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Towards enhanced varistor property and lower dielectric loss of CaCu3Ti4O12 based ceramics

Towards enhanced varistor property and lower dielectric loss of CaCu3Ti4O12 based ceramics
Towards enhanced varistor property and lower dielectric loss of CaCu3Ti4O12 based ceramics

Towards enhanced varistor property and lower dielectric loss of CaCu 3Ti 4O 12based ceramics

Jianying Li ?,Kangning Wu,Ran Jia ?,Linlin Hou,Lu Gao,Shengtao Li

State Key Laboratory of Electrical Insulation and Power Equipment,Xi'an Jiaotong University,Xi'an 710049,China

a b s t r a c t

a r t i c l e i n f o Article history:

Received 6July 2015

Received in revised form 4December 2015Accepted 14December 2015

Available online 17December 2015A novel (1?x )CaCu 3Ti 4O 12?x Y 2/3Cu 3Ti 4O 12composite ceramic was developed.Two perovskite-like grains,i.e.CaCu 3Ti 4O 12grains of 1–2μm and Y 2/3Cu 3Ti 4O 12grains of 4–6μm,can be both detected in the samples.High Schottcky barrier height and grain boundary resistance were formed via combining these two perovskite-like phases,which plays the critical role on the varistor and dielectric performance.Greatly enhanced nonlinear coef ?cient of 9.88and very low dielectric loss of 0.02can be achieved in the composite ceramics accompanied with the permittivity of ~2000,compared with reported results of 2–6and 0.05–0.8for general CaCu 3Ti 4O 12ceramics.This varistor –capacitor multifunctional characteristic makes it a promising material in the ?eld of over voltage protections of electronic devices.

?2015Elsevier Ltd.All rights reserved.

Keywords:CaCu 3Ti 4O 12

Composite ceramics Varistor performance Dielectric properties

1.Introduction

Perovskite oxides have attracted much attention due to their exten-sive properties.The speci ?c structure and especially the defects formed via substitution make perovskite oxides outstanding functional mate-rials and exhibit various properties [1–3].One of the important usages of perovskite oxides is dielectric ceramics.Various perovskite materials were discovered to possess excellent dielectric properties in the past few decades [4–6].For example,SrTiO 3has been widely used in the ?eld of over voltage protection of electronic systems due to its combin-ing varistor and capacitor characteristics [7,8].In the past decade,CaCu 3Ti 4O 12(CCTO)was reported exhibiting stable colossal permittivity (N 104)at wide temperature (100–400K)and frequency (102–105Hz)range [9,10]as well as noteworthy nonlinear current –voltage property [11–13],which makes it a potential material in the ?eld of varistor devices,especially for over voltage protections of electronic devices.In addition,compared to SrTiO 3ceramics,CCTO ceramics can be one-step sintered and free of surface layer effect [7,8].However,the nonlinear coef ?cient of CCTO is low and the dielectric loss is high for industrial application,which thus needs further detailed investigation.

So far,the internal barrier layer capacitor (IBLC)model of Schottky-type potential barriers has been widely accepted to explain its colossal permittivity and nonlinear current –voltage property [14–17].Many researches have been carried out to improve the performance of CCTO ceramics via tuning the microstructure,especially the grain boundary

structure [18–20],among which the secondary phase addition is an effective method to control grain growth and grain boundary barrier of CCTO ceramics [21–25].Yu HT et al.[23]fabricated CCTO ceramics modi ?ed by SrTiO 3and found that the abnormal grain growth was signi ?cantly suppressed,and sample with 40%SrTiO 3addition exhibited the permittivity close to 2000and dielectric loss less than 0.03at 1kHz.The nonlinearity was improved in CaCu 3Ti 4O 12–CaTiO 3composite ceramics by Bueno PR et al.as well [25].The secondary phase,generally selected as titanates and metal oxides,mostly acts as a block in CCTO ce-ramics.In addition,the family of ACu 3Ti 4O 12(ACTO,A =Y 2/3,La 2/3,Sm 2/3etc.)ceramics with similar perovskite-like structure has been found to exhibit giant dielectric response [9].It is supposed that CCTO and ACTO grains can be uniformly distributed in CCTO –ACTO composite ceramics due to the similar structure.Thus it may be a promising way to modify the barrier characteristic via forming interfaces between CCTO and another ACTO.

In this work,Y 2/3Cu 3Ti 4O 12(YCTO)was chosen as the secondary phase to prepare CCTO –YCTO composite ceramics due to its relatively homogeneous microstructure during sintering [26].The effects of chemical stoichiometric ratio on phase composition,microstructure,varistor characteristics,and dielectric performance were investigated in detail.In addition,complex impedance spectroscopy was used to explain the mechanism of the electrical response.2.Experimental procedures

(1?x )CaCu 3Ti 4O 12?x Y 2/3Cu 3Ti 4O 12((1?x )CCTO ?x YCTO,x =0.0,0.2,0.5,0.8,1.0)ceramics were prepared by traditional solid-state reaction method,and the fabrication process can be found in Fig.1.

Materials and Design 92(2016)546–551

?Corresponding authors.

E-mail addresses:lijy@https://www.doczj.com/doc/7d6683138.html, (J.Li),jiaran@https://www.doczj.com/doc/7d6683138.html, (R.

Jia).

https://www.doczj.com/doc/7d6683138.html,/10.1016/j.matdes.2015.12.0730264-1275/?2015Elsevier Ltd.All rights

reserved.

Contents lists available at ScienceDirect

Materials and Design

j o u r n a l h o me p a g e :ww w.e l s e v i e r.c o m /l o c a t e /m a t d e s

Analytic grade (99.0%purity)Y 2O 3,CaCO 3,CuO and TiO 2powders,the weight of which was calculated according to the stoichiometric ratio and listed in Table 1,were mixed by ball milling for 6–12h in ethanol.The milled mixture was dried at 80°C for 12h in oven and calcined at 950°C for 15h.The calcined powders were milled again and pressed into green body of 12mm diameter and ~2mm thickness using PVA as a binder.After that,the green body was sintered at 1100°C for 10h with the heating rate of 200°C/h and furnace cooled.

X-ray diffraction (XRD,Regaku D/MAX IIIB,Japan)was used to ana-lyze the phase formation of the ceramics.Scanning electron microcopy (SEM,KEY-ENCE VE9800,Japan)with Energy Dispersive Spectrometer (EDS)were used to characterize the surface of the calcined powders and samples.The density of the sintered samples was measured by Archimedes method.Gold electrodes were prepared on both sides of the samples with a sputter coater (KYKY SBC-128,China)for electrical measurements.J –E curves of the samples were measured using a DC power source (WJ10001D,China)and a Multi-function digital meter (HP34401A,America)at room temperature.The dielectric properties were measured by a broadband dielectric measurement system (Novocontrol,Concept 80,Germany)at a temperature range from ?140°C to 200°C and the frequency range from 10?1Hz to 107Hz.

3.Results and discussions

3.1.Phase composition and microstructure

Fig.2(a)presents the X-ray diffraction patterns of sintered (1?x )CCTO ?x YCTO samples.All samples exhibit a main phase of cubic perovskite,and only trace amount of TiO 2can be found when x =1,i.e.YCTO ceramics.Thus,it is rather dif ?cult to distinguish the phase composition from the XRD results due to the extremely similar lattice constant between YCTO and CCTO.For further analysis of element distribution,SEM with EDS analysis was carried out.Fig.1(b),SEM image of 0.2CCTO –0.8YCTO sample,shows a typical morphology of two types of grains,https://www.doczj.com/doc/7d6683138.html,rge grains of 4–6μm and small grains of 1–2μm.To illustrate the elements composition of these grains,EDS measurement was carried out on grains marked as A,B,C and D,which were selected as examples for large and small grains in Fig.1(b)and the results are listed in Table 2.It is notable that the elements compositions of A and B,https://www.doczj.com/doc/7d6683138.html,rge grains,are close to YCTO while C and D,small grains,are close to CCTO.Thus,the large and small grains can be identi ?ed as YCTO and CCTO respectively.The results suggested that composite ceramics were achieved.

To further investigate the microstructure of the composite ceramics,SEM images of (1?x )CCTO ?x YCTO (x =1,0.8,0.5,0.2,0)ceramics are shown in Fig.3.The densities of samples are listed in Table 3as well.As seen in Fig.3(a),stripy grains of ~10μm ×(40–60)μm can be de-tected in YCTO (x =1)ceramics.In Fig.3(e),a discontinuous distribution of grain size is observed in CCTO https://www.doczj.com/doc/7d6683138.html,rge grains of 40–60μm surrounded by small grains of 10–20μm can be found,which is attributed to the abnormal grain growth caused by liquid phase sintering of CuO [16,27].Meanwhile uniformly distributed grains with equiaxed shape are observed in Fig.3(b –d).The number of YCTO grains with grain

size

Fig.1.Flow diagram of fabrication processes of (1?x )CCTO ?x YCTO samples.

Table 1

Mass of raw oxides for fabrication of (1?x )CCTO ?x YCTO samples.Samples x =0.0x =0.2x =0.5x =0.8x =1.0Y 2O 30g

2.304g 5.828g 9.433g 11.884g CaCO 315.206g 12.257g 7.749g

3.136g 0g

CuO 48.539g 48.906g 49.469g 50.046g 50.438g TiO 2

36.257g

36.532g

36.953g

37.384g

37.667

g

Fig.2.X-ray diffraction patterns of sintered (1?x )CCTO ?x YCTO (x =0.0,0.2,0.5,0.8,1.0)samples (a)and SEM image of 0.2CCTO –0.8YCTO sample (b).

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J.Li et al./Materials and Design 92(2016)546–551

of 4–6μm,revealed by EDS,increases with the increase of value x .In addition,the average sizes of CCTO and YCTO grains in composite ceramic samples are much smaller than those in CCTO and YCTO samples,which indicates that the grain growth of CCTO and YCTO were both suppressed in composite ceramics.3.2.Varistor characteristics

Current –voltage characteristic is of great signi ?cance for varistors.As shown in Fig.4,nonlinear J –E characteristics can be found in (1?x )CCTO ?x YCTO ceramics at room temperature.The varistor character-istics are generally characterized by the nonlinear coef ?cient αand the

breakdown ?eld E b .The current –voltage relationship of samples can be approximately described by:α?

log I 2=I 1eTlog U 2=U 1eT

e1T

where U 1and U 2are the voltage at current I 1and I 2,respectively.αis calculated when I 1=0.1mA and I 2=1mA.The breakdown ?eld is the voltage on the unit thickness at 1mA current:E b ?

U 1mA d

e2T

where U 1mA is the voltage at 1mA current and d is the thickness of samples.

Table 2

EDS results for the marked points in Fig.1(b).Element/at.%

A B C

D O 64.8666.2561.8964.29Ca 0.870.51 4.76 4.90Ti 20.4918.0621.7720.77Cu 9.088.8710.349.15Y

4.70

6.30

1.25

0.89

Fig.3.SEM pictures of 1100°C-10h sintered (1?x )CCTO ?x YCTO ceramics:(a)x =1.0(b)x =0.8(c)x =0.5(d)x =0.2(e)x =0.

Table 3

The densities of sintered (1?x )CCTO ?x YCTO ceramics.

Samples x =0x =0.2x =0.5x =0.8x =1.0ρ(g/cm 3) 4.673 4.645 4.790 4.889 4.843ρ(%)

91.89

91.34

93.16

94.03

92.48

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J.Li et al./Materials and Design 92(2016)546–551

The nonlinear coef ?cient αand breakdown ?eld E b of samples calcu-lated according to Eqs.(1)and (2)are listed in Table 4.It was illustrated that the varistor characteristics of samples with x =0.5and 0.8were greatly improved.The nonlinear coef ?cient αof sample with x =0.8was enhanced to 9.88,which is about two times of the normal value of CCTO.Meanwhile,the breakdown ?eld was also enhanced to 11.24kV/cm which is nearly an order of magnitude higher than that of normal CCTO sample.3.3.Dielectric properties

The composite structure combining both CCTO and YCTO phases,plays a key role on the dielectric properties.Fig.5(a)presents the curves of dielectric permittivity (ε’)against frequency at room temperature.ε’of composite ceramics declined to ~2000compared to CCTO and YCTO ceramics.This can be explained by IBLC model,according to which ε’is proportional to grain size [28],and the signi ?cant suppression of average gain size led to lower ε’.

In addition,the frequency dependence of dielectric loss (tan δ)at room temperature is shown in Fig.5(b).The low-frequency loss is greatly suppressed as well as the middle frequency for samples with

x =0.5and 0.8.It is notable that tan δhas been reduced in a wide frequency range (10–105Hz),rather than a narrow range around 103Hz [29].The minimum of dielectric loss in the sample with x =0.8reaches 0.02,which is signi ?cantly reduced compared to 0.1–0.2of CCTO sample.Generally,when the effect of dc conductivity is concerned,the dielectric loss can be expressed as:tan δ?

g tσdc ωε0ε0

e3T

where ε0is the vacuum permittivity,ε′is the relative permittivity,σdc is the dc conductivity,ωis the angular frequency,and g is equivalent conductivity of relaxation.As revealed in the discussion of varistor performance,E b is greatly enhanced,indicating that the dc conductivity was depressed.The contribution of dc conductivity to dielectric loss is inversely proportional to the frequency,i.e.approximately to σdc /ωε0ε′.The decrease of dielectric loss in the wide frequency range,especially at lower frequency,can be attributed to the restraint of dc conduction component.

The sample with x =0.8exhibit extremely low dielectric loss to 0.02with permittivity ~2000.These parameters are close to SrTiO 3varistor,which has been widely used in over voltage protections of electronic devices [30].However,a complex multistage process is required in the production of the present commercial SrTiO 3varistor ceramics and a surface effect is inevitable [7,8].This single-stage process of preparation of YCTO/CCTO composite ceramics shows remarkable technological advantage.

https://www.doczj.com/doc/7d6683138.html,plex impendence spectroscopy analysis

According to IBLC model,a series circuit of two RC parallel circuits can be employed to illustrate electrical heterogeneity of grains and grain boundaries in polycrystalline ceramics.The complex impedance (Z *)of the equivalent circuit can be calculated as following:Z ??Z 0?iZ ″?

R gb 1ti ωR gb C gb t

R g

1ti ωR g C g

e4T

Z 0?

R g

1tωR g C g àá2tR gb 1tωR gb C gb

àá2e5T

Z ″?R g

ωR g C g

1tωR g C g àá"

#tR gb ωR gb C gb 1tωR gb C gb

àá"#

e6T

where R gb and C gb are the resistance and capacitance of grain bound-aries while R g and C g are the resistance and capacitance of grains.

The

Fig.4.J –E curves of (1?x )CCTO ?x YCTO ceramics sintered at 1100°C for 10h.

Table 4

Nonlinear coef ?cient αand breakdown ?eld E b of (1?x )CCTO ?x YCTO ceramics.Samples x =0x =0.2x =0.5x =0.8α

4.93 2.729.579.88E b /kV .cm ?1

1.24

2.78

10.72

11.24

Fig.5.Dielectric permittivity and dielectric loss of (1?x )CCTO ?x YCTO ceramics sintered at 1100°C for 10h (a)dielectric permittivity (b)dielectric loss.

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J.Li et al./Materials and Design 92(2016)546–551

impendence spectroscopy of (1?x )CCTO ?x YCTO ceramics at room temperature is plotted in Fig.6.According to Eq.(4),the resistance of grain R g and grain boundary R gb can be obtained from intercepts on Z ’axis.The calculated results at room temperature are plotted in Fig.9.It can be found that R g is close to 20–40Ωwhile R gb varies signi ?cantly.A notable improvement to 1200M Ωof R gb can be identi ?ed in sample with x =0.8,while the value of CCTO sample is 264M Ω.The dielectric performance of sample is dominated by the grain boundary responses at low frequency,and higher R gb leads to lower dielectric loss.The remarkable enhancement of R gb for sample with x =0.8effectively suppressed the dielectric loss,which is consist with the results in Fig.5(b).

To further study the relaxation mechanism,impendence spectrosco-py measurement at a wide temperature range (?140–200°C)was carried out.The impendence spectroscopy of sample with x =0.8at different temperatures is plotted in Fig.7.The activation energies of grain resistance and grain boundary resistance E g and E gb ,according to Arrhenius equation,can be calculated via relevant resistances at different temperatures:ln R ?

?E a

k B T

tln R 0e7T

where E a is the activation energy,and k B is the Boltzmann constant.

As shown in Fig.8,E g and E gb are calculated as 0.09eV and 1.50eV for sample with x =0.8.Calculated E g and E gb of samples (x =0.0,0.5,0.8)are plotted together in Fig.9as well.It can be seen in Fig.9that E g of all samples are close to 0.1eV while E gb varies from 0.69eV to 1.50eV.

It has been proposed that the nonlinear properties of varistors are related to the Schottky barrier in grain boundary [11].The electron transport under electric ?eld obeys the thermionic emission model leading to the nonlinear J –E characteristic in CCTO ceramics [31].Thus the Schottky barrier height can be approached by E gb .As shown in Fig.9,E gb gradually increases with the increase of value x ,which suggests that the Schottky barrier gradually developed with the addition of YCTO.The barrier height of sample with x =0.8reaches a maximum value of 1.50eV,which is twice higher than 0.69eV of CCTO sample.The high barrier height leads to high nonlinear coef ?cient,which is consistent with the measurement results of J –E performance shown in Fig.4.4.Conclusions

(1?x )CCTO ?x YCTO composite ceramics were prepared by conventional solid state reaction method.The nonlinear and dielectric properties of composite ceramics were signi ?cantly improved,especial-ly for sample with x =0.8.The nonlinear coef ?cient and the breakdown ?eld were greatly enhanced to 9.88and 11.24kV/cm respectively and the dielectric loss could be suppressed as low as 0.02with the per-mittivity of ~2000.It is considered to be a promising varistor material for over voltage protection in electronic systems.In addition,complex impendence spectroscopy analysis showed that sample with x =0.8ex-hibited elevated Schottky barrier height and grain boundary resistance of 1.5eV and 1200M Ωrespectively,while the values of CCTO ceramics are 0.65–0.72eV and 200–300M Ω[32].The elevated grain boundary barrier and resistance could block the movement of charge carriers and thus suppress the dc conductivity as well as dielectric loss,leading to excellent comprehensive dielectric performance as a potential varis-tor

material.

https://www.doczj.com/doc/7d6683138.html,plex impedance spectroscopy of (1?x )CCTO ?x YCTO ceramics at room tem-perature.Inset (a)is enlarged view at high frequency close to the origin,(b)and (c)are corresponding impedance spectroscopy at 160°C with different scale for clear view

respectively.

Fig.7.Impedance spectroscopy of 0.2CCTO –0.8YCTO sample under different temperatures (a)40°C –120°C (b)?140°C to ?70

°C.

Fig.8.Fitting results of activation energy of 0.2CCTO –0.8YCTO sample.

550J.Li et al./Materials and Design 92(2016)546–551

Acknowledgments

This work was supported by the Natural Science Foundation of China (No.51177121)and (No.51221005)and the Natural Science Foundation of Shaanxi Province of China (No.2015JM5243).References

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Fig.9.Calculated parameters according to the impendence spectroscopy of (1?x )CCTO ?x YCTO ceramics.

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J.Li et al./Materials and Design 92(2016)546–551

MaxDOS8.0工具箱简介

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