Accepted Manuscript

Effect of Zinc ions non-stoichiometry on the microstructure and microwave dielectric

properties of Li2ZnTi3O8 ceramics

Parastoo Moradi, Ehsan Taheri-Nassaj, Hamid Taghipour-Armaki

PII: S0925-8388(16)33368-0
DOI: 10.1016/j.jallcom.2016.10.326
Reference: JALCOM 39516

To appear in: Journal of Alloys and Compounds

Received Date: 28 August 2016

Revised Date: 4 October 2016
Accepted Date: 25 October 2016

Please cite this article as: P. Moradi, E. Taheri-Nassaj, H. Taghipour-Armaki, Effect of Zinc ions non-
stoichiometry on the microstructure and microwave dielectric properties of Li2ZnTi3O8 ceramics, Journal
of Alloys and Compounds (2016), doi: 10.1016/j.jallcom.2016.10.326.

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 ACCEPTED MANUSCRIPT

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 ACCEPTED MANUSCRIPT

Effect of Zinc ions non-stoichiometry on the microstructure and microwave

dielectric properties of Li2ZnTi3O8 ceramics

Parastoo Moradi1, Ehsan Taheri-Nassaj2,†, Hamid Taghipour-Armaki3

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1
Department of Materials Science and Engineering, Tarbiat Modares University, Tehran, 14115–143, Iran

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3
Organization for Education Research and Planning (OERP), Tehran, 4874-15, Iran

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E-mail: Parastoomoradi1@gmail.com, taheri@modares.ac.ir

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Abstract

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In this study, the effect of Zn2+ ions non-stoichiometry on the crystal structure, densification,
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microstructure, ionic polarizability and microwave dielectric properties of Li2ZnTi3O8 ceramics

were investigated. The non-stoichiometric Li2Zn1+xTi3O8 compositions ( −0.04 ≤ x ≤ 0.06 ) were

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prepared by the conventional solid state ceramic route. The evolution of the unit cell parameter and
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cation ordering were investigated employing XRD. The elemental analysis and microstructure of
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Li2Zn1+xTi3O8 specimens were studied by EDX and SEM, respectively. It was found that a slight

Zn2+ ions excess improves density and microwave dielectric properties, while the deficiency of Zn2+
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ions brings deterioration of the properties. When x= 0.06, well relative density of 95.1%, uniform

grains in microstructure without any second phase and best microwave dielectric properties of εr=
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25.5, Q×f= 63000GHz, τf= -18 ppm/°C were achieved in non-stoichiometric Li2Zn1.06Ti3O8 ceramic
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rather than other non-stoichiometric and stoichiometric compositions.

Keywords: Microwave dielectric properties, Non-stoichiometry, Spinel structure, Quality factor,

Ceramics

†
Corresponding author. Tel: 0098-21-82883306 /fax: 0098-21-82883381
E-mail address: taheri@modares.ac.ir (E. Taheri-Nassaj)

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1. Introduction
Recent developments in wireless and mobile communication systems have increased demand for

microwave compositions with improved microwave dielectric properties, such as high relative

permittivity, ε, high quality factor, Q, and near zero temperature coefficient of resonant frequency,

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τf [1, 2]. Nowadays, microwave dielectric ceramics have been shown to possess good microwave

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dielectric properties. The dielectric ceramics in the Li2O–ZnO–TiO2 ternary system have drawn

more attention in recent years, and among them, Li2ZnTi3O8 (LZT) ceramic is a promising

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candidate. Hernandez et al. [3]were the first to developed LZT ceramics and reported its spinel

structure and atomic positions. Thereafter, George et al. [4] obtained excellent microwave dielectric

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properties [ɛr= 25.6, Q×f= 72,000 GHz and τf= -11.2 ppm/°C] at relatively low sintering
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temperature (1075°C for 4 h). Due to low preparation cost, low sintering temperatures and excellent
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microwave dielectric properties of LZT, it is suitable for more researches and useful for LTCC

applications. Many researchers reduced dielectric losses and enhanced dielectric properties by
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different methods such as oxide additives [5-7], heat treatment [8] and changing the sintering
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conditions [9-11]. But recently, attentions are focused on improved dielectric properties via non-

stoichiometric effect. Change in stoichiometry of dielectric ceramics composition can improve

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microwave dielectric properties by reducing dielectric losses, increasing sinterability (by enhancing

the material’s transport processes) etc. [12-15].

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Kleykam [16] has investigated the effect of non-stoichiometry on the thermal properties of Li2TiO3.
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Their results indicated that the thermal conductivity decreases with deviation from stoichiometry.

Zhou et al. [14] studied Mg-excess non-stoichiometric Mg2SnO4 ceramics. In their work, the quality

factor of non-stoichiometric Mg2.15SnO4 composition was 76800 GHz which showed significant

enhancement in comparison to stoichiometric Mg2SnO4 with Q×f = 45300 GHz. Hao et al. [12]

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studied the effect of a slight A-site and B-site cation non-stoichiometry on the structure,

densification and microwave dielectric properties of Li2TiO3 ceramics. They could increase the Q×f

from 23500 to 56400 GHz. Li et al. [17] investigated the Zn-excess on the microwave dielectric

properties of Mg0.97Zn0.03TiO3 system. They improved the Q×f from 125000 to 277500 GHz with

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3mol % Zn excess. Belous et al. [18] studied the effect of slight deviation from stoichiometry in

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A2+Nb2O6 (A2+ is Mg2+, Zn2+, Co2+) and achieved high Q×f for Mg1.03Nb2O6 and Zn1.01Nb2O6

compositions. Wu et al. [19-21] investigated the effect of non-stoichiometry in BaZn1/3Nb2/3O3

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ceramics on the dielectric properties and found that some of the non-stoichiometric compositions

demonstrated the highest Q×f values. Surendran et al.[15] investigated the effect of non-

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stoichiometry on the structure and microwave dielectric properties of Ba(Mg0.33Ta0.67)O3. They
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found that the non-stoichiometric BMT compositions [Ba0.9925(Mg0.33Ta0.67)O3 and

Ba(Mg0.3183Ta0.67)O3] show better microwave dielectric properties and sinterability compared to

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stoichiometric BMT.
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The structure of the LZT ceramic is a spinel with its octahedral sites occupied by Ti4+ (12d) and
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Li+(4b) cations, and the tetrahedral sites are occupied by mixture of Li+ and Zn2+ (8c). Moreover,

cation ordering in the LZT is indicated by the formula (Li0.5Zn0.5)tet[Ti1.5Li0.5]octO4 [3]. It should be
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noted that the microwave properties of LZT depend on cation ordering and on the occupancy of the

cations in interstitial sites (octahedral and tetrahedral). This ordering plays a key role in reducing
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the intrinsic dielectric loss of LZT ceramics [8]. The occupancy of cations in interstitial (tetrahedral
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and octahedral) sites is effective on microwave dielectric properties not only for LZT ceramics but

also for all cubic spinel compounds [22],[23]. The little deviation from stoichiometry of LZT during

distribution and substitution of cations have been investigated by Kawai [24], Singh [25], Li [26]

,Huang [27], George [28].

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So far, there has been no report about non-stoichiometry effect on the LZT microwave dielectric

ceramics. In our present research, the effects of Zn2+ ions non-stoichiometry on the crystal structure,

densification, microstructure, ionic polarizability and microwave dielectric properties were

investigated.

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2. Material and methods

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In this research, non-stoichiometric compositions based on Li2Zn1+xTi3O8 [x=-0.04, -0.02, 0.0,

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+0.02 ,+0.04 and +0.06] were prepared by conventional solid-state ceramic route with Li2CO3 (Alfa

Aesar Company, 99%, Germany), ZnO, and TiO2 (Merck Chemical Company, >99%, Germany) as

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starting materials. Li2CO3, ZnO and TiO2 were heated at 300°C for 2h, 800°C for 2h and 950°C for
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4h, respectively. Non-stoichiometric amounts of heated powders were mixed by planetary mill for

6h using yttria-stabilized zirconia balls in ethanol medium in polyethylene cup. The slurry was
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dried and to prevent the volatilization of lithium, it was pressed to discs form. Thereafter, the

powders were calcined into an alumina crucible at 900°C for 4h. Thereafter, calcined powders were
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milled again for 3 h under previous conditions. After drying, obtained powders were mixed with 5%
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polyvinyl alcohol solution (10 %wt) as binder and were grinded. The obtained granulated powders

were pressed into discs of about 10 mm diameter and 4 mm thickness by applying a pressure of
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about 300 MPa. These samples were muffled by a powder with same composition of sample. To
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prevent the volatilization of lithium at sintering temperature, they were sintered at 1075°C for 4 h.
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The bulk densities of samples were measured by the Archimedes’s method according to ASTM-

C20. Also, the crystal structures of sintered samples were identified by X-ray diffraction (XRD)

(X'Pert MPD, Philips, CoKα: 1.78901 Å, Holland). The normal analysis were performed at

2θ :10° − 90° with step size of 0.02 and time per step of 0.8s and low angle at 2θ : 40.5° − 42.5°

with step size of 0.01 and time per step of 5s. The morphology of sintered samples was studied

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employing scanning electron microscopy (SEM: Philips XL30, Holland). Elemental analysis was

studied by energy-dispersive X-ray spectroscopy (EDS: RÖNTEC, Germany). The microwave

dielectric properties (εr and Q×f) were measured by cylindrical resonance cavity method employing

vector network analyzer (HP 8719C) at microwave frequency of ~ 8GHz [29]. For measurements of

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microwave dielectric properties, the diameter-to-thickness ratio of the dielectric resonator was

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adjusted to ≈2.26 to obtain the first resonance mode of TE01δ-type. The εr was calculated utilizing

QWED software. The temperature coefficient of the resonance frequency (τf) value (ppm/°C) was

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determined in the temperature range of 20 –70°C according to Equation 1:

∆f Eq.1
τf =

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f 0 × ∆T
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3. Results and discussion

3.1. Structural characterization

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Fig. 1 illustrates the X-ray diffraction patterns of non-stoichiometric Li2Zn1+xTi3O8 ceramics

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sintered at 1075°C for 4 h. All the compositions exhibit a main phase with ordered spinel structure

indexed according to P4332 space group (JCPDS card No.86-1512). Moreover, non-stoichiometry
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initiated the formation of secondary phase in deficiency of Zn2+ ions such as TiO2 (rutile, JCPDS

card No.76-0322). This might be caused by movement of Li+ ions via the 8c ↔ 12d ↔ 8c pathway
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as reported by Kawai et al [24]. This Li+ ions movement is due to the presence of Zn2+ ions vacancy
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and the internal sites occupied (octahedral space) belong to Ti4+ ions and led to the reduction of Ti4+

to Ti3+ to keep the electric charge neutral.

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Accordingly, Fig. 2 shows that the (111) reflection increased and the (220) reflection decreased,

which are both reflector of changes in Li+ ion distribution in the octahedral and tetrahedral sites[30],

respectively.

Fig.3 shows X-ray diffraction line profiles of (311) for non-stoichiometric LZT compositions. In the

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case of Zn2+ ions deficiency (Fig.3a), it can be seen that the (311) peak had a low angle shift to

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higher 2θ with reducing x value (x=-0.02), when x=-0.04, the (311) peak diffraction line is observed

back toward a lower 2θ. Thus this excursion indicated that the unit cell volume increased due to the

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occupation of transferred Li+ ions with high radius in the octahedral sites. A similar low angle

excursion to the lower 2θ is found for excess Zn2+amount in Fig.3b, this might due to the fact that

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the Zn2+ ion occupied the tetrahedral sites itself. The (311) peak move back toward a higher 2θ with
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increasing x value which indicate the fact that some excess Zn2+ ion might have occupied interstitial

sites (octahedral space). Zhou et al. [14] also reported that in x=0.2 value for Mg2+xSnO4 ceramics,
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the (311) peak was excursed to higher 2θ, they speculated that only a certain amount of Mg2+
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cations could occupy the interstitial sites of the Mg2SnO4 structure.

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Though the random shift of the XRD peak to higher or lower 2θ values as a function of non-

stoichiometry and the interpretation in Fig. 3 is not too convincing but according to correction curve
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resulted from correction equation [31], the correction value of 2θ is very low (0.0002). Hence, the

accuracy of the diffraction angles of diffraction patterns is reliable.

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Lattice parameters of samples were obtained by extrapolation equation (Eq. 2) [31] and are
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summarized in Table 1.

cos 2 θ cos 2 θ Eq.2

( + )
sin θ θ

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3.2. Sintering and densification

Fig.4 illustrates SEM images of non-stoichiometric Li2Zn1+xTi3O8 ceramics sintered at 1075°C for 4

h. Phase separation of TiO2 (rutile) to form ‘‘black cores’’ from LZT ceramics was observed in

Fig.4a for x<0 values. This secondary phase has a grain size of about 2 microns (Spot B, Fig.5), this

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might be related to the change of Ti valence which agrees with results of XRD patterns. Lu et al [9].

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also observed the formation of black cores in microstructure of LZT ceramics and reported the same

reason.

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The porosity of samples were reduced with increasing Zn2+contents (0< x ≤ 0.06 ) without any

secondary phase (Fig.4b-4d).

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Fig. 6 shows the relative densities of non-stoichiometric Li2Zn1+xTi3O8 ceramics sintered at 1075°C
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for 4 h as a function of x values in composition chemical formula and their theoretical density is

listed in Table 2. The relative density was increased with increase in Zn2+ content, and reached a
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maximum value when x=0.06, 95.1%. According to literatures, the non-stoichiometry improves
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sinterability [12, 14], therefore ion defects were created by interstitial Zn2+ ions which can expedite
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the mass transport process during sintering and improve densification. The second reason for this

improvement in densification is that rutile phase at the grain boundary with high melting point was
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removed (Fig.7). Naderer et al [32] in study of Ti non-stoichiometry effect on Bi0.5Na0.5TiO3

showed the formation of secondary phase at grain boundaries and lower density, too. It should be
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noted that there is no specified explanation for low density of sample at x= -0.02; since with
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considering error bar of sample at x= -0.04, the density in both of them is approximately similar and

the density of these samples are lower than density of stoichiometric sample (x= 0).

3.3. Microwave dielectric properties

The microwave dielectric properties of non-stoichiometric Li2Zn1+xTi3O8 ceramics sintered at

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1075°C for 4 h with function of x values are given in Fig.8. As shown in Fig.8a, the variation of

relative permittivity, ɛr was similar to variation of densification. The maximum value of ɛr (25.5) is

attributed to Li2Zn1.06Ti3O8 sample for x=0.06 with maximum density of 95.1%. Relative

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permittivity of ceramics depends on density, secondary phase, molecular volume, and ionic

polarization [1, 28]. The highest relative permittivity was observed for the best densification

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without any secondary phase; since high density means more dipole per unit volume and thus

relative permittivity is higher [4]. Although at x= -0.02, -0.04 TiO2 second phase is formed and it

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has a high relative permittivity about 100 [33]. However, the relative permittivity of these samples

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in comparison to other samples is lower; this is possible due to their low density. It seems that
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density factor prevailed in comparison to secondary phase with higher the relative permittivity. The

porosity (the porosity presence decreases relative permittivity since ɛr of air is 1) and atomic
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structure destruction of these samples are another reasons for this decrease in relative permittivity.

Effect of porosity on relative permittivity is visible by using the equation below (Eq.3):
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 3P (ε − 1)  Eq.3
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ε meas = ε corr 1 − 
 2ε corr + 1 

Where P is the porosity fraction, ɛmeas and ɛcorr are the measured and corrected permittivities,
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respectively [34].
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Fig.8b shows variation of the ionic polarizability, αD of these ceramics as function of x values that
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were estimated to clarify the effects of the Zn2+ ions non-stoichiometry on the ɛr by using the

Clausius–Mosotti (Eq.3) [35]:

V m (ε r − 1) Eq.3
αD =
b (ε r + 1)

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Where ɛr and Vm represent the measured relative permittivity and molecular volume, respectively,

and constant value b= 4/3. By increasing the Zn2+ ions content in composition, the αD was slightly

increased and maximum value obtained in x = 0.06 was equal to 32.39 Å3. Lattice volume of

samples is summarized in Table 1; according to Clausius–Mosotti equation increase in lattice

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volume, will increase polarization in unit volume and the variations of αD was like variations of the

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relative permittivity. Hence, ionic polarization increases and improves relative permittivity. Using

reported αD for different ions by Shannon [35], it can be expressed that this increase in ionic

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polarizability in non-stoichiometric LZT ceramics at x>0 is due to import of Zn2+ ion with ionic

polarizability (2.04 Å3) which is more than ionic polarizability of Li+ ion (1.2 Å3) in tetrahedral

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sites. Singh et al [25] also observed that ionic polarizability value of Li2Zn(1-x)NixTi3O8 compound
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was reduced with increase in Ni2+ ion, which is related to lower ionic polarizability of Ni2+ ion (1.23

Å3) other than that of Zn2+ ion (2.04 Å3). This indicated that the relative permittivity was mainly
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controlled by αD, since highest εr (25.5) of Li2Zn1.06Ti3O8 was obtained from maximum αD (32.39
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Å3) from this composition.

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A slight deviation from stoichiometry within this work has practical effect on quality factor (Q×f).

Quality factor depends on extrinsic and intrinsic microwave dielectric losses; the grain boundaries,
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porosity, secondary phase as extrinsic losses and crystal structure and lattice vibrations as intrinsic

losses [28]. As can be seen in Fig.8c, with decrease in Zn2+ ions content from its stoichiometry
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content, quality factor was reduced (48300 GHz for x= 0 to 44100 GHz for x= -0.04). Formation of
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secondary phase (TiO2) and reducing of density destroyed quality factor. However, the specimen

with x>0 values increased quality factor and best magnitude of the Q×f =63000 GHz was obtained

at x=0.06 when the maximum density was achieved.

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It should be noted that the loss tangent ( tan δ ) depends on AC conductivity ( σ ac ) according to

Equation 4 [36]:

σ ac Eq.4
tan δ =
ε 0ε r ω

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Where ω is angular frequency. This equation indicates the relationship between dielectric loss and

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conductivity of ceramics. The AC conductivity of spinel structures depends on cation ordering and

distribution of cations at interstitial sites [30]. Increasing the movement of Li+ ions in

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the 8c ↔ 12d ↔ 8c trajectories according to equation 4, lead to increase σ ac and finally lead to

reduced quality factor. Singh et al. [25] reported that the substitution of Ni2+ ion instead of Zn2+ ion

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favored the transition of Li+ ion at noted pathway which led to increase in conductivity. Hao et al.
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[12] also observed decrease in microwave dielectric properties at excess content of Li+ ion in

Li2TiO3 ceramics. Lu et al [9] reported high packing fraction with decrease of lattice anharmonicity
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vibration as a factor in improving quality factor by reduced intrinsic loss.

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The temperature coefficient of resonant frequency (τf) is basically dependent on interactions of the
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atoms and higher bond strength and it corresponds to lower vibration. On the other hand, τf is

influenced by the structural parameters and composition of material [9, 10] .The τf values of non-
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stoichiometric Li2Zn1+xTi3O8 ceramics as function of x values is illustrated in Fig.8d. The τf of

stoichiometric Li2ZnTi3O8 ceramic was -16 ppm/°C but the value of τf was reduced in both
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deficiency and excess of Zn2+ ions in LZT ceramic (-17 ppm/°C for x=-0.04 and -18 ppm/°C for
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x=0.06). This might be related to distortion of the crystal structure or the low τf of ZnO (-60 ppm/°C

[37]).

The microwave dielectric properties values of the stoichiometric Li2ZnTi3O8 ceramic (ɛr= 25.3,

Q×f= 48300 GHz and τf= -16 ppm/°C) were slightly lower than that reported in other literature (ɛr=

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25.6, Q×f= 72000 GHz and τf= -11.2 ppm/°C) [28]. This is possible due to change in conditions of

experiment and raw materials. It should be noted that non-stoichiometry of cations in the

Li2ZnTi3O8 ceramic is compensated by a manifestation of the oxygen anion concentration in

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Li2Zn1+xTi3O8 lattice. Oxygen defect has effects on the densification and microwave dielectric

properties, but this is above the investigation of oxygen non-stoichiometry for the sake of

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simplicity.

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4. Conclusions
The phase analysis, microstructure and microwave dielectric properties of non-stoichiometric

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Li2Zn1+xTi3O8 ceramics made of Li2O-ZnO-TiO2 system have been investigated. The non-
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stoichiometric Li2Zn1+xTi3O8 ceramics were sintered at 1075°C for 4 h. The microwave dielectric

properties of Li2ZnTi3O8 stoichiometric ceramic (x=0) are as follows: ɛr=25.3, αD=32.34Å3,

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Q×f=48300 GHz and τf= -16 ppm/°C with relative density of 94.5%. The non-stoichiometric

ceramics with excess amount of Zn2+ ions (x>0) demonstrated best microwave dielectric properties
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rather than stoichiometric ceramic (x=0). The best microwave dielectric properties, ɛr=25.5,
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αD=32.39Å3, Q×f=63000 GHz and τf=-18 ppm/°C with relative high density of 95.1% belongs to
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non-stoichiometric Li2Zn1.06Ti3O8 ceramic.

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Figures Captions

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Fig. 1. X-ray diffraction pattern of non-stoichiometric Li2Zn1+xTi3O8 ceramics, x= -0.04, x= -0.02,

x= 0.00, x= 0.02, x= 0.04, x= 0.06 sintered at 1075°C for 4 h.

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Fig. 2. Integrated relative intensity of (111)order and (220)order for non-stoichiometric Li2Zn1+xTi3O8

ceramics (x= -0.04, -0.02, 0.00, 0.02, 0.04, 0.06) sintered at 1075°C for 4 h.

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Fig. 3. X-ray diffraction line profiles of (311) for non-stoichiometric Li2Zn1+xTi3O8 ceramics (a) x=
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-0.04 and -0.02, (b) x= 0.02, 0.04 and 0.06) sintered at 1075°C for 4 h.

Fig. 4. The SEM micrographs of non-stoichiometric Li2Zn1+xTi3O8 ceramics sintered at 1075°C for
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4 h. (a) x= -0.04, (b) x= +0.02, (c) x= +0.06 and (d) less zoom x= +0.02 composition.
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Fig. 5. The SEM micrographs of BSE mod non-stoichiometric Li2Zn0.96Ti3O8 ceramics sintered at
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1075°C for 4 h. spot A: LZT phase and spot B: TiO2 (rutile) phase.

Fig. 6. Variation in relative density of the non-stoichiometric Li2Zn1+xTi3O8 ceramics sintered at

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1075°C for 4 h as a function of Zn2+ ions non-stoichiometry content.

Fig. 7. The SEM micrographs of non-stoichiometric Li2Zn1+xTi3O8 ceramics sintered at 1075°C for
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4 h. (a) x= -0.04 and (b) x= 0.06.

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Fig. 8. Variation in the (a) relative permittivity, (b) ionic polarizability, (c) quality factor, and (d)

temperature coefficient of the resonant frequency of the non-stoichiometric Li2Zn1+xTi3O8 ceramics

sintered at 1075°C for 4 h as a function of Zn2+ ions non-stoichiometry content.

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Tables Captions

Table 1. Lattice parameters and cell volumes of non-stoichiometric Li2Zn1+xTi3O8 ceramics sintered

at 1075°C for 4 h.

Table 2. Theoretical density of the non-stoichiometric Li2Zn1+xTi3O8 ceramics sintered at 1075°C

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for 4 h.

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Table 1.

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x content (%mol) -0.04 -0.02 0.00 0.02 0.04 0.06

lattice parameters (Å) 8.374 8.367 8.371 8.368 8.367 8.373

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cell volume (Å3) 587.22 585.75 586.59 585.96 585.75 587.01
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Table 2.
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Composition formula x Theoretical Density (g/cm3) Relative Density (g/cm3)

Li2Zn0.96Ti3O8 -0.04 3.94 93.1 ± 0.36

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Li2Zn0.98Ti3O8 -0.02 3.96 92.6 ± 0.18

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Li2ZnTi3O8 0 3.97 94.5 ± 0.18

Li2Zn1.02Ti3O8 0.02 3.99 94.4 ± 0.18

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Li2Zn1.04Ti3O8 0.04 4.00 94.4 ± 0.71

Li2Zn1.06Ti3O8 0.06 4.02 95.1 ± 0.00

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Highlights

• Non-stoichiometric LZT compositions prepared by the conventional solid state route.

• Deficiency of Zn2+ ion brings deterioration of the microwave dielectric properties.

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• The best microwave dielectric properties belong to Li2Zn1.06Ti3O8 ceramic.
• Deviation in Zn2+ ions content from its stoichiometry affected strongly on Q×f.

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