Microwave dielectric high-entropy ceramic Li(Gd0.2Ho0.2Er0.2Yb0.2Lu0.2)GeO4 with stable temperature coefficient for low-temperature cofired ceramic technologies

doi:10.1016/j.jmst.2021.03.057

Abstract

Abstract:

High-entropy ceramics are new single-phase materials with at least four cation or anion types. Their large configurational entropy is believed to enhance the simultaneous solubility of many components, which can be used to optimize certain properties. In this work, a high-entropy oxide, Li(Gd_0.2Ho_0.2Er_0.2Yb_0.2Lu_0.2)GeO₄ (LRG) was explored as a microwave dielectric ceramic for low-temperature cofired ceramic technologies. The LRG high-entropy ceramic with an olivine structure formed in the sintering temperature range of 1020-1100 °C. The minimal distortion (5 × 10^-4) of the [RO₆] octahedron led to a stable temperature coefficient of resonant frequency (τ_f) of -5.3 to -2.9 ppm/°C. Optimal microwave dielectric properties were achieved in the high-entropy ceramics at 1080 °C for 4 h with a relative density of 94.9%, a relative permittivity (ε_r) of 7.2, and a quality factor (Q×f) of 29000 GHz (at 15.3 GHz). For low-temperature cofired ceramic technology applications, the sintering temperature of the LRG high-entropy ceramic was reduced to 900 °C by the addition of 3 wt% H₃BO₃, which exhibited outstanding microwave dielectric properties (ε_r = 7.6, Q×f = 11700 GHz, and τ_f = -7.4 ppm/°C) and a good chemical compatibility with silver.

Key words: High-entropy ceramic, Octahedral distortion, Microwave dielectric properties, Stable τ_f

Huaicheng Xiang, Lei Yao, Junqi Chen, Aihong Yang, Haitao Yang, Liang Fang. Microwave dielectric high-entropy ceramic Li(Gd_0.2Ho_0.2Er_0.2Yb_0.2Lu_0.2)GeO₄ with stable temperature coefficient for low-temperature cofired ceramic technologies[J]. J. Mater. Sci. Technol., 2021, 93: 28-32.

Figures/Tables 6

Fig. 1. (a) XRD patterns of LRG high-entropy ceramic at different sintering temperatures. (b) Rietveld refinement of LRG high-entropy ceramic sintered at 1060 °C for 4 h. (c) Schematic of crystal structure of LRG high-entropy ceramic.

Table 1. Lattice parameters, cell volumes, and structures of LiRGeO4 (R = Gd, Ho, Er, Yb, Lu).

Material	a (Å)	b (Å)	c (Å)	V (Å³)	Structure	Refs.
LiGdGeO₄	7.30	7.30	9.61	512	Tetragonal	[22]
LiHoGeO₄	11.10	6.31	5.07	353	Orthorhombic	[22]
LiErGeO₄	11.10	6.33	5.04	352	Orthorhombic	[22]
LiYbGeO₄	10.94	6.25	5.02	343	Orthorhombic	[22]
LiLuGeO₄	11.1401	6.3333	5.0656	357.4190	Orthorhombic	This work
Li(Gd_0.2Ho_0.2Er_0.2Yb_0.2Lu_0.2)GeO₄	11.0481	6.3174	5.2062	363.3681	Orthorhombic	This work

Fig. 2. Variation of bulk density and relative density as a function of sintering temperature, and SEM images of LRG high-entropy ceramic sintered at different temperatures.

Fig. 3. Variation in (a) εr, (b) Q×f, and (d) τf of LRG high-entropy ceramic as a function of sintering temperature. (d) Schematic of change in oxygen octahedron of LRG and LiLuGeO4.

Table 2. The τf and oxygen octahedron information of Li-containing olivine microwave dielectric ceramics.

Ceramics	Crystal structure	oxygen octahedron	Type of bonds	Bond length (Å)	Octahedral distortion (Δ_octa.)	τ_f (ppm/°C)	Refs.
LiRGeO₄	Olivine	[RO]₆ octahedron	R-O1	2.2173	5×10^-4	-2.9	This work
			R-O2	2.1768
			R-O3 × 2	2.3127
			R-O3 × 2	2.2251
LiLuGeO₄	Olivine	[LuO]₆ octahedron	Lu-O1	2.2455	2.2×10^-3	-17.9	This work
			Lu-O2	2.5577
			Lu-O3 × 2	2.4299
			Lu-O3 × 2	2.2772
LiYGeO₄	Olivine	[YO]₆ octahedron	/	/	/	-27.7	[10]
LiYbSiO₄	Olivine	[YbO]₆ octahedron	/	/	7.5×10^-4	+4.52	[39]
Li₂ZnGeO₄	Olivine	/	/	/	/	-60.6	[9]
Li₂MgGeO₄	Olivine	/	/	/	/	-70.4	[9]

Fig. 4. XRD patterns of LRG + 3 wt.% H3BO3 and LRG + 3 wt.% H3BO3 + 15 wt.% Ag high-entropy ceramics sintered at 900 °C for 4 h. Inset shows backscattered electron image of LRG + 3 wt.% H3BO3 + 15 wt.% Ag ceramic.

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Microwave dielectric high-entropy ceramic Li(Gd_0.2Ho_0.2Er_0.2Yb_0.2Lu_0.2)GeO₄ with stable temperature coefficient for low-temperature cofired ceramic technologies

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