesis of ZnO nanocrystals. IEEE Trans. Nanotechnol. 6, 497 (2007).
2.Shen, L., Bao, N., Yanagisawa, K., Domen, K., Gupta, A., and Grimes, C. A.: Direct synthesis of ZnO nanoparticles by a solution-free mechanochemical reaction. Nanotechnol. 17, 5117 (2006).
3.Srikant, V. and Clarke, D.R.: On the optical band gap of zinc oxide. J. Appl. Phys. 83, 5447 (1998).
4.Bauer, C., Boschloo, G., Mukhtar, E., and Hagfeldt, A.: Electron injection and recombination in Ru(dcbpy)2(NCS)2 sensitized nanostructured ZnO. J. Phys. Chem. B 105, 5585 (2001).
5.Ohno, H.: Making nonmagnetic semiconductors ferromagnetic. Science 281, 951 (1998).
6.Sharma, P., Gupta, A., Rao, K.V., Owens, F.J., Sharma, R., Ahuja, R., Guillen, J.M.O., Johansson, B., and Gehring, G.A.: Fer-romagnetism above room temperature in bulk and transparent thin films of Mn-doped ZnO. Nat. Mater. 2, 673 (2003).
7.Wu, D., Yang, M., Huang, Z., Yin, G., Liao, X., Kang, Y., Chen, X., and Wang, H.: Preparation and properties of Ni-doped ZnO rod arrays from aqueous solution. J. Colloid Interface Sci. 330, 380 (2009).
8.Kaschner, A., Haboeck, U., Strassburg, M., Kaczmarczyk, G., Hoffmann, A., Thomsen, C., Zeuner, A., Alves, H.R., Hofmann, D.M., and Meyer, B.K.: Nitrogen-related local vibrational modes in ZnO. N. Appl. Phys. Lett. 80, 1909 (2002).
9.Viswanatha, R., Sapra, S., Gupta, S.S., Satpati, B., Satyam, P.V., Dev, B.N., and Sarma, D.D.: Synthesis and characterization of Mn-doped ZnO nanocrystals. J. Phys. Chem. B 108, 6303 (2004).
10.Biegger, E., Fonin, M., Rüdiger, U., Janβen, N., Beyer, M., Thomay, T., Bratschitsch, R., and Dedkov, Y.S.: Defect induced low temperature ferromagnetism in Zn1−xCoxO films. J. Appl. Phys. 101, 073904 (2007).
11.Hong, N.H., Sakai, J., Huong, N.T., Poirot, N., and Ruyter, A.: Role of defects in tuning ferromagnetism in diluted magnetic oxide thin films. Phys. Rev. B 72, 045336 (2005).
12.Kittilstved, K.R., Schwartz, D.A., Tuan, A.C., Heald, S.M., Chambers, S.A., and Gamelin, D.R.: Direct kinetic correlation of carriers and ferromagnetism in Co2+: ZnO. Phys. Rev. Lett. 97, 037203 (2006).
13.Liu, H., Zhang, X., Li, L., Wang, Y.X., Gao, K.H., Li, Z.Q., Zheng, R.K., Ringer, S.P., Zhang, B., and Zhang, X.X.: Role of point defects in room-temperature ferromagnetism of Cr-doped ZnO. Appl. Phys. Lett. 91, 072511 (2007).
14.Xing, G.Z., Yi, J.B., Tao, J.G., Liu, T., Wong, L.M., Zhang, Z., Li, G.P., Wang, S.J., Ding, J., Sum, T.C., Huan, C.H.A., and Wu, T.: Comparative study of structural inhomogeneity enhanced room-temperature ferromagnetism in Cu-doped ZnO nanowires. Adv. Mater. 20, 3521 (2008).
15.Venkatesan, M., Fitzgerald, C.B., Lunney, J.G., and Coey, J.M.D.: Anisotropic ferromagnetism in substituted zinc oxide. Phys. Rev. Lett. 93, 177206 (2004).
16.Coey, J.M.D., Venkatesan, M., and Fitzgerald, C.B.: Donor impurity band exchange in dilute ferromagnetic oxides. Nat. Mater. 4, 173 (2005).
17.Sundaresan, A., Bhargavi, R., Rangarajan, N., Siddesh, U., and Rao, C.N.R.: Ferromagnetism as a universal feature of nanoparticles of the otherwise nonmagnetic oxides. Phys. Rev. B 74, 161306 (2006).
18.Penn, R.L. and Banfield, J.F.: Imperfect oriented attachment: Dislocation generation in defect-free nanocrystals. Science 281, 969 (1998).
19.Banfield, J.F., Welch, S.A., Zhang, H., Ebert, T.T., and Penn, R.L.: The role of aggregation in crystal growth and transformations in nano-phase FeOOH biomineralization products. Science 289, 751 (2000).
20.Barick, K.C., Aslam, M., Dravid, V.P., and Bahadur, D.: Self-aggregation and assembly of size-tunable transition metal doped ZnO nanocrystals. J. Phys. Chem. C 112, 15163 (2008).
21.Barick, K.C. and Bahadur, D.: Synthesis, self-assembly and properties of Mn-doped ZnO nanoparticles. J. Nanosci. Nanotechnol. 7, 1935 (2007).
22.Yin, Z.G., Chen, N., Yang, F., Chai, S.L., Zhong, J., Qian, H.J., and Ibrahim, K.: Structural, magnetic properties and photoemission study of Ni-doped ZnO. Solid State Commun. 135, 430 (2005).
23. CWagner, D., Riggs, W.M., Davis, L.E., and Moulder, J.F.: Handbook of X-ray Photoelectron Spectroscopy (Perkin Elmer, Eden Prairie, MN, 1979), p. 81.
24.Yan, Y., Dalpian, G.M., Al-Jassim, M.M., and Wei, S.: Energetics and electronic structure of stacking faults in ZnO. Phys. Rev. B 70, 193206 (2004).
25.Yang, L.W., Wu, X.L., Huang, G.S., Qiu, T., and Yang, Y.M.: In situ synthesis of Mn-doped ZnO multileg nanostructures and Mn-related Raman vibration. J. Appl. Phys. 97, 014308 (2005).
26.Wang, X., Xu, J., Zhang, B., Yu, H., Wang, J., Zhang, X., Yu, J., and Li, Q.: Signature of intrinsic high-temperature ferromagnetism in cobalt-doped zinc oxide nanocrystals. Adv. Mater. 18, 2476 (2006).
27.Phan, T.L., Vincent, R., Cherns, D., Nghia, N.X., and Ursaki, V.V.: Raman scattering in Me-doped ZnO nanorods (Me = Mn, Co, Cu, and Ni) prepared by thermal diffusion. Nanotechnol. 19, 475702 (2008).
28.Barick, K.C. and Bahadur, D.: Influence of Mn doping on structural and vibrational properties of self-assembled Mn-doped ZnO nanocrystals. J. Nanosci. Nanotechnol. 8, 4263 (2008).
29.Bundesmann, C., Ashkenov, N., Schubert, M., Spemann, D., Butz, T., Kaidashev, E.M., Lorenz, M., and Grundmann, M.: Raman scattering in ZnO thin films doped with Fe, Sb, Al, Ga, and Li. Appl. Phys. Lett. 83, 1974 (2003).
30.Sato-Berrú, R.Y., Vázquez-Olmos, A., Fernández-Osorio, A.L., and Sotres-martínez, S.: Micro-Raman investigation of transition-metal-doped ZnO nanoparticles. J. Raman Spectrosc. 38, 1073 (2007).
31.Wu, J.J., Wen, H.I., Tseng, C.H., and Liu, S.C.: Well-aligned ZnO nanorods via hydrogen treatment of ZnO films. Adv. Funct. Mater. 14, 806 (2004).
32.Kong, Y.C., Yu, D.P., Zhang, B., Fang, W., and Feng, S.Q.: Ultraviolet-emitting ZnO nanowires synthesized by a physical vapor deposition approach. Appl. Phys. Lett. 78, 407 (2001).
33.Norberg, N.S., Kittilstved, K.R., Amonette, J.E., Kukkadapu, R.K., Schwartz, D.A., and Gamelin, D.R.: Synthesis of colloidal Mn2+: ZnO quantum dots and high-T C ferromagnetic nanocrystalline thin films. J. Am. Chem. Soc. 126, 9387 (2004).
34.Parra-Palomino, A., Perales-Perez, O., Singhal, R., Tomar, M., Hwang, J., and Voyles, P. M.: Structural, optical, and magnetic characterization of monodisperse Fe-doped ZnO nanocrystals. J. Appl. Phys. 103, 07D121 (2008).


Related content

Powered by UNSILO

Defects in three-dimensional spherical assemblies of Ni-doped ZnO nanocrystals

  • K.C. Barick (a1), M. Aslam (a2), Jinsong Wu, Vinayak P. Dravid (a3) and D. Bahadur (a1)...


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.