Journal Home > Volume 9 , issue 1

The thin film of heat-sensitive materials has been widely concerned with the current trend of miniaturization and integration of sensors. In this work, Mn1.56Co0.96Ni0.48O4 (MCNO) thin films were prepared on SiO2/Si substrates by sputtering with Mn–Co–Ni alloy target and then annealing in air at different temperatures (650–900 ℃). The X-ray diffraction (XRD) and field emission scanning electron microscopy (FE-SEM) analysis indicated that the main crystalline phase of MCNO thin films was spinel crystal structure; the surface of the thin films was very dense and uniform. The electrical properties of the thin films were studied in the temperature range of –5–50 ℃. The MCNO thin film with a low room temperature resistance R25 of 71.1 kΩ and a high thermosensitive constant B value of 3305 K was obtained at 750 ℃. X-ray photoelectron spectroscopy (XPS) analysis showed that the concentration of Mn3+ and Mn4+ cations in MCNO thin films is the highest when annealing temperature is 750 ℃. The complex impedance analysis revealed internal conduction mechanism of the MCNO thin film and the resistance of the thin film was dominated by grain boundary resistance.


menu
Abstract
Full text
Outline
About this article

Mn–Co–Ni–O thin films prepared by sputtering with alloy target

Show Author's information Ruifeng LIQiuyun FU( )Xiaohua ZOUZhiping ZHENGWei LUOLiang YAN
Engineering Research Center for Functional Ceramics of Ministry of Education, School of Optical and Electronic Information, Huazhong University of Science and Technology, Wuhan 430074, China

Abstract

The thin film of heat-sensitive materials has been widely concerned with the current trend of miniaturization and integration of sensors. In this work, Mn1.56Co0.96Ni0.48O4 (MCNO) thin films were prepared on SiO2/Si substrates by sputtering with Mn–Co–Ni alloy target and then annealing in air at different temperatures (650–900 ℃). The X-ray diffraction (XRD) and field emission scanning electron microscopy (FE-SEM) analysis indicated that the main crystalline phase of MCNO thin films was spinel crystal structure; the surface of the thin films was very dense and uniform. The electrical properties of the thin films were studied in the temperature range of –5–50 ℃. The MCNO thin film with a low room temperature resistance R25 of 71.1 kΩ and a high thermosensitive constant B value of 3305 K was obtained at 750 ℃. X-ray photoelectron spectroscopy (XPS) analysis showed that the concentration of Mn3+ and Mn4+ cations in MCNO thin films is the highest when annealing temperature is 750 ℃. The complex impedance analysis revealed internal conduction mechanism of the MCNO thin film and the resistance of the thin film was dominated by grain boundary resistance.

Keywords:

MCNO, thin film, sputtering, annealing
Received: 20 March 2019 Revised: 20 June 2019 Accepted: 17 August 2019 Published: 05 February 2020 Issue date: February 2020
References(29)
[1]
C Ma, W Ren, L Wang, et al. Structural, optical, and electrical properties of (Mn1.56Co0.96Ni0.48O4)1–x(LaMnO3)x composite thin films. J Eur Ceram Soc 2016, 36: 4059-064.
[2]
WW Kong, L Chen, B Gao, et al. Fabrication and properties of Mn1.56Co0.96Ni0.48O4 free-standing ultrathin chips. Ceram Int 2014, 40: 8405-8409.
[3]
A Feteira. Negative temperature coefficient resistance (NTCR) ceramic thermistors: An industrial perspective. J Am Ceram Soc 2009, 92: 967-983.
[4]
F Zhang, W Zhou, C Ouyang, et al. Annealing effect on the structural and electrical performance of Mn–Co–Ni–O films. AIP Adv 2015, 5: 117137.
[5]
R Jadhav, D Kulkarni, V Puri. Structural and electrical properties of fritless Ni(1–x)CuxMn2O4 (0 ≤ x ≤ 1) thick film NTC ceramic. J Mater Sci: Mater Electron 2010, 21: 503-508.
[6]
S Jagtap, S Rane, S Gosavi, et al. Low temperature synthesis and characterization of NTC powder and its ‘lead free’ thick film thermistors. Microelectron Eng 2010, 87: 104-107.
[7]
W Zhou, LB Zhang, C Ouyang, et al. Micro structural, electrical and optical properties of highly (220) oriented spinel Mn–Co–Ni–O film grown by radio frequency magnetron sputtering. Appl Surf Sci 2014, 311: 443-447.
[8]
L He, ZY Ling, MY Wu, et al. Thermal and humidity sensing behaviors of Mn1.85Co0.3Ni0.85O4 thin films: Effects of adjusting the surface morphology. Appl Surf Sci 2017, 410: 201-205.
[9]
WW Kong, W Wei, B Gao, et al. Mn1.56Co0.96Ni0.48O4±δ flexible thin films fabricated by pulsed laser deposition for NTC applications. Mat Sci Eng B 2016, 206: 39-44.
[10]
DA Kukuruznyak, JG Moyer, FS Ohuchi. Improved aging characteristics of NTC thermistor thin films fabricated by a hybrid sol–gel–MOD process. J Am Ceram Soc 2006, 89: 189-192.
[11]
Q Shi, W Ren, WW Kong, et al. High B value Mn–Co–Ni spinel films on alumina substrate by RF sputtering. J Mater Sci: Mater Electron 2017, 28: 9876-9881.
[12]
W Zhou, XF Xu, C Ouyang, et al. Annealing effect on the structural, electrical and 1/f noise properties of Mn–Co– Ni–O thin films. J Mater Sci: Mater Electron 2014, 25: 1959-1964.
[13]
L He, ZY Ling, YT Huang, et al. Effects of annealing temperature on microstructure and electrical properties of Mn–Co–Ni–O thin films. Mater Lett 2011, 65: 1632-1635.
[14]
YJ Ge, ZM Huang, Y Hou, et al. Low temperature growth of manganese cobalt nickelate films by chemical deposition. Thin Solid Films 2008, 516: 5931-5934.
[15]
K Park, JK Lee. Mn–Ni–Co–Cu–Zn–O NTC thermistors with high thermal stability for low resistance applications. Scripta Mater 2007, 57: 329-332.
[16]
H Han, H Lee, J Lim, et al. Hopping conduction in (Ni,Co,Mn)O4 prepared by different synthetic routes: Conventional and spark plasma sintering. Ceram Int 2017, 43: 16070-16075.
[17]
TH Dolla, K Pruessner, DG Billing, et al. Sol–gel synthesis of MnxNi1–xCo2O4 spinel phase materials: Structural, electronic, and magnetic properties. J Alloys Compd 2018, 742: 78-89.
[18]
J Wu, ZM Huang, W Zhou, et al. Investigation of cation distribution, electrical, magnetic properties and their correlation in Mn2–xCo2xNi1–xO4 films. J Appl Phys 2014, 115: 113703.
[19]
WW Kong, W Wei, B Gao, et al. A study on the electrical properties of Mn–Co–Ni–O thin films grown by radio frequency magnetron sputtering with different thicknesses. Appl Surf Sci 2017, 423: 1012-1018.
[20]
Guang J, Chang AM, Xu JB, et al. Low-temperature (< 300 ℃) growth and characterization of single-[100]-oriented Mn– Co–Ni–O thin films. Mater Lett 2013, 107: 103-106.10.1016/j.matlet.2013.05.079
[21]
LB Zhang, Y Hou, W Zhou, et al. Investigation on optical properties of NiMn2O4 films by spectroscopic ellipsometry. Solid State Commun 2013, 159: 32-35.
[22]
JM Varghese, A Seema, KR Dayas. Microstructural, electrical and reliability aspects of chromium doped Ni–Mn–Fe–O NTC thermistor materials. Mat Sci Eng B 2008, 149: 47-52.
[23]
R Schmidt, A Basu, AW Brinkman, et al. Electron-hopping modes in NiMn2O4+δ materials. Appl Phys Lett 2005, 86: 073501.
[24]
BI Shklovskii, AL Efros. Percolation theory. In: Electronic Properties of Doped Semiconductors. Springer Series in Solid-State Sciences, Vol. 45. Springer Berlin Heidelberg, 1984: 94-136.
[25]
DL Fang, CH Zheng, CS Chen, et al. Aging of nickel manganite NTC ceramics. J Electroceram 2009, 22: 421-427.
[26]
L He, ZY Ling. Electrical conduction of intrinsic grain and grain boundary in Mn–Co–Ni–O thin film thermistors: Grain size influence. J Appl Phys 2011, 110: 093708.
[27]
FD Morrison, DC Sinclair, AR West. Characterization of lanthanum-doped barium titanate ceramics using impedance spectroscopy. J Am Ceram Soc 2001, 84: 531-538.
[28]
L He, ZY Ling, DX Ling, et al. The microstructure and humidity sensing properties of the Mn3.15Co0.3Ni0.8O4 thin film with a three-dimensional nano-network structure. Ceram Int 2016, 42: 7605-7610.
[29]
X Sun, SL Leng, H Zhang, et al. Electrical properties and temperature sensitivity of Li/Mg modified Ni0.7Zn0.3O based ceramics. J Alloys Compd 2018, 763: 975-982.
Publication history
Copyright
Acknowledgements
Rights and permissions

Publication history

Received: 20 March 2019
Revised: 20 June 2019
Accepted: 17 August 2019
Published: 05 February 2020
Issue date: February 2020

Copyright

© The author(s) 2019

Acknowledgements

This work was supported by National Key R&D Program of China (Grant No. 2017YFB0406405) and National Natural Science Foundation of China (Grant No. 61571203).

Rights and permissions

Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made.

The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder.

To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.

Reprints and Permission requests may be sought directly from editorial office.

Return