Abstract
The effect of Cr dopant on the structural, optical, magnetic properties and local electronic structure of aqueous synthesis derived Zn1−xCrxS diluted magnetic semiconductor nano crystals have systematically investigated. The nano crystalline structure and crystallite size have been estimated by X-ray diffraction measurements with Rietveld refinement and high-resolution transmission electron microscopy. Effective increase of the lattice parameter has been observed in doped samples. Raman spectroscopy has been employed to study the crystalline quality, structural disorder and defects in the host lattice. The tetrahedral coordination of the sulfur ions surrounding the zinc ions has been studied by FTIR analysis. The decrease of energy band gap for Cr doped samples has observed. Blue emission has been observed by photo luminescence spectroscopy due to defect formation (Cri) in Cr-doped samples. The local electronic structures of Zn and Cr sites are thoroughly studied by synchrotron based X-ray absorption spectroscopy comprising of both X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS). EXAFS studies indicate the presence of secondary phase within the sphalerite lattice of diluted Zn1−xCrxS nanocrystals while XANES studies exhibit single pre-edge feature. The amplitude of such pre edge is found to be independent of Cr amount on doped ZnS nanocrystals. The results demonstrated that diluted Cr3+ ions are substituted on the host ZnS nanocrystal. The Cr doped ZnS sample shows paramagnetism at room (300 K) and at low (5 K) temperature. The Cr–S bonds are the crucial premise for paramagnetic ordering.
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J. Hu, T.W. Odom, C.M. Lieber, Chemistry and physics in one dimension: synthesis and properties of nanowires and nanotubes. Acc. Chem. Res. 32, 435–445 (1999)
O. Sahin, S. Horoz, Synthesis of Ni:ZnS quantum dots and investigation of their properties. J. Mater. Sci. 29, 16775–16781 (2018)
Y. Gao, A. Tonizzo, A. Walser, M. Potasek, R. Dorsinville, Enhanced optical nonlinearity of surfactant-capped CdS quantum dots embedded in an optically transparent polystyrene thin film. Appl. Phys. Lett. 92, 033106 (2008)
R.A. Ganeev, M. Baba, M. Morita, D. Rau, H. Fujii, A.I. Ryasnyansky, N. Ishizawa, M. Suzuki, H. Kuroda, Nonlinear optical properties of CdS and ZnS nanoparticles doped into zirconium oxide films. J. Opt. A 6, 447–453 (2004)
A.L. Rogach, Semiconductor Nanocrystal Quantum Dots Synthesis, Assembly, Spectroscopy and Applications (Springer, Wien, 2008)
K. Ichino, Y. Morimoto, H. Kobayashi, Molecular beam epitaxy and structural properties of ZnCrS. Phys. Status Solidi C 3, 776–779 (2006)
D.V. Martyshkin, V.V. Fedorov, C. Kim, I.S. Moskalev, S.B. Mirov, Mid-IR random lasing of Cr-doped ZnS nanocrystals. J. Opt. 12, 024005 (2010)
P. Kaur, S. Kumar, A. Sing, C.L. Chen, C.L. Dong, T.S. Chan, K.P. Lee, C. Srivastava, S.M. Rao, M.K. Wu, Investigations on doping induced changes in structural, electronic structure and magnetic behavior of spintronic Cr-ZnS nanoparticles. Superlattices Microst. 83, 785–795 (2015)
P. Kaur, S. Kumar, A. Singh, S.M. Rao, Improved magnetism in Cr doped ZnS nanoparticles with nitrogen co-doping synthesized using chemical co-precipitation technique. J. Mater. Sci. 26, 9158–9163 (2015)
X. Zeng, J. Zhang, F. Huang, Optical and magnetic properties of Cr-doped ZnS nanocrystallites. J. Appl. Phys. 111, 123525 (2012)
D.A. Reddy, A. Divya, G. Murali, R.P. Vijayalakshmin, B.K. Reddy, Synthesis and optical properties of Cr doped ZnS nanoparticles capped by 2-mercaptoethanol. Physica B 406, 1944–1949 (2011)
Z. Zhang, J. Li, J. Jian, R. Wu, Y. Sun, S. Wang, Y. Ren, J. Li, Preparation of Cr- doped ZnS nanosheets with room temperature ferromagnetism via a solvothermal route. J. Cryst. Growth 372, 39–42 (2013)
S. Chawla, S. Sharma, J. Shah, Fabrication of ZnS:Cr nanoparticles with super paramagnetism and fluorescence properties. Mater. Lett. 108, 189–192 (2013)
B. Car, S. Medling, C. Corrado, F. Bridges, J.Z. Zhang, Probing the local structure of dilute Cu dopants in fluorescent ZnS nanocrystals using EXAFS. Nanoscale 3, 4182–4189 (2011)
M. Ahtee, L. Unonius, M. Nurmela, P.A. Suortti, A Voigtian as profile shape function in Rietveld refinement. Appl. Cryst. 17, 352–357 (1984)
J.I. Langford, A rapid method for analyzing the breadths of diffraction and spectral lines using the Voigt function. J. Appl. Cryst. 11, 10–14 (1978)
R.W.G. Wyckoff, Crystal Structures (Interscience, New York, 1964), p. 4
https://imagej.net/. Accessed 17 Nov 2017
M.A. Garcia, F.E. Pinel, J.D.L. Venta, A. Quesada, V. Bouzas, J.F. Fernández, J.J. Romero, M.M.S. González, J.L. Costa-Krämer, Sources of experimental errors in the observation of nanoscale magnetism. J. Appl. Phys. 105, 013925 (2009)
https://icsd.fiz-karlsruhe.de. Accessed 31 May 2017
O.C. Samy, P. Olivier, A. Pavel, K. Lhoussain, H.N. Mohamed, A.H. Dalaver, H. Moussab, G. Christophe, B.J. Marie, P. Eric, Photocatalysis with chromium-doped TiO2: bulk and surface doping. ChemSusChem. 7, 1361–1371 (2014)
F.M.F. De Groot, Novel techniques and approaches to unravel the nature of X-ray absorption spectra. AIP Conf. Proc. 37, 882 (2007)
H. Chen, D. Shi, J. Qi, B. Wang, Structure, electronic and magnetic properties of Cr- doped (ZnS) 12 clusters: a first-principles study. Phys. Lett. A 374, 4133–4139 (2010)
H.V. Philipsborn, Crystal growth and characterization of chromium sulfo and seleno spinels. J. Cryst. Growth 9, 296–304 (1971)
http://abulafia.mt.ic.ac.uk/shannon/radius.php. Accessed 31 May 2017
A.L. Patterson, The diffraction of X-rays by small crystalline particles. Phys. Rev. 56, 972–977 (1939)
C. Yang, G. An, X. Zhao, ZnS porous fluorescent nanostructures synthesized by a soft template approach. J. Mater. Sci. 26(5), 3324–3329 (2015)
M. Birkholz, Thin Film Analysis by X-ray Scattering (Wiley, Weinheim, 2006)
G.K. Williamson, W.H. Hall, X-ray line broadening from filed aluminium and wolfram. Acta Metall. 1, 22–31 (1953)
B.A. Weinstein, Phonon dispersion of zinc chalcogenides under extreme pressure and the metallic transformation. Solid State Commun. 24(9), 595–598 (1977)
J. Schneider, R.D. Kirby, Raman scattering from ZnS poly types. Phys. Rev. B 6, 1290 (1972)
G. Murugados, M.R. Kumar, Synthesis, optical properties of monodispersed Ni2+ doped ZnS nanoparticles. Appl. Nanosci 4, 67–75 (2014)
B. Liang, L. Andrews, Infrared spectra and density functional theory calculations of group 6 transition metal sulfides in solid argon. J. Phys. Chem. A 106, 6945–6951 (2002)
Y. Guo, X. Cao, X. Lan, C. Zhao, X. Xue, Y. Song, Solution-based doping of manganese into colloidal ZnO nanorods. J. Phys. Chem. C 112, 8832–8838 (2008)
S.J. Gilliland, J.A. Sans, J.F. Sanchez-Royo, G. Almonacid, B. Garcia-Domene, A. Segura, G. Tobias, E. Canadell, Role of p-d and s-d interactions in the electronic structure and band gap of Zn1−xMxO (M = Cr, Mn, Fe Co, Ni, and Cu): photoelectron and optical spectroscopy and first-principles band structure calculations. Phys. Rev. B. 86, 155203 (2012)
S.H. Wei, A. Zunger, Role of metal d states in II-VI semiconductors. Phys. Rev. B 37(15), 8958 (1988)
Z. Deng, L. Tong, M. Flores, S. Lin, J.X. Cheng, H. Yan, Y. Liu, High quality manganese doped zinc sulfide quantum rods with tunable dual color and multiphoton emissions. J. Am. Chem. Soc. 133(14), 5389–5396 (2011)
D. Denzler, M. Olschewski, K. Sattler, Luminescence studies of localized gap states in colloidal ZnS nano crystals. J. Appl. Phys. 84(5), 2841–2845 (1998)
A.A. Bol, A. Meijerink, Long-lived Mn2+ emission in nanocrystalline ZnS:Mn2+. Phys. Rev. B 58(24), R15997 (1998)
Acknowledgements
S.Ghorai acknowledges to Council of Scientific and Industrial Research (CSIR), Govt. of India for Junior Research Fellowship & Senior Research Fellowship. AKG is thankful to DST-FIST program; to DST-PURSE program; to UGC-UPE program; to UGC-CAS program. AKG is also thankful to DST, India; DAE-BRNS; CSIR and UGC Govt. of India for financial support (Grant No.: SR/S2/CMP-0038/2008; 2011/37P/11/BRNS/1038-103(1302)/13/EMR-II, and Grant no. F.No.42-787/2013 (SR), respectively). We acknowledge to Dr. A. Banerjee for magnetic measurements and Dr. V. Sathe for Raman measurements UGC-DAE, Indore; to “Central Instrument Facility Centre” (CFIC), IITBHU for providing XRD, HRTEM measurements.
Funding
This investigation was funded by DST, DAE-BRNS and UGC, India (Grant No.: SR/S2/CMP-0038/2008, Grant no. 2011/37P/11/BRNS/1038-1 and Grant No. F. No. 42-787/2013 (SR), respectively).
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Ghorai, S., Patra, N., Bhattacharyya, D. et al. Influence of chromium concentration on the structural, electronic structure, optical and temperature dependent magnetic properties of ZnS nanocrystals. J Mater Sci: Mater Electron 30, 11652–11664 (2019). https://doi.org/10.1007/s10854-019-01524-5
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DOI: https://doi.org/10.1007/s10854-019-01524-5