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Elucidations on the Effect of Lanthanum Doping in ZnO Towards Enhanced Performance Nanogenerators

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Abstract

Energy harvesting using semiconducting piezoelectric materials is one of the key areas of current research due to its high biocompatibility, low impedance, and high temperature workable range. In this work, we have optimized the doping of Lanthanum in ZnO towards the realization of enhanced output nanogenerator. We have varied the percentage of lanthanum (0, 1, 2.5, 5 and 7.5%) in the ZnO and systematically studied the piezoelectric response of each device. The piezoelectric output improved three to fourfolds by the incorporation of Lanthanum above 2.5%. The voltage response was further escalated by the controlled annealing in an oxygen environment. The doped and annealed device show eight to ninefolds improved output (~ 13.5 V) compared to the intrinsic device (~ 1.6 V). Material properties were investigated thoroughly along with the piezoelectric using various characterization tools. The device show a high maximum power density (~ 2.5 mW/m2) and was used to charge several commercial capacitors. Finally, the device was demonstrated to work in intruder-safety alarm system application as low-cost device.

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Abbreviations

ZnO:

Zinc oxide

La:

Lanthanum

ITO:

Indium tin oxide

PET:

Polyethylene terephthalate

PVA:

Polyvinyl alcohol

PDMS:

Polydimethylsiloxane

K:

Shape factor

Λ:

Wavelength of X-ray

D:

Crystallite size

Θ:

Braggs diffraction angle

Vp–p :

Peak to peak voltage

A:

Active area of the device

R:

Load resistance

References

  1. Rajagopalan, P., Singh, V., & Palani, I. A. (2016). Investigations on the influence of substrate temperature in developing enhanced response ZnO nano generators on flexible polyimide using spray pyrolysis technique. Materials Research Bulletin,84, 340–345. https://doi.org/10.1016/j.materresbull.2016.08.025.

    Article  Google Scholar 

  2. Rajagopalan, P., Singh, V., & Palani, I. A. (2018). Enhancement of ZnO-based flexible nano generators via a sol–gel technique for sensing and energy harvesting applications. Nanotechnology,29(10), 105406. https://doi.org/10.1088/1361-6528/aaa6bd.

    Article  Google Scholar 

  3. Zhu, Y., Li, Q., Wang, P., Zang, W., Xing, L., & Xue, X. (2015). Enhanced piezo-humidity sensing of Sb-doped ZnO nanowire arrays as self-powered/active humidity sensor. Materials Letters,154, 77–80. https://doi.org/10.1016/j.matlet.2015.04.060.

    Article  Google Scholar 

  4. Khandelwal, G., Chandrasekhar, A., Pandey, R., Maria Joseph Raj, N. P., & Kim, S.-J. (2018). Phase inversion enabled energy scavenger: A multifunctional triboelectric nanogenerator as benzene monitoring system. Sensors and Actuators B: Chemical. https://doi.org/10.1016/j.snb.2018.11.110.

    Article  Google Scholar 

  5. Rajagopalan, P., Singh, V., Palani, I. A., & Kim, S. J. (2018). Superior response in ZnO nanogenerator via interfaced heterojunction for novel smart gas purging system. Extreme Mechanics Letters,26, 18–25. (in press).

    Article  Google Scholar 

  6. Turkmen, A. C., & Celik, C. (2018). Energy harvesting with the piezoelectric material integrated shoe. Energy,150, 556–564. https://doi.org/10.1016/j.energy.2017.12.159.

    Article  Google Scholar 

  7. Kim, J. E., Kim, H., Yoon, H., Kim, Y. Y., & Youn, B. D. (2015). An Energy conversion model for cantilevered piezoelectric vibration energy harvesters using only measurable parameters. International Journal of Precision Engineering and Manufacturing-Green Technology,2(1), 51–57. https://doi.org/10.1007/s40684-015-0007-x.

    Article  Google Scholar 

  8. Park, J.-H., Lim, T.-W., Kim, S.-D., & Park, S.-H. (2016). Design and experimental verification of flexible plate-type piezoelectric vibrator for energy harvesting system. International Journal of Precision Engineering and Manufacturing-Green Technology,3(3), 253–259. https://doi.org/10.1007/s40684-016-0033-3.

    Article  Google Scholar 

  9. Pandey, R., Maria Joseph Raj, N. P., Singh, V., Iyamperumal Anand, P., & Kim, S.-J. (2019). Novel interfacial bulk heterojunction technique for enhanced response in ZnO nanogenerator. ACS Applied Materials & Interfaces,1, 2. https://doi.org/10.1021/acsami.8b19321.

    Article  Google Scholar 

  10. Cui, J., Yoon, H., & Youn, B. D. (2018). An omnidirectional biomechanical energy harvesting (OBEH) sidewalk block for a self-generative power grid in a smart city. International Journal of Precision Engineering and Manufacturing-Green Technology,5(4), 507–517.

    Article  Google Scholar 

  11. Ghemari, Z., Saad, S., & Khettab, K. (2019). Improvement of the vibratory diagnostic method by evolution of the piezoelectric sensor performances. International Journal of Precision Engineering and Manufacturing, 20(8), 1361–1369.

    Article  Google Scholar 

  12. Cao, L.-M., Li, Z.-X., Guo, C., Li, P.-P., Meng, X.-Q., & Wang, T.-M. (2019). Design and test of the MEMS coupled piezoelectric-electromagnetic energy harvester. International Journal of Precision Engineering and Manufacturing,20(4), 673–686.

    Article  Google Scholar 

  13. Banerjee, S., & Roy, S. (2018). A dimensionally reduced order piezoelectric energy harvester model. Energy,148, 112–122. https://doi.org/10.1016/j.energy.2018.01.116.

    Article  Google Scholar 

  14. Sultana, A., Alam, M. M., Ghosh, S. K., Middya, T. R., & Mandal, D. (2019). Energy harvesting and self-powered microphone application on multifunctional inorganic-organic hybrid nanogenerator. Energy,166, 963–971. https://doi.org/10.1016/j.energy.2018.10.124.

    Article  Google Scholar 

  15. Kim, K.-B., Cho, J. Y., Jeon, D. H., Ahn, J. H., Hong, S. D., Jeong, Y.-H., et al. (2018). Enhanced flexible piezoelectric generating performance via high energy composite for wireless sensor network. Energy,159, 196–202. https://doi.org/10.1016/j.energy.2018.06.048.

    Article  Google Scholar 

  16. Yin, B., Qiu, Y., Zhang, H., Lei, J., Chang, Y., Ji, J., et al. (2015). Piezoelectric performance enhancement of ZnO flexible nanogenerator by a NiO–ZnO p–n junction formation. Nano Energy,14, 95–101. https://doi.org/10.1016/j.nanoen.2015.01.032.

    Article  Google Scholar 

  17. Wang, X. B., Song, C., Li, D. M., Geng, K. W., Zeng, F., & Pan, F. (2005). The influence of different doping elements on microstructure, piezoelectric coefficient and resistivity of sputtered ZnO film. Applied Surface Science,253, 1639–1643. https://doi.org/10.1016/j.apsusc.2006.02.059.

    Article  Google Scholar 

  18. Yang, Y. C., Song, C., Wang, X. H., Zeng, F., & Pan, F. (2008). Giant piezoelectric d33 coefficient in ferroelectric vanadium doped ZnO films. Applied Physics Letters,92(1), 012907. https://doi.org/10.1063/1.2830663.

    Article  Google Scholar 

  19. Laurenti, M., Castellino, M., Perrone, D., Asvarov, A., Canavese, G., & Chiolerio, A. (2017). Lead-free piezoelectrics: V(3 +) to V(5 +) ion conversion promoting the performances of V-doped Zinc Oxide. Scientific Reports,7, 41957. https://doi.org/10.1038/srep41957.

    Article  Google Scholar 

  20. Nour, E. S., Echresh, A., Liu, X., Broitman, E., Willander, M., & Nur, O. (2015). Piezoelectric and opto-electrical properties of silver-doped ZnO nanorods synthesized by low temperature aqueous chemical method. AIP Advances,5(7), 077163. https://doi.org/10.1063/1.4927510.

    Article  Google Scholar 

  21. Yadav, H., Sinha, N., Goel, S., & Kumar, B. (2016). Eu-doped ZnO nanoparticles for dielectric, ferroelectric and piezoelectric applications. Journal of Alloys and Compounds,689, 333–341. https://doi.org/10.1016/j.jallcom.2016.07.329.

    Article  Google Scholar 

  22. Goel, S., Sinha, N., Yadav, H., Godara, S., Joseph, A. J., & Kumar, B. (2017). Ferroelectric Gd-doped ZnO nanostructures: Enhanced dielectric, ferroelectric and piezoelectric properties. Materials Chemistry and Physics,202, 56–64. https://doi.org/10.1016/j.matchemphys.2017.08.067.

    Article  Google Scholar 

  23. Goel, S., Sinha, N., Yadav, H., Joseph, A. J., & 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. Physica E: Low-dimensional Systems and Nanostructures,91, 72–81. https://doi.org/10.1016/j.physe.2017.04.010.

    Article  Google Scholar 

  24. Sinha, N., Goel, S., Joseph, A. J., Yadav, H., Batra, K., Gupta, M. K., et al. (2018). Y-doped ZnO nanosheets: Gigantic piezoelectric response for an ultra-sensitive flexible piezoelectric nanogenerator. Ceramics International,44(7), 8582–8590. https://doi.org/10.1016/j.ceramint.2018.02.066.

    Article  Google Scholar 

  25. Uddin, M. T., Nicolas, Y., Olivier, C., Toupance, T., Servant, L., Muller, M. M., et al. (2012). Nanostructured SnO2–ZnO heterojunction photocatalysts showing enhanced photocatalytic activity for the degradation of organic dyes. Inorganic Chemistry,51(14), 7764–7773. https://doi.org/10.1021/ic300794j.

    Article  Google Scholar 

  26. Kumar, A., Herng, T. S., Zeng, K., & Ding, J. (2012). Bipolar charge storage characteristics in copper and cobalt co-doped zinc oxide (ZnO) thin film. ACS Applied Materials & Interfaces,4(10), 5276–5280. https://doi.org/10.1021/am301220h.

    Article  Google Scholar 

  27. Krishnamoorthy, K., Pazhamalai, P., & Kim, S. J. (2017). Ruthenium sulfide nanoparticles as a new pseudocapacitive material for supercapacitor. Electrochimica Acta,227, 85–94. https://doi.org/10.1016/j.electacta.2016.12.171.

    Article  Google Scholar 

  28. Li, D., Huang, J.-F., Cao, L.-Y., Li, J.-Y., OuYang, H.-B., & Yao, C.-Y. (2014). Microwave hydrothermal synthesis of Sr2+ doped ZnO crystallites with enhanced photocatalytic properties. Ceramics International,40(2), 2647–2653. https://doi.org/10.1016/j.ceramint.2013.10.061.

    Article  Google Scholar 

  29. Anandan, S., Vinu, A., Sheeja Lovely, K. L. P., Gokulakrishnan, N., Srinivasu, P., Mori, T., et al. (2007). Photocatalytic activity of La-doped ZnO for the degradation of monocrotophos in aqueous suspension. Journal of Molecular Catalysis A: Chemical,266(1–2), 149–157. https://doi.org/10.1016/j.molcata.2006.11.008.

    Article  Google Scholar 

  30. Chen, J. T., Wang, J., Zhang, F., Zhang, G. A., Wu, Z. G., & Yan, P. X. (2008). The effect of La doping concentration on the properties of zinc oxide films prepared by the sol–gel method. Journal of Crystal Growth,310(10), 2627–2632. https://doi.org/10.1016/j.jcrysgro.2008.01.011.

    Article  Google Scholar 

  31. Sahoo, S., Sharma, G. L., & Katiyar, R. S. (2012). Raman spectroscopy to probe residual stress in ZnO nanowire. Journal of Raman Spectroscopy,43(1), 72–75. https://doi.org/10.1002/jrs.3004.

    Article  Google Scholar 

  32. Wang, N., Liu, J., Gu, W., Song, Y., & Wang, F. (2016). Toward synergy of carbon and La2O3 in their hybrid as an efficient catalyst for the oxygen reduction reaction. RSC Advances,6(81), 77786–77795. https://doi.org/10.1039/c6ra17104d.

    Article  Google Scholar 

  33. Luo, J. T., Yang, Y. C., Zhu, X. Y., 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. Physical Review B. https://doi.org/10.1103/physrevb.82.014116.

    Article  Google Scholar 

  34. Sinha, N., Ray, G., Bhandari, S., Godara, S., & Kumar, B. (2014). Synthesis and enhanced properties of cerium doped ZnO nanorods. Ceramics International,40(8, Part A), 12337–12342. https://doi.org/10.1016/j.ceramint.2014.04.079.

    Article  Google Scholar 

  35. Cardoso, J., Oliveira, F. F., Proenca, M. P., & Ventura, J. (2018). The influence of shape on the output potential of ZnO nanostructures: Sensitivity to parallel versus perpendicular forces. Nanomaterials (Basel). https://doi.org/10.3390/nano8050354.

    Article  Google Scholar 

  36. Saravanakumar, B., & Kim, S.-J. (2014). Growth of 2D ZnO nanowall for energy harvesting application. The Journal of Physical Chemistry C,118(17), 8831–8836. https://doi.org/10.1021/jp502057p.

    Article  Google Scholar 

  37. Gupta, M. K., Lee, J.-H., Lee, K. Y., & Kim, S.-W. (2013). Two-dimensional vanadium-doped ZnO nanosheet-based flexible direct current nanogenerator. ACS Nano,7(10), 8932–8939.

    Article  Google Scholar 

  38. Shin, S.-H., Lee, M. H., Jung, J.-Y., Seol, J. H., & Nah, J. (2013). Piezoelectric performance enhancement of ZnO flexible nanogenerator by a CuO–ZnO p–n junction formation. Journal of Materials Chemistry C,1(48), 8103–8107. https://doi.org/10.1039/c3tc31664e.

    Article  Google Scholar 

  39. Xue, X., Nie, Y., He, B., Xing, L., Zhang, Y., & Wang, Z. L. (2013). Surface free-carrier screening effect on the output of a ZnO nanowire nanogenerator and its potential as a self-powered active gas sensor. IOP Nanotechnology,24, 225501. https://doi.org/10.1088/0957-4484/24/22/225501.

    Article  Google Scholar 

  40. Baek, S. K., Kwak, S. S., Kim, J. S., Kim, S. W., & Cho, H. K. (2016). Binary oxide p–n heterojunction piezoelectric nanogenerators with an electrochemically deposited high p-type Cu2O layer. ACS Applied Materials & Interfaces,8(34), 22135–22141. https://doi.org/10.1021/acsami.6b03649.

    Article  Google Scholar 

  41. Ong, W. L., Huang, H., Xiao, J., Zeng, K., & Ho, G. W. (2014). Tuning of multifunctional Cu-doped ZnO films and nanowires for enhanced piezo/ferroelectric-like and gas/photoresponse properties. Nanoscale,6, 1680. https://doi.org/10.1039/c3nr05034c.

    Article  Google Scholar 

  42. Hsu, C. L., Li, H. H., & Hsueh, T. J. (2013). Water- and humidity-enhanced UV detector by using p-type La-doped ZnO nanowires on flexible polyimide substrate. ACS Applied Materials & Interfaces,5(21), 11142–11151. https://doi.org/10.1021/am403364r.

    Article  Google Scholar 

  43. Tian, S., Zhang, Y., Zeng, D., Wang, H., Li, N., Xie, C., et al. (2015). Surface doping of La ions into ZnO nanocrystals to lower the optimal working temperature for HCHO sensing properties. Physical Chemistry Chemical Physics,17(41), 27437–27445. https://doi.org/10.1039/c5cp04816h.

    Article  Google Scholar 

  44. Jeong, D. K., Kang, J.-H., Ha, J.-S., & Ryu, S.-W. (2017). Enhanced piezoelectric operation of NiO/GaN heterojunction generator by suppressed internal carrier screening. Journal of Physics. D. Applied Physics,50(42), 425101. https://doi.org/10.1088/1361-6463/aa882a.

    Article  Google Scholar 

  45. Mrabet, C., Kamoun, O., Boukhachem, A., Amlouk, M., & Manoubi, T. (2015). Some physical investigations on hexagonal-shaped nanorods of lanthanum-doped ZnO. Journal of Alloys and Compounds,648, 826–837. https://doi.org/10.1016/j.jallcom.2015.07.009.

    Article  Google Scholar 

  46. Korake, P. V., Dhabbe, R. S., Kadam, A. N., Gaikwad, Y. B., & Garadkar, K. M. (2014). Highly active lanthanum doped ZnO nanorods for photodegradation of metasystox. Journal of Photochemistry and Photobiology B: Biology,130, 11–19. https://doi.org/10.1016/j.jphotobiol.2013.10.012.

    Article  Google Scholar 

  47. Shet, S., Ahn, K.-S., Yan, Y., Deutsch, T., Chrustowski, K. M., Turner, J., et al. (2008). Carrier concentration tuning of bandgap-reduced p-type ZnO films by codoping of Cu and Ga for improving photoelectrochemical response. Journal of Applied Physics,103, 073504. https://doi.org/10.1063/1.2888578.

    Article  Google Scholar 

  48. Shin, S.-H., Kim, Y.-H., Lee, M. H., Jung, J.-Y., Seol, J. H., & Nah, J. (2014). Lithium-doped zinc oxide nanowires–polymer composite for high performance flexible piezoelectric nanogenerator. ACS Nano,8(10), 10844–10850.

    Article  Google Scholar 

  49. Dangbegnon, J. K., Roro, K. T., & Botha, J. R. (2008). Towards p-type ZnO using post-growth annealing. Physica Status Solidi (a),205(1), 155–158. https://doi.org/10.1002/pssa.200776828.

    Article  Google Scholar 

  50. Zhang, Y., Liu, C., Liu, J., Xiong, J., Liu, J., Zhang, K., et al. (2016). Lattice strain induced remarkable enhancement in piezoelectric performance of ZnO-based flexible nanogenerators. ACS Applied Materials & Interfaces,8, 1381–1387. https://doi.org/10.1021/acsami.5b10345.

    Article  Google Scholar 

  51. Lee, J.-H., Lee, K. Y., Kumar, B., & Kim, S.-W. (2012). Synthesis of Ga-doped ZnO nanorods using an aqueous solution method for a piezoelectric nanogenerator. Journal of Nanoscience and Nanotechnology,12(4), 3430–3433. https://doi.org/10.1166/jnn.2012.5632.

    Article  Google Scholar 

  52. Chen, X., Xu, S., Yao, N., & Shi, Y. (2010). 1.6 V nanogenerator for mechanical energy harvesting using PZT nanofibers. Nano Letters,10(6), 2133–2137. https://doi.org/10.1021/nl100812k.

    Article  Google Scholar 

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Acknowledgements

The author Pandey R is grateful to Research Instrument Center, JNU Jeju for providing characterization facilities. Pandey R. would further like to thank the (MHRD), India, for providing the Teaching Assistantship (TA). Pandey R is also Thankful to Indo Korea Research Internship by DST, India and NRF, Korea. Pandey R is thankful to Prof Kim Sang Jae for IKRI. Pandey R is grateful to Prof P M Shirage, Dr Prateek bhojane, Ms Lichhavi Sinha, Mr Aayush Gupta and Mr. S S Mani Prabhu for helping and improving in the content of the manuscript. A part of the research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIT) (2019R1A2C3009747, 2018R1A4A1025998).

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Rajagopalan, P., Jakhar, P., Palani, I.A. et al. Elucidations on the Effect of Lanthanum Doping in ZnO Towards Enhanced Performance Nanogenerators. Int. J. of Precis. Eng. and Manuf.-Green Tech. 7, 77–87 (2020). https://doi.org/10.1007/s40684-019-00151-z

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