Lattice evolution, order transformation, and microwave dielectric properties of the Zn1−xLi2xTiO3 (0 ≤ x ≤ 1) system ceramics

Qianbiao Du; Longxiang Jiang; Linzhao Ma; Jianhong Duan; Zeyan Zhou; Hao Li

doi:10.26599/JAC.2024.9220927

AI Chat Paper

Note: Please note that the following content is generated by AMiner AI. SciOpen does not take any responsibility related to this content.

Chat more with AI

| Sign up

Browse by Subject

Search for peer-reviewed journals with full access.

Journals A - Z

About Us

Discover the SciOpen Platform and Achieve Your Research Goals with Ease.

About Us

Publish with Us

Support

Search articles, authors, keywords, DOl and etc.

Published Date

Reset Search

{{expandStatus?'Exit ':''}}Advanced Search

Journals A - Z

About Us

Publish with Us

Support

PDF (17.5 MB)

Cite

EndNote(RIS) BibTeX

Collect

Submit Manuscript

AI Chat Paper

Show Outline

Outline

Show full outline

Hide outline

Outline

Show full outline

Hide outline

Research Article | Open Access

Lattice evolution, order transformation, and microwave dielectric properties of the Zn_1−xLi_2xTiO₃ (0 ≤ x ≤ 1) system ceramics

Qianbiao Du^¹, Longxiang Jiang^¹, Linzhao Ma^¹, Jianhong Duan^¹, Zeyan Zhou^²(

), Hao Li^¹(

)

1College of Electrical and Information Engineering, Hunan University, Changsha 410082, China

2College of Materials Science and Engineering, Hunan University, Changsha 410082, China

Show Author Information

Graphical Abstract

Abstract

Research on doping modification of ZnTiO₃ ceramics to enhance microwave dielectric properties has been hindered by poor performance, unclear structure-function mechanisms. To expand the applicability of ZnTiO₃ ceramics, this study explores Zn_1–xLi_2xTiO₃ (0 ≤ x ≤ 1) ceramics using a phase engineering strategy. Our findings reveal that the introduction of Li⁺ into the ZnTiO₃ system initiates a multiple phase transition, starting at x = 0.1. Initially, ilmenite ZnTiO₃ transforms into a cubic ordered spinel phase (space group P4332). Subsequently, a transition to a disordered spinel phase (space group Fd $\bar{3}$ m) occurs at x = 0.5, culminating in the formation of a monoclinic rock salt-structured Li₂TiO₃ phase. Significantly, two sets of ceramics with near-zero temperature coefficients of resonance frequency (τ_f) were obtained at x = 0.1 and 0.75. Moreover, the quality factor (Q×f) demonstrated a 4.4-fold increase compared to that of ZnTiO₃ ceramics at x = 0.25 (105,013 GHz). Additionally, it was observed that the Ti⁴⁺ polarization in Zn_1−xLi_2xTiO₃ ceramics was underestimated by 11.3%–13.3%, causing the measured dielectric constant (ε_r) exceeding the theoretical dielectric constant (ε_th). The ionic polarizability of Ti⁴⁺ was adjusted to stabilize around 3.29 Å³. Evaluation using multiple methods, including Phillips–van Vechten–Levine (P–V–L) theory, Raman vibrational mode analysis, bond valence, bond energy theory, and octahedral distortion, confirms that the Ti–O bonds within the octahedron predominantly affect ε_r, the increasing lattice energy (U) contributes to the enhancement of Q×f, and the strengthened Li–O bond energy effectively regulates τ_f.

Keywords

microwave dielectric ceramics phase transitions Phillips–van Vechten–Levine (P–V–L)Zn_1−xLi_2xTiO₃

Electronic Supplementary Material

Download File(s)

JAC0927_ESM.pdf (1.1 MB)

References

[1]

Sebastian MT, Ubic R, Jantunen H. Low-loss dielectric ceramic materials and their properties. Int Mater Rev 2015, 60: 392–412.

Crossref Google Scholar

[2]

Hill MD, Cruickshank DB, MacFarlane IA. Perspective on ceramic materials for 5G wireless communication systems. Appl Phys Lett 2021, 118: 120501.

Crossref Google Scholar

[3]

Zhang X, Fang ZX, Yang HY, et al. Lattice evolution, ordering transformation and microwave dielectric properties of rock-salt Li_{3+ x}Mg_{2−2 x}Nb_{1− x}Ti_{2 x}O₆ solid-solution system: A newly developed pseudo ternary phase diagram. Acta Mater 2021, 206: 116636.

Crossref Google Scholar

[4]

Bao J, Zhang YP, Kimura H, et al. Crystal structure, chemical bond characteristics, infrared reflection spectrum, and microwave dielectric properties of Nd₂(Zr_{1− x}Ti_x)₃(MoO₄)₉ ceramics. J Adv Ceram 2023, 12: 82–92.

Crossref Google Scholar

[5]

Pan ZW, Yu XD, Wang QC, et al. Stabilization and tunable microwave dielectric properties of the rutile polymorph in α-PbO₂-type GaTaO₄-based ceramics. J Mater Chem C 2014, 2: 4957–4966.

Crossref Google Scholar

[6]

Belous A, Ovchar O, Durilin D, et al. High-Q microwave dielectric materials based on the spinel Mg₂TiO₄. J Am Ceram Soc 2006, 89: 3441–3445.

Crossref Google Scholar

[7]

Li L, Chen XM, Fan XC. Microwave dielectric characteristics and finite element analysis of MgTiO₃–CaTiO₃ layered dielectric resonators. J Eur Ceram Soc 2006, 26: 3265–3271.

Crossref Google Scholar

[8]

Cao M, Li L, Wu SY, et al. Dominant role of ceramic connectivity in microwave dielectric properties of porous ceramics. Acta Mater 2023, 258: 119207.

Crossref Google Scholar

[9]

Guo HH, Fu MS, Zhou D, et al. Design of a high-efficiency and -gain antenna using novel low-loss, temperature-stable Li₂Ti_{1− x}(Cu_1/3Nb_2/3)_xO₃ microwave dielectric ceramics. ACS Appl Mater Inter 2021, 13: 912–923.

Crossref Google Scholar

[10]

Li W, Fang L, Tang Y, et al. Microwave dielectric properties in the Li_{4+ x}Ti₅O₁₂ (0 ≤ x ≤ 12) ceramics. J Alloys Compd 2017, 701: 295–300.

Crossref Google Scholar

[11]

George S, Sebastian MT. Synthesis and microwave dielectric properties of novel temperature stable high Q, Li₂ATi₃O₈ (A = Mg, Zn) ceramics. J Am Ceram Soc 2010, 93: 2164–2166.

Crossref Google Scholar

[12]

Zhang YD, Zhou D. Pseudo phase diagram and microwave dielectric properties of Li₂O–MgO–TiO₂ ternary system. J Am Ceram Soc 2016, 99: 3645–3650.

Crossref Google Scholar

[13]

Nolan NT, Seery MK, Pillai SC. Crystallization and phase-transition characteristics of sol–gel-synthesized zinc titanates. Chem Mater 2011, 23: 1496–1504.

Crossref Google Scholar

[14]

Yang HY, Li EZ, Yang YF, et al. Co₂O₃ substitution effects on the structure and microwave dielectric properties of low-firing (Zn_0.9Mg_0.1)TiO₃ ceramics. Ceram Int 2018, 44: 5010–5016.

Crossref Google Scholar

[15]

Jaramillo-Fierro X, Cuenca G, Ramón J. Comparative study of the effect of doping ZnTiO₃ with rare earths (La and Ce) on the adsorption and photodegradation of cyanide in aqueous systems. Int J Mol Sci 2023, 24: 3780.

Crossref Google Scholar

[16]

Wei SH, Chang SF, Qian J, et al. Selective cocatalyst deposition on ZnTiO_{3− x}N_y hollow nanospheres with efficient charge separation for solar-driven overall water splitting. Small 2021, 17: 2100084.

Crossref Google Scholar

[17]

Mohammadi MR, Fray DJ. Low temperature nanostructured zinc titanate by an aqueous particulate sol-gel route: Optimisation of heat treatment condition based on Zn : Ti molar ratio. J Eur Ceram Soc 2010, 30: 947–961.

Crossref Google Scholar

[18]

Dulin FH, Rase DE. Phase equilibria in the system ZnO–TiO₂. J Am Ceram Soc 1960, 43: 125–131.

Crossref Google Scholar

[19]

Bartram SF, Slepetys RA. Compound formation and crystal structure in the system ZnO–TiO₂. J Am Ceram Soc 1961, 44: 493–499.

Crossref Google Scholar

[20]

Lei SH, Fan HQ, Ren XH, et al. Novel sintering and band gap engineering of ZnTiO₃ ceramics with excellent microwave dielectric properties. J Mater Chem C 2017, 5: 4040–4047.

Crossref Google Scholar

[21]

Kim HT, Kim Y, Valant M, et al. Titanium incorporation in Zn₂TiO₄ spinel ceramics. J Am Ceram Soc 2001, 84: 1081–1086.

Crossref Google Scholar

[22]

Kim HT, Kim SH, Nahm S, et al. Low-temperature sintering and microwave dielectric properties of zinc metatitanate-rutile mixtures using boron. J Am Ceram Soc 1999, 82: 3043–3048.

Crossref Google Scholar

[23]

Chang YS, Chang YH, Chen IG, et al. Synthesis, formation and characterization of ZnTiO₃ ceramics. Ceram Int 2004, 30: 2183–2189.

Crossref Google Scholar

[24]

Inaguma Y, Aimi A, Shirako Y, et al. High-pressure synthesis, crystal structure, and phase stability relations of a LiNbO₃-type polar titanate ZnTiO₃ and its reinforced polarity by the second-order Jahn-Teller effect. J Am Chem Soc 2014, 136: 2748–2756.

Crossref Google Scholar

[25]

Raji S, Masin B, Bhagya KM, Ashok K, Vishnuc S, Sreemoolanadhan H, Prabhakaran K, . Low-temperature sintering of ZnTiO₃ using CaV₂O₆ as a liquid-forming additive for LTCC applications. Ceram Int 2024, 50: 9206–9213.

Crossref Google Scholar

[26]

Wu SP, Luo JH, Cao SX. Microwave dielectric properties of B₂O₃–doped ZnTiO₃ ceramics made with sol–gel technique. J Alloys Compd 2010, 502: 147–152.

Crossref Google Scholar

[27]

Li EZ, Zhang P, Duan SX, et al. Low temperature sintering of low-loss ZnTiO₃ microwave dielectric ceramics with Zn–B–Si glass. J Alloys Compd 2015, 647: 866–872.

Crossref Google Scholar

[28]

Zhang JY, Li J, Sun YH, et al. Densification, microwave dielectric properties and rattling effect of LiYbO₂ ceramics with low ε_r and anomalous positive τ_f. J Eur Ceram Soc 2022, 42: 7455–7460.

Crossref Google Scholar

[29]

Liu K, Shi L, Wang XY, et al. Li⁺ enrichment to improve the microwave dielectric properties of Li₂ZnTi₃O₈ ceramics and the relationship between structure and properties. J Eur Ceram Soc 2023, 43: 1483–1491.

Crossref Google Scholar

[30]

Zuo RZ, Qi H, Qin F, et al. A new Li-based ceramic of Li₄MgSn₂O₇: Synthesis, phase evolution and microwave dielectric properties. J Eur Ceram Soc 2018, 38: 5442–5447.

Crossref Google Scholar

[31]

Zhang J, Zuo RZ. Effect of ordering on the microwave dielectric properties of spinel-structured (Zn_{1− x}(Li_2/3Ti_1/3)_x)₂TiO₄ ceramics. J Am Ceram Soc 2016, 99: 3343–3349.

Crossref Google Scholar

[32]

Du QB, Wen QZ, Jiang LX, et al. A novel low-temperature sintering microwave dielectric ceramic Li₄SrCaSi₂O₈ with low- ϵ_r and low loss. Ceram Int 2023, 49: 22617–22622.

Crossref Google Scholar

[33]

Pan HL, Wu HT. Crystal structure, infrared spectra and microwave dielectric properties of new ultra low-loss Li₆Mg₇Ti₃O₁₆ ceramics. Ceram Int 2017, 43: 14484–14487.

Crossref Google Scholar

[34]

Huang FY, Su H, Li YX, et al. Low-temperature sintering and microwave dielectric properties of CaMg_{1− x}Li_{2 x}Si₂O₆ ( x = 0−0.3) ceramics. J Adv Ceram 2020, 9: 471–480.

Crossref Google Scholar

[35]

Du XY, Su H, Zhang HW, et al. Effects of Li-ion substitution on the microwave dielectric properties of low-temperature sintered ceramics with nominal composition Li_{2 x}Mg_{2− x}SiO₄. Ceram Int 2018, 44: 2300–2303.

Crossref Google Scholar

[36]

Xiang HC, Fang L, Fang WS, et al. A novel low-firing microwave dielectric ceramic Li₂ZnGe₃O₈ with cubic spinel structure. J Eur Ceram Soc 2017, 37: 625–629.

Crossref Google Scholar

[37]

Pang LX, Zhou D. A low-firing microwave dielectric material in Li₂O–ZnO–Nb₂O₅ system. Mater Lett 2010, 64: 2413–2415.

Crossref Google Scholar

[38]

Pang LX, Zhou D. Microwave dielectric properties of low-firing Li₂MO₃ (M = Ti, Zr, Sn) ceramics with B₂O₃–CuO addition. J Am Ceram Soc 2010, 93: 3614–3617.

Crossref Google Scholar

[39]

Zhou HF, Liu XB, Chen XL, et al. Preparation, phase structure and microwave dielectric properties of CoLi_2/3Ti_4/3O₄ ceramic. Mater Res Bull 2012, 47: 1278–1280.

Crossref Google Scholar

[40]

Zhou HF, Gong JZ, Wang N, et al. A novel temperature stable microwave dielectric ceramic with low sintering temperature and high quality factor. Ceram Int 2016, 42: 8822–8825.

Crossref Google Scholar

[41]

Fang WS, Sun YM, Fang L, et al. Temperature stable microwave dielectric ceramics in Li_{1.33 x}Zn_{2−2 x}Ti_{1+0.67 x}O₄ (0.75 < x < 1) cubic spinels and their chemical compatibility with silver. J Alloys Compd 2017, 722: 1002–1007.

Crossref Google Scholar

[42]

Singh SK, Kiran SR, Murthy VRK. Structural, Raman spectroscopic and microwave dielectric studies on spinel Li₂Zn_{(1− x )}Ni_xTi₃O₈ compounds. Mater Chem Phys 2013, 141: 822–827.

Crossref Google Scholar

[43]

Li B, Tang B, Zhang SR, et al. Low temperature sintering and microwave dielectric properties of (Zn_0.65Mg_0.35)TiO₃ ceramics with BiVO₄. J Mater Sci 2010, 45: 6461–6466.

Crossref Google Scholar

[44]

Wang YJ, Zhang ZY, Li J, et al. Effect of cation occupancy on crystal structure and microwave dielectric characteristics of spinel-structured (1− x)Zn₂TiO_{4− x}Li₂MgTi₃O₈ ceramics. Ceram Int 2024, 50: 13500–13507.

Crossref Google Scholar

[45]

Li YX, Li H, Tang B, et al. Microwave dielectric properties of low-fired Li₂ZnTi₃O₈–TiO₂ composite ceramics with Li₂WO₄ addition. J Mater Sci—Mater El 2015, 26: 1181–1185.

Crossref Google Scholar

[46]

Lei T, Chen JW, Xu ZQ, et al. Microwave dielectric properties of the low-temperature-fired Li₂ZnTi₃O₈–Li₂TiO₃ ceramics for LTCC applications. J Mater Sci—Mater El 2018, 29: 14705–14709.

Crossref Google Scholar

[47]

Mendelson MI. Average grain size in polycrystalline ceramics. J Am Ceram Soc 1969, 52: 443–446.

Crossref Google Scholar

[48]

McClure DS. The distribution of transition metal cations in spinels. J Phys Chem Solids 1957, 3: 311–317.

Crossref Google Scholar

[49]

Burdett JK, Price GD, Price SL. Role of the crystal-field theory in determining the structures of spinels. J Am Chem Soc 1982, 104: 92–95.

Crossref Google Scholar

[50]

Hu W, Liu HX, Hao H, et al. Influence of TiO₂ additive on the microwave dielectric properties of α-CaSiO₃–Al₂O₃ ceramics. Ceram Int 2015, 41: S510–S514.

Crossref Google Scholar

[51]

Chen XQ, Li H, Zhang PC, et al. SrZnV₂O₇: A low-firing microwave dielectric ceramic with high-quality factor. J Am Ceram Soc 2021, 104: 5110–5119.

Crossref Google Scholar

[52]

Penn SJ, Alford NM, Templeton A, et al. Effect of porosity and grain size on the microwave dielectric properties of sintered alumina. J Am Ceram Soc 1997, 80: 1885–1888.

Crossref Google Scholar

[53]

Shannon RD. Dielectric polarizabilities of ions in oxides and fluorides. J Appl Phys 1993, 73: 348–366.

Crossref Google Scholar

[54]

Du K, Fan J, Zou ZY, et al. Crystal structure, phase compositions, and microwave dielectric properties of malayaite-type Ca_{1− x}Sr_xSnSiO₅ ceramics. J Am Ceram Soc 2020, 103: 6369–6377.

Crossref Google Scholar

[55]

Kim ES, Chun BS, Freer R, et al. Effects of packing fraction and bond valence on microwave dielectric properties of A²⁺B⁶⁺O⁴ (A²⁺: Ca, Pb, Ba; B⁶⁺: Mo, W) ceramics. J Eur Ceram Soc 2010, 30: 1731–1736.

Crossref Google Scholar

[56]

Kim ES, Jeon CJ. Microwave dielectric properties of ATiO₃ (A=Ni,Mg,Co,Mn) ceramics. J Eur Ceram Soc 2010, 30: 341–346.

Crossref Google Scholar

[57]

Liao QW, Li LX, Ding X. Phase constitution, structure analysis and microwave dielectric properties of Zn_0.5Ti_{1− x}Zr_xNbO₄ ceramics. Solid State Sci 2012, 14: 1385–1391.

Crossref Google Scholar

[58]

Li LX, Li YT, Qiao JL, et al. Developing high- Q× f value MgNb_{2− x}Ta_xO₆ (0 ≤ x ≤ 08) columbite ceramics and clarifying the impact mechanism of dielectric loss: Crystal structure, Raman vibrations, microstructure, lattice defects, chemical bond characteristics, structural parameters, and microwave dielectric properties in-depth studies. J Mater Sci Technol 2023, 146: 186–199.

Crossref Google Scholar

[59]

Brese NE, O’Keeffe M. Bond-valence parameters for solids. Acta Cryst 1991, 47: 192–197.

Crossref Google Scholar

[60]

Shannon RD. Oxygen position, octahedral distortion, and bond-valence parameter from bond lengths in Ti_{1− x}Sn_xO₂ (0 ≤ x ≤ 1). J Am Ceram Soc 2000, 83: 3205–3207.

Crossref Google Scholar

[61]

Luo YR. Bond dissociation energies. In: CRC Handbook of Chemistry and Physics. William M. Haynes, Ed. CRC Press, 2012.

[62]

Batsanov SS. Dielectric methods of studying the chemical bond and the concept of electronegativity. Russ Chem Rev 1982, 51: 684–697.

Crossref Google Scholar

[63]

Borbón S, Lugo S, Pineda N, et al. ZnTiO₃ nanoparticles for application as photoanode in dye-sensitized solar cells (DSSC). Phys B 2022, 630: 413704.

Crossref Google Scholar

[64]

Guo HH, Zhou D, Pang LX, et al. Influence of (Mg_1/3Nb_2/3) complex substitutions on crystal structures and microwave dielectric properties of Li₂TiO₃ ceramics with extreme low loss. J Materiomics 2018, 4: 368–382.

Crossref Google Scholar

[65]

Xiao K, Tang Y, Tian YF, et al. Enhancement of the cation order and the microwave dielectric properties of Li₂ZnTi₃O₈ through composition modulation. J Eur Ceram Soc 2019, 39: 3064–3069.

Crossref Google Scholar

[66]

Huang FY, Su H, Zhang Q, et al. The structural characteristics and microwave dielectric properties of Ti⁴⁺ doped CaMgSi₂O₆ ceramics. Ceram Int 2022, 48: 33615–33623.

Crossref Google Scholar

Journal of Advanced Ceramics

Volume 13 Issue 8,
August 2024

Pages 1178-1188

DOI: 10.26599/JAC.2024.9220927

Cite this article:

Du Q, Jiang L, Ma L, et al. Lattice evolution, order transformation, and microwave dielectric properties of the Zn_1−xLi_2xTiO₃ (0 ≤ x ≤ 1) system ceramics. Journal of Advanced Ceramics, 2024, 13(8): 1178-1188. https://doi.org/10.26599/JAC.2024.9220927

864

Views

179

Downloads

Crossref

Web of Science

Scopus

CSCD

Google Scholar
Citation

Altmetrics

Received: 03 April 2024

Revised: 07 June 2024

Accepted: 11 June 2024

Published: 30 August 2024

This is an open access article under the terms of the Creative Commons Attribution 4.0 International License (CC BY 4.0, http://creativecommons.org/licenses/by/4.0/).