Abstract
In this article, we report on high-temperature ferroelectricity and enhanced piezoelectricity observed in europium and gadolinium (Eu3+/Gd3+) co-doped ZnO nanocrystals, although pristine ZnO does not exhibit ferroelectricity and is feeble piezoelectric. First, the nanocrystals of pristine ZnO and Eu3+/Gd3+ co-doped ZnO were grown using wet chemical synthesis. The products were characterized for powder X-ray diffraction and scanning electron microscopy analysis. 1D nanopencils (NPCs) like habit were obtained for pristine ZnO. Eu3+/Gd3+ co-doping resulted in habit modification blunt-tip pristine ZnO NPCs to sharp-tip Eu3+/Gd3+ co-doped ZnO NPCs, which resembles sisal-like architecture. Various X-ray peak broadening analysis methods such as Debye–Scherrer and Williamson–Hall (W-H; UDM, USDM, UDEDM) were used to calculate the crystallite size, lattice strain, stress, and energy density of both pristine and Eu3+/Gd3+ co-doped ZnO nanocrystals. Variation of dielectric constant (ε′), dielectric loss (tan δ) and ac conductivity (σac) with frequency of applied field as well as with temperature were studied. Ferroelectric character in sisal-like Eu3+/Gd3+ co-doped ZnO NPCs was proven using the temperature-dependent curve of dielectric constant as well as using polarization hysteresis loop. High ferro- to para-electric phase transition temperature (Tc = 227 °C) was obtained for as-grown product. The sisal-like Eu3+/Gd3+ co-doped ZnO NPCs exhibit feeble ferroelectricity (Ec ~ 16.49 kV/cm and Pr ~ 0.38 μC/cm2) and enhanced piezoelectricity (d33 ~ 55 pm/V) at room temperature. Our results indicate that the sisal-like Eu3+/Gd3+ co-doped ZnO micro-flower assembled by NPCs is a promising bio-compatible piezo-/ferro-electric material for designing components for piezoelectric nanogenerators and memory devices.
Similar content being viewed by others
References
Sinha N, Goel S, Joseph AJ, Yadav H, Batra K, Gupta MK, Kumar B (2018) Y-doped ZnO nanosheets: gigantic piezoelectric response for an ultra-sensitive flexible piezoelectric nanogenerator. Ceram Int 44:8582–8590. https://doi.org/10.1016/j.ceramint.2018.02.066
Wang ZL, Song J (2006) Piezoelectric nanogenerators based on zinc oxide nanowire arrays. Science (80- ) 312:242–246. https://doi.org/10.1126/science.1124005
Campbell C (1989) Surface acoustic wave devices and their signal processing applications. Academic Press, San Diego
Zi Y, Wang J, Wang S, Li S, Wen Z, Guo H, Wang ZL (2016) Effective energy storage from a triboelectric nanogenerator. Nat Commun 7:10987. https://doi.org/10.1038/ncomms10987
Deng W, Zhang B, Jin L, Chen Y, Chu W, Zhang H, Zhu M, Yang W (2017) Enhanced performance of ZnO microballoon arrays for a triboelectric nanogenerator. Nanotechnology 28:135401. https://doi.org/10.1088/1361-6528/aa5f34
Kumar R, Al-Dossary O, Kumar G, Umar A (2015) Zinc oxide nanostructures for NO2 gas–sensor applications: a review. Nano-Micro Lett 7:97–120. https://doi.org/10.1007/s40820-014-0023-3
Zhu L, Zeng W (2017) Room-temperature gas sensing of ZnO-based gas sensor: a review. Sensors Actuators A Phys 267:242–261. https://doi.org/10.1016/j.sna.2017.10.021
Goel S, Sinha N, Yadav H, Joseph AJ, Kumar B (2017) Experimental investigation on the structural, dielectric, ferroelectric and piezoelectric properties of La doped ZnO nanoparticles and their application in dye-sensitized solar cells. Phys E Low-dimensional Syst Nanostructures 91:72–81. https://doi.org/10.1016/j.physe.2017.04.010
Zang Z (2018) Efficiency enhancement of ZnO/Cu2O solar cells with well oriented and micrometer grain sized Cu2O films. Appl Phys Lett 112:042106. https://doi.org/10.1063/1.5017002
Li C, Zang Z, Han C, Hu Z, Tang X, du J, Leng Y, Sun K (2017) Highly compact CsPbBr3 perovskite thin films decorated by ZnO nanoparticles for enhanced random lasing. Nano Energy 40:195–202. https://doi.org/10.1016/j.nanoen.2017.08.013
Li C, Han C, Zhang Y, Zang Z, Wang M, Tang X, du J (2017) Enhanced photoresponse of self-powered perovskite photodetector based on ZnO nanoparticles decorated CsPbBr3 films. Sol Energy Mater Sol Cells 172:341–346. https://doi.org/10.1016/j.solmat.2017.08.014
Lee S-H, Han S-H, Jung HS, Shin H, Lee J, Noh JH, Lee S, Cho IS, Lee JK, Kim J, Shin H (2010) Al-doped ZnO thin film: a new transparent conducting layer for ZnO nanowire-based dye-sensitized solar cells. J Phys Chem C 114:7185–7189. https://doi.org/10.1021/jp1008412
Tsukazaki A, Ohtomo A, Onuma T, Ohtani M, Makino T, Sumiya M, Ohtani K, Chichibu SF, Fuke S, Segawa Y, Ohno H, Koinuma H, Kawasaki M (2004) Repeated temperature modulation epitaxy for p-type doping and light-emitting diode based on ZnO. Nat Mater 4:42–46. https://doi.org/10.1038/nmat1284
Laurenti M, Garino N, Porro S, Fontana M, Gerbaldi C (2015) Zinc oxide nanostructures by chemical vapour deposition as anodes for Li-ion batteries. J Alloys Compd 640:321–326. https://doi.org/10.1016/j.jallcom.2015.03.222
Zang Z, Zeng X, Du J et al (2016) Femtosecond laser direct writing of microholes on roughened ZnO for output power enhancement of InGaN light-emitting diodes. Opt Lett 41:3463–3466. https://doi.org/10.1364/OL.41.003463
Zhao M-H, Wang Z-L, Mao SX (2004) Piezoelectric characterization of individual zinc oxide nanobelt probed by piezoresponse force microscope. Nano Lett 4:587–590. https://doi.org/10.1021/nl035198a
Joseph AJ, Goel S, Hussain A, Kumar B (2017) Ferro-/pyroelectric response of 0.57BF-0.31PMN-0.12PT ternary ceramic far away from morphotropic phase boundaries. Ceram Int 43:16676–16683. https://doi.org/10.1016/j.ceramint.2017.09.058
Joseph AJ, Sinha N, Goel S et al (2018) 0.37BF-0.31PMN-0.32PT: a superior piezo-/pyro-/ferro-electric ternary ceramic at MPB. Ceram Int. https://doi.org/10.1016/j.ceramint.2018.07.089
Hussain A, Sinha N, Bhandari S, Yadav H, Kumar B (2016) Synthesis of 0.64Pb(Mg 1/3 Nb 2/3)O3–0.36PbTiO3 ceramic near morphotropic phase boundary for high performance piezoelectric, ferroelectric and pyroelectric applications. J Asian Ceram Soc 4:337–343. https://doi.org/10.1016/j.jascer.2016.06.004
Joseph AJ, Kumar B (2018) Study of true-remanent polarization using remanent hysteresis task and resistive leakage analysis in ferroelectric 0.64Pb(Mg1/3Nb2/3)O3-0.36PbTi3 ceramics. Solid State Commun 271:11–15. https://doi.org/10.1016/j.ssc.2017.12.017
Hussain A, Sinha N, Joseph AJ, Dhankhar K, Goel S, Kumar B (2017) Improvement in dielectric, piezoelectric and ferroelectric properties of 0.64PMN–0.36PT ceramics by Sb modification. J Mater Sci Mater Electron 28:14298–14307. https://doi.org/10.1007/s10854-017-7289-4
Joseph AJ, Sinha N, Goel S, et al (2018) True-remanent, resistive-leakage and mechanical studies of flux grown 0.64PMN-0.36PT single crystals. Arab J Chem. doi: https://doi.org/10.1016/j.arabjc.2018.06.012
Goel S, Sinha N, Hussain A, Joseph AJ, Yadav H, Kumar B (2018) Sunset yellow dyed triglycine sulfate single crystals: enhanced thermal, mechanical, optical and di-/piezo-/ferro-/pyro-electric properties. J Mater Sci Mater Electron 29:13449–13463. https://doi.org/10.1007/s10854-018-9470-9
Hussain A, Sinha N, Joseph AJ, Goel S, Singh B, Bdikin I, Kumar B (2018) Mechanical investigations on piezo-/ferrolectric maleic acid-doped triglycine sulphate single crystal using nanoindentation technique. Arab J Chem. https://doi.org/10.1016/j.arabjc.2018.02.001
Yadav H, Sinha N, Goel S, Hussain A, Kumar B (2016) Growth and structural and physical properties of diisopropylammonium bromide molecular single crystals. J Appl Crystallogr 49:2053–2062. https://doi.org/10.1107/S1600576716014552
Goel S, Sinha N, Yadav H, Joseph AJ, Kumar B (2018) 2D porous nanosheets of Y-doped ZnO for dielectric and ferroelectric applications. J Mater Sci Mater Electron 29:13818–13832. https://doi.org/10.1007/s10854-018-9513-2
Aggarwal N, Kaur K, Vasishth A, Verma NK (2016) Structural, optical and magnetic properties of gadolinium-doped ZnO nanoparticles. J Mater Sci Mater Electron 27:13006–13011. https://doi.org/10.1007/s10854-016-5440-2
Roqan IS, Venkatesh S, Zhang Z, Hussain S, Bantounas I, Franklin JB, Flemban TH, Zou B, Lee JS, Schwingenschlogl U, Petrov PK, Ryan MP, Alford NM (2015) Obtaining strong ferromagnetism in diluted Gd-doped ZnO thin films through controlled Gd-defect complexes. J Appl Phys 117:073904. https://doi.org/10.1063/1.4908288
Franco A, Pessoni HVS, Soares MP (2014) Room temperature ferromagnetism in Eu-doped ZnO nanoparticulate powders prepared by combustion reaction method. J Magn Magn Mater 355:325–330. https://doi.org/10.1016/j.jmmm.2013.12.028
Onodera A, Tamaki N, Kawamura Y, Sawada T, Yamashita H (1996) Dielectric activity and ferroelectricity in piezoelectric semiconductor Li-doped ZnO. Jpn J Appl Phys 35:5160–5162. https://doi.org/10.1143/JJAP.35.5160
Onodera A, Tamaki N, Jin K, Yamashita H (1997) Ferroelectric properties in piezoelectric semiconductor Zn1−xMxO (M=Li, Mg). Jpn J Appl Phys 36:6008–6011. https://doi.org/10.1143/JJAP.36.6008
Onodera A, Yoshio K, Satoh H, Yamashita H, Sakagami N (1998) Li-substitution effect and ferroelectric properties in piezoelectric semiconductor ZnO. Jpn J Appl Phys 37:5315–5317. https://doi.org/10.1143/JJAP.37.5315
Nagata T, Shimura T, Nakano Y, Ashida A, Fujimura N, Ito T (2001) Ferroelectricity in Li-doped ZnO:X thin films and their application in optical switching devices. Jpn J Appl Phys 40:5615–5618. https://doi.org/10.1143/JJAP.40.5615
Yang YC, Song C, Wang XH, Zeng F, Pan F (2008) Cr-substitution-induced ferroelectric and improved piezoelectric properties of Zn1−xCrxO films. J Appl Phys 103:074107. https://doi.org/10.1063/1.2903152
Srinet G, Kumar R, Sajal V (2014) High Tc ferroelectricity in Ba-doped ZnO nanoparticles. Mater Lett 126:274–277. https://doi.org/10.1016/j.matlet.2014.04.054
Dhananjay KSB (2006) Dielectric properties of c-axis oriented Zn1−xMgxO thin films grown by multimagnetron sputtering. Appl Phys Lett 89:082905. https://doi.org/10.1063/1.2266891
Yang YC, Song C, Wang XH, Zeng F, Pan F (2008) Giant piezoelectric d33 coefficient in ferroelectric vanadium doped ZnO films. Appl Phys Lett 92:012907. https://doi.org/10.1063/1.2830663
Luo JT, Yang YC, Zhu XY, Chen G, Zeng F, Pan F (2010) Enhanced electromechanical response of Fe-doped ZnO films by modulating the chemical state and ionic size of the Fe dopant. Phys Rev B 82:014116. https://doi.org/10.1103/PhysRevB.82.014116
Chen YJ, Brahma S, Liu CP, Huang J-L (2017) Enhancement of the piezoelectric coefficient in hexagonal MgxZn1-xO films at lower mg compositions. J Alloys Compd 728:1248–1253. https://doi.org/10.1016/j.jallcom.2017.08.278
Goel S, Sinha N, Yadav H, Kumar B (2018) On the prediction of external shape of ZnO nanocrystals. Phys E Low-dimensional Syst Nanostructures. https://doi.org/10.1016/j.physe.2018.08.014
Yadav H, Sinha N, Goel S, Kumar B (2016) Eu-doped ZnO nanoparticles for dielectric, ferroelectric and piezoelectric applications. J Alloys Compd 689:333–341. https://doi.org/10.1016/j.jallcom.2016.07.329
Goel S, Sinha N, Yadav H, Godara S, Joseph AJ, Kumar B (2017) Ferroelectric Gd-doped ZnO nanostructures: enhanced dielectric, ferroelectric and piezoelectric properties. Mater Chem Phys 202:56–64. https://doi.org/10.1016/j.matchemphys.2017.08.067
Batra K, Sinha N, Goel S, Yadav H, Joseph AJ, Kumar B (2018) Enhanced dielectric, ferroelectric and piezoelectric performance of Nd-ZnO nanorods and their application in flexible piezoelectric nanogenerator. J Alloys Compd 767:1003–1011. https://doi.org/10.1016/j.jallcom.2018.07.187
Atabaev T, Lee J, Shin Y, Han DW, Choo K, Jeon U, Hwang J, Yeom J, Kim HK, Hwang YH (2017) Eu, Gd-codoped yttria nanoprobes for optical and T1-weighted magnetic resonance imaging. Nanomaterials 7:35. https://doi.org/10.3390/nano7020035
Ruan K, Chen X, Liang T, Wu G, Bao D (2008) Improved photoluminescence and electrical properties of Eu- and Gd-codoped bismuth titanate ferroelectric thin films. J Appl Phys 103:086104. https://doi.org/10.1063/1.2907735
Wang GD, Chen H, Tang W et al (2016) Gd and Eu co-doped nanoscale metal–organic framework as a T1–T2 dual-modal contrast agent for magnetic resonance imaging. Tomography 2:179–187. https://doi.org/10.3938/jkps.56.868
Yang SJ, Park CR (2008) Facile preparation of monodisperse ZnO quantum dots with high quality photoluminescence characteristics. Nanotechnology 19:035609. https://doi.org/10.1088/0957-4484/19/03/035609
Kong XY, Wang ZL (2003) Spontaneous polarization-induced nanohelixes, nanosprings, and nanorings of piezoelectric nanobelts. Nano Lett 3:1625–1631. https://doi.org/10.1021/nl034463p
Pan ZW (2001) Nanobelts of semiconducting oxides. Science (80- ) 291:1947–1949. https://doi.org/10.1126/science.1058120
Gao PX, Wang ZL (2003) Mesoporous polyhedral cages and shells formed by textured self-assembly of ZnO nanocrystals. J Am Chem Soc 125:11299–11305. https://doi.org/10.1021/ja035569p
Gupta R, Chauhan RP, Chakarvarti SK, Kumar R (2018) Effect of SHI on properties of template synthesized Cu nanowires. Ionics (Kiel) 1–12. https://doi.org/10.1007/s11581-018-2578-3
Hussain A, Sinha N, Dhankhar K, Joseph AJ, Kumar B (2018) Giant piezoelectric behavior in relaxor ferroelectric environment friendly Na0.52K0.44Li0.04Nb0.84Ta0.10Sb0.06O3 ceramics for high temperature applications. J Mater Sci Mater Electron 29:6403–6411. https://doi.org/10.1007/s10854-018-8620-4
Goel S, Sinha N, Yadav H, Hussain A, Kumar B (2016) Effect of crystal violet dye on the structural, optical, mechanical and piezoelectric properties of ADP single crystal. Mater Res Bull 83:77–87. https://doi.org/10.1016/j.materresbull.2016.05.023
Goel S, Sinha N, Yadav H, Joseph AJ, Hussain A, Kumar B (2017) Optical, piezoelectric and mechanical properties of xylenol orange doped ADP single crystals for NLO applications. Arab J Chem. https://doi.org/10.1016/j.arabjc.2017.03.003
Goel S, Yadav H, Sinha N, Singh B, Bdikin I, Rao DC, Gopalaiah K, Kumar B (2017) An insight into the synthesis, crystal structure, geometrical modelling of crystal morphology, Hirshfeld surface analysis and characterization of N-(4-methylbenzyl)benzamide single crystals. J Appl Crystallogr 50:1498–1511. https://doi.org/10.1107/S1600576717012316
Goel S, Yadav H, Sinha N, Singh B, Bdikin I, Kumar B (2018) X-ray, dielectric, piezoelectric and optical analyses of a new nonlinear optical 8-hydroxyquinolinium hydrogen squarate crystal. Acta Crystallogr Sect B Struct Sci Cryst Eng Mater 74:12–23. https://doi.org/10.1107/S2052520617013038
Yadav H, Sinha N, Goel S, Singh B, Bdikin I, Saini A, Gopalaiah K, Kumar B (2017) Growth, crystal structure, Hirshfeld surface, optical, piezoelectric, dielectric and mechanical properties of bis(L-asparaginium hydrogensquarate) single crystal. Acta Crystallogr Sect B Struct Sci Cryst Eng Mater 73:347–359. https://doi.org/10.1107/S2052520617002906
Sinha N, Ray G, Bhandari S, Godara S, Kumar B (2014) Synthesis and enhanced properties of cerium doped ZnO nanorods. Ceram Int 40:12337–12342. https://doi.org/10.1016/j.ceramint.2014.04.079
Acknowledgements
We are grateful for the financial assistance from the ARMREB, DRDO, India (Sanction No. ARMREB/MAA/2015/163) and DST, India (Sanction No. EMR/2015/000385) for carrying out this work. One of the authors, N.S., is grateful to the Principal, SGTB Khalsa College, for support. S.G., A.H., and A.J.J. acknowledge CSIR and DRDO for Senior Research Fellowship.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare that they have no conflict of interest.
Rights and permissions
About this article
Cite this article
Goel, S., Sinha, N., Hussain, A. et al. Di-/piezo-/ferro-electric characterizations of 3D hierarchical sisal-like Eu3+/Gd3+ co-doped ZnO micro-flowers assembled with 1D nanopencils. Ionics 25, 1373–1386 (2019). https://doi.org/10.1007/s11581-018-2721-1
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11581-018-2721-1