钒取代对LaTaO4陶瓷微观结构和微波介电性能的影响

doi:10.15541/jim20240482

无机材料学报 ›› 2025, Vol. 40 ›› Issue (6): 697-703.DOI: 10.15541/jim20240482

钒取代对LaTaO₄陶瓷微观结构和微波介电性能的影响

李文元¹^,²(), 徐佳楠¹^,², 邓瀚澳¹, 常爱民¹, 张博¹()

1.中国科学院新疆理化技术研究所, 特殊环境条件功能材料与器件重点实验室, 新疆电子信息材料与器件重点实验室, 乌鲁木齐 830011
2.中国科学院大学材料科学与光电技术学院, 北京 100049

收稿日期:2024-11-13 修回日期:2024-12-31 出版日期:2025-06-20 网络出版日期:2025-01-09
通讯作者: 张博, 研究员. E-mail: zhangbocas@ms.xjb.ac.cn
作者简介:李文元(1999-), 男, 博士研究生. E-mail: liwenyuan22@mails.ucas.ac.cn
基金资助:
国家自然科学基金(62471468);中国科学院青年创新促进会项目(Y2023117);新疆自然科学基金(2024D01E32);新疆天山英才培养计划(2023TSYCCX0092)

Effect of V⁵⁺ Substitution on Microstructure and Microwave Dielectric Properties of LaTaO₄ Ceramics

LI Wenyuan¹^,²(), XU Jianan¹^,², DENG Han'ao¹, CHANG Aimin¹, ZHANG Bo¹()

1. State Key Laboratory of Functional Materials and Devices for Special Environmental Conditions, Xinjiang Key Laboratory of Electronic Information Materials and Devices, Xinjiang Technical Institute of Physics & Chemistry, Chinese Academy of Sciences, Urumqi 830011, China
2. Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China

Received:2024-11-13 Revised:2024-12-31 Published:2025-06-20 Online:2025-01-09
Contact: ZHANG Bo, professor. E-mail: zhangbocas@ms.xjb.ac.cn
About author:LI Wenyuan (1999-), male, PhD candidate. E-mail: liwenyuan22@mails.ucas.ac.cn
Supported by:
National Natural Science Foundation of China(62471468);Youth Innovation Promotion Association of CAS(Y2023117);Natural Science Foundation of Xinjiang(2024D01E32);Xinjiang Tianshan Talent Training Program(2023TSYCCX0092)

摘要/Abstract

摘要：

微波介质陶瓷是5G/6G通信技术的关键材料, 广泛应用于谐振器、滤波器、介质基板等电子元器件。随着无线移动通信频率的不断提升, 对微波介质陶瓷提出了更高要求, 特别是需要更高的品质因数(Q)和接近零的谐振频率温度系数(τ_f), 以有效补偿高频信号在传输过程中迅速衰减, 并提高其工作稳定性。本研究采用固相烧结法制备了La(Ta_1-_xV_x)O₄(LTV-x, 0≤x≤0.4)陶瓷, 并通过晶体结构精修、透射电子显微镜和微波介电测试, 研究了其结构和介电性能。在该体系中合成了两种具有优异微波介电性能的La(Ta_1-_xV_x)O₄陶瓷, 分别为LTV-0.3(相对介电常数ε_r=22.15, Q×f=90100 GHz, τ_f=-9.52×10^-6 ℃^-1)和LTV-0.4(ε_r=21.75, Q×f=84100 GHz, τ_f=-4.50×10^-6 ℃^-1)陶瓷。研究发现, V⁵⁺取代诱导了LaTaO₄从单斜相(P21/c)向正交相(Cmc21)转变, 并有效降低了相变温度。随着x增加, ε_r和τ_f均呈下降趋势。Q×f不仅与相对密度有关, 还与晶胞的堆积分数有关。鉴于其低损耗和良好的温度稳定性, 该系列陶瓷材料在移动通信基站、卫星导航和雷达通信等领域展现出良好的应用前景。

关键词: LaTaO₄, 微波介电性能, 谐振频率温度系数, 离子取代, 堆积分数

Abstract:

Microwave dielectric ceramics are essential materials for 5G/6G communication technology and are primarily employed in fabrication of electronic components such as resonators, filters and dielectric substrates. With the increasing frequency of wireless mobile communication, it is necessary to develop microwave dielectric ceramics with higher quality factor (Q) and near-zero temperature coefficient of resonance frequency (τ_f), thus effectively compensating for rapid attenuation of high-frequency signals in transmission process and enhancing stability of their operation. Consequently, La(Ta_1-_xV_x)O₄ (LTV-x, 0≤x≤0.4) ceramics were prepared by solid-phase sintering. The structure and dielectric properties of ceramics were investigated using crystal structure refinement, transmission electron microscopy and microwave dielectric property measurements. Two specific compositions of La(Ta_1-_xV_x)O₄ ceramics with excellent microwave dielectric properties were synthesized in this system, namely LTV-0.3 (relative dielectric constant ε_r=22.15, Q×f=90100 GHz, τ_f=-9.52×10^-6 ℃^-1) and LTV-0.4 (ε_r=21.75, Q×f=84100 GHz, τ_f=-4.50×10^-6 ℃^-1) ceramics. Results indicate that V⁵⁺ substitution induces the phase transition of LaTaO₄from monoclinic (P21/c) to orthorhombic (Cmc21) phases, while the phase transition temperature is effectively reduced. Their ε_r and τ_f values decrease with increasing x due to phase transition. The Q×f values are influenced not only by relative density but also by packing fraction of the unit cell. Considering their low loss and good temperature stability, these ceramic materials demonstrate promising potential for applications in mobile communication base stations, satellite navigation and radar communication technologies.

Key words: LaTaO₄, microwave dielectric property, temperature coefficient of resonance frequency, ionic substitution, packing fraction

中图分类号:

TQ174

李文元, 徐佳楠, 邓瀚澳, 常爱民, 张博. 钒取代对LaTaO₄陶瓷微观结构和微波介电性能的影响[J]. 无机材料学报, 2025, 40(6): 697-703.

LI Wenyuan, XU Jianan, DENG Han'ao, CHANG Aimin, ZHANG Bo. Effect of V⁵⁺ Substitution on Microstructure and Microwave Dielectric Properties of LaTaO₄ Ceramics[J]. Journal of Inorganic Materials, 2025, 40(6): 697-703.

图/表 6

图1 1400 ℃烧结4 h制备的LTV-x(0≤x≤0.4)陶瓷的(a)XRD图谱和(b~f) Rietveld精修拟合图

Fig. 1 XRD patterns (a) and Rietveld refinement XRD patterns (b-f) of LTV-x ceramics sintered at 1400 ℃ for 4 h

图2 LTV-x陶瓷的SEM照片和A区的EDS元素面分析

Fig. 2 SEM images of LTV-x ceramics and EDS mappings of area A (a-e) SEM images of LTV-x ceramics (x=(a) 0, (b) 0.1, (c) 0.2, (d) 0.3, (e) 0.4); (f) Variation of grain size as a function of composition; (g-j) EDS mappings of area A in (d)

图3 LTV-0.3陶瓷的TEM和HRTEM表征结果

Fig. 3 TEM and HRTEM characterizations of LTV-0.3 ceramics (a, b) TEM images; (a1, b1) SAED patterns corresponding to area 1 and 2; (a2, b2) HRTEM images of orthorhombic-phase LaTaO4 and monoclinic-phase LaVO4 corresponding to area Ⅰ and Ⅱ

图4 LTV-x陶瓷在不同温度烧结的表观密度和1400 ℃烧结的相对密度

Fig. 4 Apparent densities of LTV-x ceramics sintered at different temperatures and relative densities of ceramics sintered at 1400 ℃

图5 1400 ℃烧结LTV-x陶瓷的微波介电性能

Fig. 5 Microwave dielectric properties of LTV-x ceramics sintered at 1400 ℃ (a) Permittivity (εr: measured; εtheo: calculated by Shannon’s additive rule and Clausius-Mossotti relation; εcor: modified by Bosman and Havinga correction); (b) Q×f, relative density, and packing fraction; (c) Evolution of τf as a functions of x for LTV-x ceramics

表S1 Rietveld精修得到的LTV-x陶瓷的晶胞参数和可靠因子

Table S1 Lattice parameters and reliable factors of LTV-x ceramics obtained by the Rietveld profile refinement method

x	Atom	Atom position			Mult	Occupancy	Refining reliability factor		Volume/Å³
x	Atom	x	y	z	Mult	Occupancy	R_wp/%	R_p/%	Volume/Å³
0	La1	0.0000	0.6292	0.2500	4	1.0000	8.45	6.18	326.04
	Ta1	0.0000	0.1036	0.2500	4	1.0000
	O1	0.1460	0.2042	0.1572	8	1.0000
	O2	0.2624	0.4663	0.3170	8	1.0000
0.1	La1	0.0000	0.6292	0.2500	4	1.0000	7.54	5.71	325.41
	Ta1	0.0000	0.1036	0.2500	4	0.9000
	V1	0.0000	0.1036	0.2500	4	0.1000
	O1	0.1460	0.2042	0.1572	8	1.0000
	O2	0.2624	0.4663	0.3170	8	1.0000
0.2	La1	0.0000	0.6292	0.2500	4	1.0000	8.62	6.42	324.98
	Ta1	0.0000	0.1036	0.2500	4	0.8000
	V1	0.0000	0.1036	0.2500	4	0.2000
	O1	0.1460	0.2042	0.1572	8	1.0000
	O2	0.2624	0.4663	0.3170	8	1.0000
0.3	La1	0.0000	0.6292	0.2500	4	1.0000	7.39	5.97	323.85
	Ta1	0.0000	0.1036	0.2500	4	0.7000
	V1	0.0000	0.1036	0.2500	4	0.3000
	O1	0.1460	0.2042	0.1572	8	1.0000
	O2	0.2624	0.4663	0.3170	8	1.0000
0.4	La1	0.0000	0.6292	0.2500	4	1.0000	9.27	7.24	323.61
	Ta1	0.0000	0.1036	0.2500	4	0.6000
	V1	0.0000	0.1036	0.2500	4	0.4000
	O1	0.1460	0.2042	0.1572	8	1.0000
	O2	0.2624	0.4663	0.3170	8	1.0000

参考文献 26

[1]	LI J, WANG Z, GUO Y, et al. Influences of substituting of (Ni_1/3Nb_2/3)⁴⁺ for Ti⁴⁺on the phase compositions, microstructures, and dielectric properties of Li₂Zn[Ti_1-_x(Ni_1/3Nb_2/3)_x]₃O₈(0≤x≤0.3) microwave ceramics. J. Adv. Ceram., 2023, 12(4): 760.
[2]	FENG C, ZHOU X, TAO B, et al. Crystal structure and enhanced microwave dielectric properties of the Ce₂[Zr_1-_x(Al_1/2Ta_1/2)_x]₃(MoO₄)₉ ceramics at microwave frequency. J. Adv. Ceram., 2022, 11(3): 392.
[3]	WANG J, CHONG X Y, ZHOU R, et al. Microstructure and thermal properties of RETaO₄ (RE=Nd, Eu, Gd, Dy, Er, Yb, Lu) as promising thermal barrier coating materials. Scr. Mater., 2017, 126: 24.
[4]	CHEN L, JIANG Y H, CHONG X Y, et al. Synthesis and thermophysical properties of RETa₃O₉ (RE=Ce, Nd, Sm, Eu, Gd, Dy, Er) as promising thermal barrier coatings. J. Am. Ceram. Soc., 2018, 101: 1266.
[5]	WU P, CHONG X Y, WU F S, et al. Investigation of the thermophysical properties of (Y_1-_xYb_x)TaO₄ ceramics. J. Eur. Ceram. Soc., 2020, 40(8): 3111.
[6]	WANG G, ZHANG D N, HUANG X, et al. Crystal structure and enhanced microwave dielectric properties of Ta⁵⁺ substituted Li₃Mg₂NbO₆ ceramics. J. Am. Ceram. Soc., 2020, 103(1): 214.
[7]	LEE H J, HONG K S, KIM I T. Crystal structure and microwave dielectric properties of M(Nb_xTa_1-_x)₂O₆ solid solution (M=Mg or Zn). J. Mater. Res., 2011, 12: 1437.
[8]	ZHANG P, ZHAO Y G, LIU J, et al. Enhanced microwave dielectric properties of NdNbO₄ ceramic by Ta⁵⁺ substitution. J. Alloys Compd., 2015, 649: 90.
[9]	HAUGSRUD R, NORBY T. Proton conduction in rare-earth ortho-niobates and ortho-tantalates. Nat. Mater., 2006, 5: 193.
[10]	FORBES T Z, NYMAN M, RODRIGUEZ M A, et al. The energetics of lanthanum tantalate materials. J. Solid State Chem., 2010, 183: 2516.
[11]	MACHIDA M, MURAKAMI S, KIJIMA T, et al. Photocatalytic property and electronic structure of lanthanide tantalates, LnTaO₄ (Ln=La, Ce, Pr, Nd, and Sm). J. Phys. Chem. B, 2001, 105: 3289.
[12]	SHANNON R D. Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallogr., 1976, 32: 751.
[13]	BOSMAN A J, HAVINGA E E. Temperature dependence of dielectric constants of cubic ionic compounds. Phys. Rev., 1963, 129: 1593.
[14]	SHANNON R D. Dielectric polarizabilities of ions in oxides and fluorides. Appl. Phys., 1993, 73: 348.
[15]	HAKKI B W, COLEMAN P D. A dielectric resonator method of measuring inductive capacities in the millimeter range. IEEE Trans. Microw. Theory Tech., 1960, 8(4): 402.
[16]	KIM D W, KWOND K, YOON S H, et al. Microwave dielectric properties of rare-earth ortho-niobates with ferroelasticity. J. Am. Ceram. Soc., 2006, 89(12): 3861.
[17]	GUO D, ZHOU D, LI W B, et al. Phase evolution, crystal structure, and microwave dielectric properties of water-insoluble (1-x)LaNbO₄-xLaVO₄ (0≤x≤0.9) ceramics. Inorg. Chem., 2017, 56(15): 9321.
[18]	BAO J, DU J L, LIU L T. A new type of microwave dielectric ceramic based on K₂O-SrO-P₂O₅ composition with high quality factor and low sintering temperature. Ceram. Int., 2021, 48: 784.
[19]	LIAO Q W, LI L X, REN X, et al. New low-loss microwave dielectric material ZnTiNbTaO₈. J. Am. Ceram. Soc., 2011, 94: 3237.
[20]	WU F F, ZHOU D, DU C, et al. Temperature stable Sm(Nb_1-_xV_x)O₄ (0.0≤x≤0.9) microwave dielectric ceramics with ultra-low dielectric loss for dielectric resonator antenna applications. J. Mater. Chem. C, 2021, 9: 9962.
[21]	YANG M, ZOU H X, YANG H M, et al. Phase composition and microwave dielectric properties of NaSrB₅₊₅_xO_9+7.5_x composite ceramics. J. Eur. Ceram. Soc., 2023, 43(5): 1964.
[22]	XIANG H C, FANG L, JIANG X W, et al. A novel temperature stable microwave dielectric ceramic with garnet structure: Sr₂NaMg₂V₃O₁₂. J. Am. Ceram. Soc., 2016, 99: 399.
[23]	WANG Y, ZUO R Z, ZHANG C, et al. Low-temperature-fired ReVO₄ (Re=La, Ce) microwave dielectric ceramics. J. Am. Ceram. Soc., 2015, 98(1): 1.
[24]	KIM W S, KIM T H, KIM E S, et al. Microwave dielectric properties and far infrared reflectivity spectra of the (Zr_0.8Sn_0.2)TiO₄ ceramics with additives. Jpn. J. Appl. Phys., 1998, 37: 5367.
[25]	CAO Y C, ZHANG L B, MEI H R, et al. Crystal structure, phonon characteristics, and dielectric properties of CaMgGe₂O₆: a novel diopside microwave dielectric ceramic. Ceram. Int., 2022, 48(6): 8783.
[26]	DU K, YIN C Z, YANG J Q, et al. Crystal structure, far-infrared spectra, and microwave dielectric properties of bazirite-type BaZr(Si_1-_xGe_x)₃O₉ ceramics. Ceram. Int., 2022, 48(3): 3592.

钒取代对LaTaO₄陶瓷微观结构和微波介电性能的影响

Effect of V⁵⁺ Substitution on Microstructure and Microwave Dielectric Properties of LaTaO₄ Ceramics

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 6

参考文献 26

相关文章 15

编辑推荐

Metrics

本文评价

[1]	唐莹, 李洁, 相怀成, 方维双, 林慧兴, 杨俊峰, 方亮. Rattling效应: 一种影响微波介质陶瓷谐振频率温度系数的新机制[J]. 无机材料学报, 2025, 40(6): 656-666.
[2]	尹长志, 成名飞, 雷微程, 蔡弋炀, 宋小强, 付明, 吕文中, 雷文. Ga³⁺掺杂对SrAl₂Si₂O₈陶瓷晶体结构及微波介电性能的影响[J]. 无机材料学报, 2025, 40(6): 704-710.
[3]	熊思宇, 莫尘, 朱肖伟, 朱国斌, 陈德钦, 刘来君, 施晓东, 李纯纯. 超低介电常数LiB_xAl_1-_xSi₂O₆微波介质陶瓷的低温烧结[J]. 无机材料学报, 2025, 40(5): 536-544.
[4]	屈婧婧, 魏星, 刘飞, 袁昌来, 陈国华, 黄先培. 热处理对Mg-Al-Si-Ti-B系微晶玻璃析晶及介电性能的影响[J]. 无机材料学报, 2018, 33(12): 1309-1315.
[5]	刘飞, 黄先培, 袁昌来, 陈国华. 烧结温度和CaTiO₃添加对不稳定层状Ca_n₊₁Ti_nO₃_n+₁(n = 1)陶瓷体系结构与介电性能的影响[J]. 无机材料学报, 2017, 32(5): 489-494.
[6]	屈婧婧, 魏星, 宋小辉, 袁昌来, 刘飞. B位(Mg_1/3Ta_2/3)⁴⁺置换对新型Sr基(Sr, Nd, Ca)TiO₃微波陶瓷结构及介电性能的影响[J]. 无机材料学报, 2017, 32(3): 293-298.
[7]	张瑶, 丁士华, 刘杨琼, 段绍英, 肖鹏, 韩林材. Ba_1-_xMg_xAl₂Si₂O₈晶体结构与微波介电性能的研究[J]. 无机材料学报, 2017, 32(1): 91-95.
[8]	张康, 李蔚, 林慧兴. MgO/Eu₂O₃共掺杂对Al₂O₃陶瓷微波介电性能的影响[J]. 无机材料学报, 2015, 30(9): 984-988.
[9]	苏静杰, 杨梓, 李义锋, 唐伟忠, 安晓明, 郭辉. 分体圆柱谐振腔法用于金刚石膜微波介电性能测试的研究[J]. 无机材料学报, 2015, 30(7): 751-756.
[10]	屈婧婧, 魏星, 经本钦, 刘飞, 袁昌来. 高Q值(1-x)(Sr_0.2Nd_0.208Ca_0.488)TiO₃-xNd(Ti_0.5Mg_0.5)O₃微波陶瓷的微结构及介电性能研究[J]. 无机材料学报, 2015, 30(11): 1213-1217.
[11]	刘林, 方有维, 邓新峰, 庄文东, 唐斌, 张树人. (Ba_1-xSr_x)La₄Ti₄O₁₅(x=0.8~0.95)陶瓷的微结构及微波介电性能研究[J]. 无机材料学报, 2012, 27(3): 281-284.
[12]	刘昊, 沈春英, 卢正东, 丘泰. (1-x)(Mg_0.9Co_0.1)TiO₃-x(Ca_0.61La_0.26)TiO₃陶瓷的微波介电性能[J]. 无机材料学报, 2011, 26(6): 664-668.
[13]	赵莉, 沈春英, 丘泰. (1- x)(Mg_0.7Zn_0.3)TiO₃– xCa_0.61La_0.26TiO₃系陶瓷的微波介电性能研究[J]. 无机材料学报, 2011, 26(2): 219-224.
[14]	卢正东,沈春英,李亮,杨建,丘泰. (1-x)(Mg_0.7Zn_0.3)TiO₃－x(Ca_0.61Nd_0.26)TiO₃系微波介质陶瓷介电性能研究[J]. 无机材料学报, 2010, 25(3): 332-336.
[15]	雷文,吕文中,王晓川,梁军,江建军. CaTiO₃对(1-x)ZnAl₂O₄-xMg₂TiO₄(x=0.21)微波介质陶瓷结构和性能的影响[J]. 无机材料学报, 2009, 24(5): 957-961.