Significantly enhanced varistor properties of CaCu3Ti4O12 based ceramics by designing superior grain boundary: Deepening and broadening interface states

doi:10.1016/j.jmst.2021.07.057

Abstract

Abstract:

Significantly enhanced varistor properties via tailoring interface states were obtained in Ca_1-2_x_/3Y_xCu₃Ti₄O₁₂-SrCu₃Ti₄O₁₂ composite ceramics. The breakdown field was improved to 35.8 kV cm^-1 and the nonlinear coefficient in 0.1-1 mA cm^-2 was enhanced to 14.6 for Ca_0.67Y_0.5Cu₃Ti₄O₁₂-SrCu₃Ti₄O₁₂. Noticeably, the withstand voltage of single grain boundary reached up to 24 V while the reported ones were constant to about 3 V. Greatly improved properties were attributed to the formation of superior grain boundary rather than the reduced grain size. Surprisingly, with distinct discrepancy of nonlinear performance in the composites, the resistance and activation energy of grain boundary exhibited little differences. Based on the double Schottky barrier at grain boundary and the field-assisted thermal emission model, it was found that the excellent electrical nonlinearity arose from the formation of deeper and broader interface states at grain boundary. In this case, interface states were not easily entirely filled and the barrier could maintain its height under applied voltage. This work provides a novel routine for enhancing the varistor properties of CaCu₃Ti₄O₁₂ based ceramics by manipulating interface states at grain boundary.

Key words: Schottky barrier, Grain boundary, Varistor ceramics, Interface states

Zhuang Tang, Kai Ning, Zhiyao Fu, Ze Lian, Kangning Wu, Shoudao Huang. Significantly enhanced varistor properties of CaCu₃Ti₄O₁₂ based ceramics by designing superior grain boundary: Deepening and broadening interface states[J]. J. Mater. Sci. Technol., 2022, 108: 82-89.

Figures/Tables 13

Fig. 1. Nonlinear coefficient and breakdown field in reports of CCTO based ceramics.

Fig. 2. XRD patterns (a) and the enlarged view of the (220) peak (b) of the composite samples.

Table 1. Lattice constant (a), theoretical density (ρth), experimental density (ρex), and relative density (ρr) of the YCCTO-SCTO composite samples.

Samples	a (Å)	ρ_th (g cm^-3)	ρ_ex (g cm^-3)	ρ_r (%)
CCTO-SCTO	7.4030	5.21	4.77	91.6
0.1YCCTO-SCTO	7.4024	5.23	5.02	96.0
0.5YCCTO-SCTO	7.3974	5.26	4.76	90.5
0.9YCCTO-SCTO	7.3966	5.29	4.53	85.6

Fig. 3. Microstructures of 0 (a), 0.1 (b), 0.5 (c), 0.9 (d) YCCTO-SCTO composites.

Table 2. Ca/Sr distribution in various area of YCCTO-SCTO composite ceramic samples.

Elements (wt%)	CCTO-SCTO			0.1YCCTO-SCTO			0.5YCCTO-SCTO			0.9YCCTO-SCTO
Empty Cell	A1	A2	A3	B1	B2	B3	C1	C2	C3	D1	D2	D3
Ca	6.13	2.42	0.58	6.45	3.27	0.88	5.92	3.53	0.33	5.77	2.84	0.34
Sr	0.00	14.31	49.72	0.00	13.41	47.32	0.00	12.60	44.03	0.00	12.07	39.39
Y	0.00	0.00	0.00	0.30	0.99	4.11	0.36	1.86	14.78	2.83	4.77	20.90

Fig. 4. Nonlinear current-voltage characteristics (a) and dielectric properties (b) of the composite ceramics.

Table 3. Breakdown field (Egb), nonlinear coefficient (α), withstood voltage on single grain boundary (Ugb) of the YCCTO-SCTO composite ceramics.

Parameters	CCTO-SCTO	0.1YCCTO-SCTO	0.5YCCTO-SCTO	0.9YCCTO-SCTO
E_b (kV cm^-1)	25.34	32.36	35.82	22.42
α	7.28	8.09	14.65	8.33
U_gb (V)	8.82	20.68	24.42	15.86

Fig. 5. Impedance spectra (a) and Arrhenius plots of resistivity of grain boundary (b) of the composite ceramic samples.

Fig. 6. Comparison of breakdown field (a), nonlinear coefficient (b), grain boundary resistivity (c) and its activation energy (d) of the composite samples to that of CCTO ceramics. (The numbers of 0-4 refer to CCTO, CCTO-SCTO, 0.1YCCTO-SCO, 0.5YCCTO-SCTO and 0.9YCTO-SCTO, respectively.).

Fig. 7. Summary of the reported breakdown field and withstand voltage on single GB.

Fig. 8. Dependence of capacitance on voltage of the composite samples.

Table 4. Donor density Nd, interface density Ns, Schottky barrier height under zero voltage ϕ0 and depletion layer width of the YCCTO-SCTO composite ceramics.

Samples	ϕ₀ (eV)	N_d (10²⁴ m^-3)	Q_i0/e (10¹⁷ m^-2)	w (nm)
CCTO-SCTO	0.94	8.39	5.29	31.53
0.1YCCTO-SCTO	0.96	10.79	6.05	28.03
0.5YCCTO-SCTO	0.98	6.20	4.65	37.51
0.9YCCTO-SCTO	1.01	24.23	9.32	19.23

Fig. 9. Schematic of double Schottky barrier (a) and voltage dependence of barrier height and interfacial charge density of the composite ceramics (b). Schematic diagram of forming board and deep interface states in CCTO based composites (c) and calculated distribution of interface states of the composite samples (d).

References 47

[1]	Y. Wang, W. Jie, C. Yang, X. Wei, J. Hao, Adv. Funct. Mater. 29 (2019) 1808118.
[2]	F. Yan, Y. Shi, X. Zhou, K. Zhu, B. Shen, J. Zhai, Chem. Eng. J. 417 (2020) 127945. DOI URL
[3]	L. Zhang, Y. Pu, M. Chen, T. Wei, X. Peng, Chem. Eng. J. 383 (2020) 123154. DOI URL
[4]	A.P. Ramirez, M.A. Subramanian, M. Gardel, G. Blumberg, D. Li, T. Vogt, S.M. Shapiro, Solid State Commun. 115 (2000) 217-220. DOI URL
[5]	R. Schmidt, M.C. Stennett, N.C. Hyatt, J. Pokorny, J. Prado-Gonjal, M. Li, D.C. Sin- clair, J. Eur. Ceram. Soc. 32 (2012) 3313-3323. DOI URL
[6]	M.A. Subramanian, A.W. Sleight, Solid State Sci. 4 (2002) 347-351. DOI URL
[7]	M. Ahmadipour, M.F. Ain, Z.A. Ahmad, Nano Micro Lett. 8 (2016) 291-311.
[8]	N.T. Taylor, F.H. Davies, S.G. Davies, C.J. Price, S.P. Hepplestone, Adv. Mater. 31 (2019) 1904746. DOI URL
[9]	S.Y. Chung, I.D. Kim, S.J. Kang, Nat. Mater. 3 (2004) 774-778. DOI URL
[10]	M.A. Ramírez, P.R. Bueno, J.A. Varela, E. Longo, Appl. Phys. Lett. 89 (2006) 212102. DOI URL
[11]	M. Maleki Shahraki, S. Alipour, P. Mahmoudi, A. Karimi, Ceram. Int. 44 (2018) 20386-20390. DOI URL
[12]	Z. Tang, K. Wu, J. Li, S. Huang, J. Eur. Ceram. Soc. 40 (2020) 3437-34 4 4. DOI URL
[13]	Z. Peng, J. Li, P. Liang, Z. Yang, X. Chao, J. Eur. Ceram. Soc. 37 (2017) 4637-4644. DOI URL
[14]	B. Cheng, Y. Lin, W. Deng, J. Cai, J. Lan, C. Nan, X. Xiao, J. He, J. Electroceram. 29 (2012) 250-253. DOI URL
[15]	T. Li, Z. Chen, F. Chang, J. Hao, J. Zhang, J. Alloys Compd. 484 (2009) 718-722. DOI URL
[16]	L. Liu, L. Fang, Y. Huang, Y. Li, D. Shi, S. Zheng, S. Wu, C. Hu, J. Appl. Phys. 110 (2011) 094101. DOI URL
[17]	J. Yuan, Y. Lin, H. Lu, B. Cheng, C. Nan, J. Am. Ceram. Soc. 94 (2011) 1966-1969. DOI URL
[18]	T. Li, Y. Sun, H.Y. Dai, D.W. Liu, J. Chen, R.Z. Xue, Z.Q. Chen, J. Alloys Compd. 829 (2020) 154595. DOI URL
[19]	L. Liu, H. Fan, P. Fang, X. Chen, Mater. Res. Bull. 43 (2008) 1800-1807. DOI URL
[20]	P. Mao, J. Wang, L. Zhang, S. Liu, Y. Zhao, Q. Sun, J. Mater. Sci. Mater. Electron. 30 (2019) 13401-13411. DOI URL
[21]	S. Pongpaiboonkul, T.M. Daniels, J.H. Hodak, A. Wisitsoraat, S.K. Hodak, Appl. Surf. Sci. 540 (2021) 148373. DOI URL
[22]	E.C. Grzebielucka, J.F.H. Leandro Monteiro, E.C.F. de Souza, C.P. Ferreira Borges, A.V.C. de Andrade, E. Cordoncillo, H. Beltrán-Mir, S.R.M. Antunes, J. Mater. Sci. Technol. 41 (2020) 12-20. DOI
[23]	L. Ren, L. Yang, C. Xu, X. Zhao, R. Liao, J. Alloys Compd. 768 (2018) 652-658. DOI URL
[24]	Z. Tang, K. Wu, J. Li, S. Huang, Ceram. Int. 46 (2020) 16949-16955. DOI URL
[25]	J. Boonlakhorn, N. Chanlek, P. Thongbai, P. Srepusharawoot, J. Phys. Chem. C 124 (2020) 20682-20692. DOI URL
[26]	J. Li, K. Wu, R. Jia, L. Hou, L. Gao, S. Li, Mater. Des. 92 (2016) 546-551. DOI URL
[27]	P. Mao, J. Wang, L. He, L. Zhang, A. Annadi, F. Kang, Q. Sun, Z. Wang, H. Gong, ACS Appl. Mater. Interfaces 12 (2020) 4 8781-4 8793.
[28]	D.C. Sinclair, T.B. Adams, F.D. Morrison, A.R. West, Appl. Phys. Lett. 80 (2002) 2153-2155. DOI URL
[29]	A. Cho, C.S. Han, M. Kang, W. Choi, J. Lee, J. Jeon, S. Yu, Y.S. Jung, Y.S. Cho, ACS Appl. Mater. Interfaces 10 (2018) 16203-16209. DOI URL
[30]	K. Wu, Y. Wang, Z. Hou, S. Li, J. Li, Z. Tang, Y. Lin, J. Phys. D Appl. Phys. 54 (2021) 045301. DOI URL
[31]	Z. Tang, Y. Huang, K. Wu, J. Li, J. Eur. Ceram. Soc. 38 (2018) 1569-1575. DOI URL
[32]	J. Boonlakhorn, P. Kidkhunthod, B. Putasaeng, T. Yamwong, P. Thongbai, S. Maensiri, J. Mater. Sci. Mater. Electron. 26 (2015) 2329-2337. DOI URL
[33]	L. Tang, F. Xue, P. Guo, Z. Xin, Z. Luo, W. Li, Ceram. Int. 44 (2018) 18535-18540. DOI URL
[34]	D. Mori, M. Shimoi, Y. Kato, T. Katsumata, K. Hiraki, T. Takahashi, Y. Inaguma, Ferroelectrics 414 (2011) 180-189. DOI URL
[35]	K. Wu, Y. Huang, J. Li, S. Li, Appl. Phys. Lett. 111 (2017) 042902. DOI URL
[36]	Y. Huang, K. Wu, Z. Xing, C. Zhang, X. Hu, P. Guo, J. Zhang, J. Li, J. Appl. Phys. 125 (2019) 084103. DOI URL
[37]	K. Wu, Y. Huang, L. Hou, Z. Tang, J. Li, S. Li, J. Mater. Sci. Mater. Electron. 29 (2018) 4 488-4 494.
[38]	P. Mao, J. Wang, S. Liu, L. Zhang, Y. Zhao, K. Wu, Z. Wang, J. Li, Ceram. Int. 45 (2019) 15082-15090. DOI
[39]	J. Wang, Z. Lu, T. Deng, C. Zhong, Z. Chen, J. Eur. Ceram. Soc. 38 (2018) 3505-3511. DOI URL
[40]	P. Saengvong, J. Boonlakhorn, N. Chanlek, B. Putasaeng, P. Thongbai, Ceram. Int. 46 (2020) 9780-9785. DOI URL
[41]	J. Jumpatam, B. Putasaeng, N. Chanlek, J. Boonlakhorn, P. Thongbai, N. Phromviyo, P. Chindaprasirt, Mater. Res. Bull. 133 (2021) 111043. DOI URL
[42]	R. Jia, X. Zhao, J. Li, X. Tang, Mater. Sci. Eng B 185 (2014) 79-85. DOI URL
[43]	A.A. Felix, L.A. Saska, V.D.N. Bezzon, M. Cilense, Cilense, Ceram. Int 45 (2019) 14305-14311.
[44]	K. Prompa, E. Swatsitang, C. Saiyasombat, T. Putjuso, Ceram. Int. 44 (2018) 13267-13277. DOI URL
[45]	J. Jumpatam, B. Putasaeng, T. Yamwong, P. Thongbai, S. Maensiri, J. Eur. Ceram. Soc. 34 (2014) 2941-2950. DOI URL
[46]	P. Thongbai, J. Boonlakhorn, B. Putasaeng, T. Yamwong, S. Maensiri, J. Am. Ceram. Soc. 96 (2013) 379-381. DOI URL
[47]	G. Blatter, F. Greuter, Phys. Rev. B 33 (1986) 3952-3966. PMID

Significantly enhanced varistor properties of CaCu₃Ti₄O₁₂ based ceramics by designing superior grain boundary: Deepening and broadening interface states

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