(Ti0.5W0.5)5+掺杂MgNb2O6陶瓷的晶体结构与太赫兹介电性能

doi:10.15541/jim20240512

无机材料学报 ›› 2025, Vol. 40 ›› Issue (6): 647-655.DOI: 10.15541/jim20240512

(Ti_0.5W_0.5)⁵⁺掺杂MgNb₂O₆陶瓷的晶体结构与太赫兹介电性能

黄子鹏¹^,²^,³(), 贾文晓¹^,²^,³, 李玲霞¹^,²^,³()

1.微电子学院, 天津大学, 天津 300072
2.先进陶瓷与加工技术教育部重点实验室, 天津大学, 天津 300072
3.天津市成像与感知微电子技术重点实验室, 天津 300072

收稿日期:2024-12-10 修回日期:2025-02-27 出版日期:2025-06-20 网络出版日期:2025-03-06
通讯作者: 李玲霞, 教授. E-mail: tjulingxiali_666@163.com
作者简介:黄子鹏(1994-), 男, 博士研究生. E-mail: hzptju613@163.com
基金资助:
国家自然科学基金(52172122);国家重点研发计划(2023YFB3812200);天津市自然科学基金(22JCQNJC00260)

Crystal Structure and Terahertz Dielectric Properties of (Ti_0.5W_0.5)⁵⁺ Doped MgNb₂O₆ Ceramics

HUANG Zipeng¹^,²^,³(), JIA Wenxiao¹^,²^,³, LI Lingxia¹^,²^,³()

1. School of Microelectronics, Tianjin University, Tianjin 300072, China
2. Key Laboratory for Advanced Ceramics and Machining Technology of Ministry of Education, Tianjin University, Tianjin 300072, China
3. Tianjin Key Laboratory of Imaging and Sensing Microelectronic Technology, Tianjin University, Tianjin 300072, China

Received:2024-12-10 Revised:2025-02-27 Published:2025-06-20 Online:2025-03-06
Contact: LI Lingxia, professor. E-mail: tjulingxiali_666@163.com
About author:HUANG Zipeng (1994-), male, PhD candidate. E-mail: hzptju613@163.com
Supported by:
National Natural Science Foundation of China(52172122);National Key R&D Program of China(2023YFB3812200);Natural Science Foundation of Tianjin(22JCQNJC00260)

摘要/Abstract

摘要：

MgNb₂O₆陶瓷具有烧结温度适中和介电损耗低等优点, 在无线通信领域有着广泛的应用。随着6G通信技术研发工作的开展, 通信频率将从微波频段迈向太赫兹频段。MgNb₂O₆陶瓷应用于太赫兹通信器件中可有效降低插入损耗, 增大相对带宽, 提高增益。然而, 目前仍缺乏关于MgNb₂O₆结构与太赫兹介电性能关联机制的深入研究。针对上述问题, 本研究采用固相反应法制备了MgNb_2-_x(Ti_0.5W_0.5)_xO₆(x=0~0.03)陶瓷。采用Rietveld精修、复杂化学键理论和太赫兹时域光谱等分析手段研究了MgNb_2-_x(Ti_0.5W_0.5)_xO₆(x=0~0.03)陶瓷的晶体结构与太赫兹介电性能之间的关联机制。基于上述分析手段, 在单相MgNb₂O₆体系中引入整体不稳定性指数表征晶格内应变, 建立了晶格内应变以及晶格能与太赫兹介电损耗的关联机制。研究结果表明, 掺入的(Ti_0.5W_0.5)⁵⁺离子可修饰晶体结构, 随着掺杂量增加, 减小了内应变, 增加了晶体结构的稳定性, 增大了晶格能, 进而降低了介电损耗。此外, 原子堆积密度随(Ti_0.5W_0.5)⁵⁺离子掺杂量增加而增大, 这意味着离子间排列更加紧密, 从而有效抑制了晶体的非简谐性振动, 进一步降低了介电损耗。最终, 1340 ℃烧结的MgNb_2-_x(Ti_0.5W_0.5)_xO₆(x=0.03)陶瓷具有优异的太赫兹介电性能: 介电常数(ε_r)为19.32, 介电损耗为0.003(@0.30 THz), 吸收系数为1.64 cm^-1(@0.30 THz)。本研究制备的MgNb_2-_x(Ti_0.5W_0.5)_xO₆(x=0.03)陶瓷在太赫兹器件中具有良好的应用前景。

关键词: MgNb₂O₆陶瓷, 晶体结构, 复杂化学键理论, 内应变, 太赫兹介电性能

Abstract:

MgNb₂O₆ ceramics offer advantages such as moderate sintering temperature and low dielectric loss, making them widely applicable in the field of wireless communications. However, the correlation mechanism between MgNb₂O₆ structure and terahertz dielectric properties remains inadequately understood. To address this gap, MgNb_2-_x(Ti_0.5W_0.5)_xO₆ (x=0-0.03) ceramics were prepared by solid state reaction method in this study. The crystal structure of MgNb_2-_x(Ti_0.5W_0.5)_xO₆ (x=0-0.03) ceramics and its correlation with terahertz dielectric properties were studied using Rietveld refinement, complex chemical bond theory, and terahertz time domain spectroscopy. The global instability index was introduced to characterize the in-lattice strain in single-phase MgNb₂O₆ system, establishing a correlation among in-lattice strain, lattice energy and terahertz dielectric loss. The results show that (Ti_0.5W_0.5)⁵⁺ ions can modify the crystal structure. With the increase in doping amount, the internal strain reduces, and the stability of crystal structure and lattice energy increases, leading to decrease in dielectric loss. In addition, the atomic packing density increases with higher (Ti_0.5W_0.5)⁵⁺ ion doping, which effectively inhibits the anharmonic vibration of the crystal and further reduces the dielectric loss. At a sintering temperature of 1340 ℃, MgNb_2-_x(Ti_0.5W_0.5)_xO₆ (x=0.03) ceramics have excellent terahertz dielectric properties, with a dielectric constant (ε_r) of 19.32, a dielectric loss of 0.003 (@0.30 THz), and an absorption coefficient of 1.64 cm^-1 (@0.30 THz). The MgNb_2-_x(Ti_0.5W_0.5)_xO₆ (x=0.03) ceramics prepared in this study have a good application prospect in terahertz devices.

Key words: MgNb₂O₆ ceramic, crystal structure, complex chemical bond theory, internal strain, terahertz dielectric property

中图分类号:

O484

黄子鹏, 贾文晓, 李玲霞. (Ti_0.5W_0.5)⁵⁺掺杂MgNb₂O₆陶瓷的晶体结构与太赫兹介电性能[J]. 无机材料学报, 2025, 40(6): 647-655.

HUANG Zipeng, JIA Wenxiao, LI Lingxia. Crystal Structure and Terahertz Dielectric Properties of (Ti_0.5W_0.5)⁵⁺ Doped MgNb₂O₆ Ceramics[J]. Journal of Inorganic Materials, 2025, 40(6): 647-655.

图/表 10

图1 MgNb2-x(Ti0.5W0.5)xO6(x=0~0.03)陶瓷的XRD分析

Fig. 1 XRD analyses of MgNb2-x(Ti0.5W0.5)xO6 (x=0-0.03) ceramics (a) XRD patterns; (b) Cell parameters obtained by XRD refinement

表1 MgNb2-x(Ti0.5W0.5)xO6(x=0~0.03)陶瓷XRD精修结果的可靠因子

Table 1 Reliability factor of XRD refinement results of MgNb2-x(Ti0.5W0.5)xO6 (x=0-0.03) ceramics

Parameter	x=0	x=0.01	x=0.02	x=0.03
R_wp/%	10.36	13.56	7.95	6.32
R_p/%	6.52	8.56	5.56	4.33

图2 MgNb2O6陶瓷的(a) XRD精修结果及(b)晶体结构图

Fig. 2 (a) XRD refinement result and (b) crystal structure of MgNb2O6 ceramic

图3 1340 ℃烧结的MgNb2-x(Ti0.5W0.5)xO6(x=0~0.03)陶瓷的表面微观形貌

Fig. 3 Surface morphologies of MgNb2-x(Ti0.5W0.5)xO6 (x=0-0.03) ceramics sintered at 1340 ℃ (a) x=0; (b) x=0.01; (c) x=0.02; (d) x=0.03; Insets: particle size distribution

表2 XRD精修得到的MgNb2-x(Ti0.5W0.5)xO6(x=0~0.03)陶瓷中的键长(Å)

Table 2 Bond lengths (Å) in MgNb2-x(Ti0.5W0.5)xO6 (x=0-0.03) ceramics obtained from XRD refinement

Bond		x=0.01	x=0.02
Mg–O1$\times $2	2.0012	1.9033	2.0632	2.0821
Mg–O2(1)$\times $2	1.9892	2.0423	2.0032	2.0262
Mg–O2(2)$\times $2	2.0122	2.4343	2.0792	2.0631
Nb–O1(1)$\times $1	2.0223	2.1123	2.0642	2.0322
Nb–O1(2)$\times $1	2.1072	2.1612	2.0092	2.0082
Nb–O2$\times $1	1.9621	1.8313	1.8341	1.8441
Nb–O3(1)$\times $1	2.1461	1.9962	2.1121	2.1431
Nb–O3(2)$\times $1	2.0542	2.1362	2.1362	2.1191
Nb–O3(3)$\times $1	2.0662	2.1723	2.0152	2.0002

图4 MgNb2-x(Ti0.5W0.5)xO6(x=0~0.03)陶瓷中Mg-O、Nb-O键的化学键特性

Fig. 4 Chemical bond characteristics of Mg-O and Nb-O bonds in MgNb2-x(Ti0.5W0.5)xO6 (x=0-0.03) ceramics (a) Average bond ionicity; (b) Average covalency; (c) Total lattice energy; (d) Total bond energy

图5 MgNb2-x(Ti0.5W0.5)xO6(x=0~0.03)陶瓷的(a)太赫兹介电常数和(b)密度

Fig. 5 (a) Terahertz dielectric constants and (b) densities of MgNb2-x(Ti0.5W0.5)xO6 (x=0-0.03) ceramics

图6 MgNb2-x(Ti0.5W0.5)xO6(x=0~0.03)陶瓷的(a)太赫兹介电损耗与(b)吸收系数

Fig. 6 (a) Terahertz dielectric loss and (b) absorption coefficient of MgNb2-x(Ti0.5W0.5)xO6 (x=0-0.03) ceramics

表3 MgNb2-x(Ti0.5W0.5)xO6(x=0~0.03)陶瓷的B位化学键键价(Sij(B-O))和整体不稳定性指数(GII)

Table 3 B position chemical bond valences (Sij(B-O)) and global instability indexes (GII) of MgNb2-x(Ti0.5W0.5)xO6 (x=0-0.03) ceramics

Parameter	x=0	x=0.01	x=0.02	x=0.03
S_ij(B-O)	4.0657	4.1612	4.5383	4.5777
GII	0.7896	0.6069	0.3914	0.3458

表4 MgNb2-x(Ti0.5W0.5)xO6(x=0~0.03)陶瓷的原子堆积密度

Table 4 Atomic packing densities of MgNb2-x(Ti0.5W0.5)xO6 (x=0-0.03) ceramics

Parameter	x=0	x=0.01	x=0.02	x=0.03
Atomic packing density/%	71.25	71.33	71.46	71.50

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(Ti_0.5W_0.5)⁵⁺掺杂MgNb₂O₆陶瓷的晶体结构与太赫兹介电性能

Crystal Structure and Terahertz Dielectric Properties of (Ti_0.5W_0.5)⁵⁺ Doped MgNb₂O₆ Ceramics

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