Controlling structural and electronic properties of ZnO NPs: Density-functional tight-binding method

Öz

We carried out a thorough examination of the structural and electronic features of undoped and Nitrogen (N)-doped ZnO nanoparticles (NPs) by the density-functional tight-binding (DFTB) method. By increasing the percent of N atoms in undoped ZnO NPs, the number of bonds (n), order parameter (R) and radial distribution function (RDF) of two-body interactions such as Zn-Zn, N-N, O-O, N-O, etc. were investigated using novel algorithms. Our results show that the total n of Zn-Zn interactions is greater than that of Zn-Zn, N-N, N-O, and O-O; thus, it means that Zn atoms have a greater preference for N or O atoms. The RDFs of Zn and O atoms increase based on the increase in the content of N atoms. The R of Zn, O and N atoms demonstrate that O and N atoms tend to locate at the center, whereas Zn atoms tend to reside on the surface. The density of state (DOS) indicates that the undoped and N-doped ZnO NPs demonstrate a semiconductor-like behavior that is coherent with measured data. The HOMO-LUMO energy gap decreases from -4.717 to -0.853 eV. n increase in the content of N atoms contributes to the destabilization of ZnO NPs due to a decrease in the energy gap.

Anahtar Kelimeler

• Nanoparticle,N-doped ZnO,Electronic Structure,Data Science

Kaynakça

1. Aradi, B., Hourahine, B., Frauenheim, T. (2007). DFTB+, a Sparse Matrix-Based Implementation of the DFTB Method. J. Phys. Chem. A 111, 5678-5684.
2. Barzinjy, A. A., Mustafa, S., Ismael, H. H. J. (2019). Characterization of ZnO NPs Prepared from Green Synthesis Using Euphorbia Petiolata Leaves. EAJSE 4, 74-83.
3. Chang S-P., Chen, K-J. (2012). Zinc Oxide NP Photodetector. J. Nanomater. 2012, 1-5.
4. Czajkowski, M. A., Koperski, J. (1999). The Cd2 and Zn2 van der Waals dimers revisited. Correction for some molecular potential parameters. Spectrochim. Acta, Part A 55, 2221-2229.
5. Gaus, M., Goez, A., & Elstneri, M. (2013). Parametrization and Benchmark of DFTB3 for Organic Molecules. J. Chem. Theory Comput. 9, 338-354.
6. Kubillus, M., Kubař, T., Gaus, M., Řezáč, J., & Elstner, M. (2015). Parameterization of the DFTB3 Method for Br, Ca, Cl, F, I, K, and Na in Organic and Biological Systems. J. Chem. Theory Comput. 11, 332–342.
7. Kurban, M. (2018). Size and composition dependent structure of ternary Cd-Te-Se nanoparticles. Turk. J. Phys. 42, 443-454.
8. Kurban, M. Malcıoğlu, O. B. Erkoç Ş. (2016). Structural and thermal properties of Cd-Zn-Te ternary NPs: Molecular-dynamics simulations. Chem. Phys. 464, 40-45.

9. Kushwaha, A. K. (2012). Lattice dynamical calculations for HgTe, CdTe and their ternary alloy CdxHg1−xTe. Comp. Mater Sci. 65, 315-319.
10. NIST Standard Reference Database (2019). Experimental bond lengths. https://cccbdb.nist.gov/expbondlengths1.asp. (Access Date: 10.05.2019).
11. Wang, CL., Zhang, H., Zhang, JH., Li, MJ., Sun, HZ., Yang, B. (2007). Application of Ultrasonic Irradiation in Aqueous Synthesis of Highly Fluorescent CdTe/CdSCore-Shell Nanocrystals. J. Phys. Chem. C111, 2465-2469.
12. Wu, X., Wei, Z., Liu, Q., Pang, T., Wu, G. (2016). Structure and bonding in quaternary Ag-Au-Pd-Pt clusters. J Alloy. Compd. 687, 115-120.
13. Yang, P., Tretiak, S., Masunov, A. E., Ivanov, S. (2008). Quantum chemistry of the minimal CdSe clusters. J. Chem. Phys. 129, 074709-1—074709-12.
14. Zhang, Y., Nayak, TR., Hong, H., Cai, W. (2013). Biomedical applications of zinc oxide nanomaterials. Curr. Mol. Med. 13(10), 1633-1645.