Abstract
As no complete and comprehensive studies have been previously reported for La-doped nanocrystalline SrZrO3 (SZO), we researched herein a detailed investigation for pure and La-doped samples. A modified solid-state reaction process, including successive cycles of milling and sintering at high temperature, was followed to produce SZO and Sr0.9La0.1ZrO3 (SLZO) powdered ingots. Rietveld analysis of X-ray diffractometer data predicts that the two samples exhibit orthorhombic structure with an increase in crystallite size by ~25% for doped sample. A great reduction in Raman modes intensity (~60%) and an annihilation of several vibration modes were detected using Raman spectroscopy. The degree of ordering on the B-site was recorded to be higher in La-doped sample. According to ultraviolet–visible (UV–Vis) absorption, a decrease in the optical gap width (E g) from 4.40 eV to 4.21 eV was achieved by La incorporation due to the presence of additional defect states such as oxygen and Sr vacancies at the band edge. The process of electron–hole recombination was studied using photoluminescence (PL) spectroscopy. Deconvolution of PL spectra yielded four emission bands: one green band, one blue band, and two violet bands. Highly intense violet emission at λ = 393 nm approximately five times greater than that detected for pure SZO is realized as La3+ substitutes for Sr2+. Such property nominates SLZO for technological applications requiring highly intense violet emission, e.g., light-emitting diodes.
Similar content being viewed by others
References
Ahtee A, Ahtee M, Glazer AM, Hewat AW. The structure of orthorhombic SrZrO3 by neutron powder diffraction. Acta Crystallogr B. 1976;32:3243.
Ali Z, Atta A, Abbas Y, Sedeek K, Adam A, Abdeltawab E. Multiferroic BiFeO3 thin films: structural and magnetic characterization. Thin Solid Films. 2015;577:124.
Fabbri E, Pergolesi D, Traversa E. Materials challenges toward proton-conducting oxide fuel cells: a critical review. Chem Soc Rev. 2010;39(11):4355.
Malavasi L, Fisher CAJ, Islam MS. Oxide-ion and proton conducting electrolyte materials for clean energy applications: structural and mechanistic features. Chem Soc Rev. 2010;39(11):4370.
Duan Y, Ohodnicki P, Chorpening B, Hackett G. Electronic structural, optical and phonon lattice dynamical properties of pure- and La-doped SrTiO3: an ab initio thermodynamics study. Solid State Chem. 2017;256:239.
Duan Y, Ohodnicki P, Chorpening B, Abernathy HW, Hakett G. Theoretical investigation of the electronic, structural, optical and thermodynamic properties of LaxSr1–xTiO3 (x = 0, 0.125, 0.25). ECS Trans. 2017;78(1):2865.
Schultz AM, Brown TD, Buric MP, Lee SW, Gerdes K, Ohodnicki PR. High temperature fiber-optic evanescent wave hydrogen sensors using La-doped SrTiO3 for SOFC applications. Sens Acuators B Chem. 2015;221:1307.
Schultz AM, Brown TD, Ohodnicki PR. Optical and cheme-resistive sensing in extreme environments: La-doped SrTiO3 films for hydrogen sensing at high temperatures. J Phys Chem C. 2015;119(11):6211.
Wei W, Dai Y, Guo M, Yu L, Huang B. Density functional characterization of the electronic structure and optical properties of N-doped, La-doped, and N/La-codoped SrTiO3. J Phys Chem C. 2009;113(33):15046.
Zhou X, Yan N, Chuang KT, Lou J. Progress in La-doped SrTiO3 (LST)-based anode materials for solid oxide fuel cells. RSC Adv. 2014;4(1):118.
Choi M, Posadas AB, Rodriguez CA, O’Hara A, Seinige H, Kellock AJ, Frank MM, Tsoi M, Zollner S, Narayanan V, Demkov AA. Structural, optical and electrical properties of strained La-doped SrTiO3 films. J Appl Phys. 2014;116:043705.
Suriyayothin N, Error NG. Effect of La additions on the electrical conductivity of SrZrO3. In: The 86th annual meeting of the American Ceramic Society, Pittsburgh (Pennsylvania). 1984. 1.
Suriyayothin N, Padmanabhan R. Transmission electron microscopy investigations of second phases in the system (La, Sr)ZrO3. Mater Sci Eng. 1987;95:295.
Sedeek K, Said ShA, Hantour H, Makram N, Amer TZ. Innovative synthesis and properties of Fe doped nanocrystalline strontium zirconate for the development of visible light driven photocatalyst. Results Phys. 2019;12:1038.
Sedeek K, Said SA, Amer TZ, Makram N, Hantour H. Band gap tuning in nanocrystalline SrTi0.9Fe0.1O2.968 perovskite type for photocatalytic and photovoltaic applications. Ceram Int. 2019;45(1):1202.
Ahmad T, Ganguli AK. Synthesis, characterization and dielectric properties of nanocrystalline strontium zirconate prepared through a modified reverse miceller route. Mater Lett. 2006;60(29–30):3660.
Verma AS, Kumar A, Bhardwaj SR. Correlation between ionic charge and the lattice constant of cubic perovskite solids. Phys Status Solidi (B). 2008;245(8):1520.
Shannon RD, Prewitt CT. Effective ionic radii in oxides and fluorides. Acta Cryst. 1969;B25:925.
Howard CJ, Knight KS, Kennedy BJ, Kisi EH. The structural phase transitions in strontium zirconate. J Phys Condens Matter. 2000;12(45):L677.
Suriyayothin N, Eror NG. Solubility limit of La in SrZrO3. J Mater Sci. 1984;19(9):2775.
Cavalcante LS, Simões AZ, Sczancoski JC, Longo VM, Erlo R, Escote MT, Longo E, Varela JA. SrZrO3 powders obtained by chemical method: synthesis, characterization and optical absorption behaviour. Solid State Sci. 2007;9(11):1020.
Amisi S, Bousquet E, Katcho K, Ghosez P. First-principles study of structural and vibrational properties of SrZrO3. Phys Rev B. 2012;85:064112.
Kamishima O, Hattori T, Ohta K, Chiba Y, Ishigame M. Raman scattering of single-crystal SrZrO3. J Phys Condens Matter. 1999;11(27):5355.
Kumar A, Kumari S, Borkar H, Katiyar RS, Scott JF. Experimental verification of the ab initio phase transition sequence in SrZrO3 and comparisons with SrHfO3 and SrSnO3. NPJ Comput Mater. 2017;3(2):1.
Tarrida M, Larguem H, Madon M. Structural investigations of (Ca, Sr)ZrO3 and Ca(Sn, Zr)O3 perovskite compounds. Phys Chem Miner. 2009;36(7):403.
Dopal PS, Dixit A, Katiyar RS. Effect of lanthanum substitution on the Raman spectra of barium titanate thin films. J Raman Spectrosc. 2007;38(2):142.
Zheng H, de Gyorgyfalva GDCC, Quimby R, Bagshaw H, Ubic R, Reaney IM, Yarwood J. Raman spectroscopy of B-site order–disorder CaTiO3-based microwave ceramics. J Eur Ceram Soc. 2003;23(14):2653.
Rashad MM, Mostafa AG, Rayan DA. Structural and optical properties of nanocrystalline mayenite Ca12Al14O33 powders synthesized using a novel route. J Mater Sci Mater Electron. 2016;27(3):2614.
Kubelka P, Munk F. The Kubelka–Munk theory of reflectance. Ein Beitrag zur Optik der Farbanstriche Z Technol Phys. 1931;12:593.
Barrón V, Torrent J. Use of the Kubelka—Munk theory to study the influence of iron oxides on soil colour. J Soil Sci. 1986;37(4):499.
Yun JN, Zhang ZY, Yan JF, Zhoa W. First principle study of structural stability and electronic structure of La-doped Sr1.9375La0.0625TiO3.965. J Appl Phys. 2010;107:103711.
Palik ED. Handbook of optical constants of solid II. Boston: Academic Press; 1991. 187.
Lee D, Lee Y. Correlation between optical and structural properties in SrZrO3 nanocrystals. New Phys Sae Mulli. 2012;62:1137.
Flores AMH, Martínez LMT, Moctezuma E, Sánchez OC. Enhanced photocatalytic activity for hydrogen evolution of SrZrO3 modified with earth abundant metal oxides (MO, M = Cu, Ni, Fe, Co). Fuel. 2016;181:670.
Vanheusden K, Warren WL, Seager CH, Tallent DR, Voigt JA, Gnade BE. Mechanisms behind green photoluminescence in ZnO phosphor powders. J Appl Phys. 1996;79(10):7983.
Longo VM, Cavalcante LS, Erlo R, Mastelaro VR, de Figueiredo AT, Sambrano JR, de Làzaro S, Freitas AZ, Gomes L Jr, Vieira ND, Varela JA, Longo E. Strong violet–blue light photoluminescence emission at room temperature in SrZrO3: joint experimental and theoretical study. Acta Mater. 2008;56(10):2191.
Zhang A, Lü M, Wang Sh, Zhou G, Zhou Y. Novel photoluminescence of SrZrO3 nanocrystals synthesized through a facile combustion method. J Alloys Compd. 2007;433(1–2):L7.
Lee DJ, Kim DH, Park JW, Lee YS. Room-temperature violet-blue emission for SrZrO3 nanocrystals synthesized by using the combustion method. J Korean Phys Soc. 2011;59:2797.
Pathak N, Gupta SK, Ghosh PS, Arya A, Natarajan V, Kadam RM. Probing local site environments and distribution of manganese in SrZrO3:Mn; PL and EPR spectroscopy complimented by DFT calculations. RSC Adv. 2015;5(23):17501.
Gupta SK, Ghosh PS, Pathak N, Arya A, Natarajan V. Understanding the local environment of Sm3+ in doped SrZrO3 and energy transfer mechanism using time-resolved luminescence: a combined theoretical and experimental approach. RSC Adv. 2014;4(55):29202.
Huang J, Zhou L, Wang Z, Lan Y, Tong Z, Gong F, Sun J, Li L. Photoluminescence properties of SrZrO3: Eu3+ and BaZrO3: Eu3+ phosphors with perovskite structure. J Alloys Compd. 2009;487(1–2):L5.
Longo VM, Cavalcante LS, Costa MGS, Moreira ML, Figueiredo AT, Andrés J, Varela JA, Longo E. First principles calculations on the origin of violet-blue and green light photoluminescence emission in SrZrO3 and SrTiO3 perovskites. Theor Chem Acc. 2009;124:385.
Davies RA, Islam MS, Gale JD. Dopant and proton incorporation in perovskite-type zirconates. Solid State Ion. 1999;126(3–4):323.
Minervini L, Grimes RW. Disorder in pyrochlore oxides. J Am Ceram Soc. 2000;83(8):1873.
Acknowledgements
The authors are grateful to the Grants Commission of Al-Azhar University, Cairo, Egypt for supporting this work. The authors are Thankful to Nanotechnology Characterization Center (NCC)-Cairo University and Central Metallurgical Research Institute (CMRDI)-El Tebeen for extending the XRD and UV–Vis diffused reflectance facility.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Sedeek, K., Makram, N., Hantour, H. et al. An explicit and novel structure, lattice dynamics, and photoemission of La-doped nanocrystalline SrZrO3 perovskite. Rare Met. 40, 105–112 (2021). https://doi.org/10.1007/s12598-019-01326-y
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s12598-019-01326-y