Accepted Manuscript

Perovskite (La,Sr)MnO3 with Tunable Electrical Properties by the Sr-doping

Ke-lan Yan, Run-hua Fan, Min Chen, Kai Sun, Long-wei Yin, Hui Li, Shi-bing
Pan, Ming-xun Yu

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 Perovskite (La,Sr)MnO3 with Tunable Electrical Properties by the
Sr-doping Effect
Ke-lan Yan1, Run-hua Fan 1*, Min Chen, 1 Kai Sun 1, Long-wei Yin 1, Hui Li 1, Shi-bing Pan 1,2,
Ming-xun Yu2
1
Key Laboratory for Liquid-Solid Structural Evolution and Processing of Materials (Ministry of
Education), Shandong University, Jinan 250061, China
2
Shandong Non-metallic Materials, Jinan, 250031, China
*To whom correspondence should be addressed.Tel:+86 531 88393396; E-mail: [email protected]

ABSTACT: Recently, the negative index materials (NIMs), also called double negative materials

(DNMs) are receiving an increasing attention due to their many unique electromagnetic

properties and attractive applications prospect. DNMs are now well established in “artificial”

metamaterials, but it remains a challenge from the perspective of “natural” materials, especially

in single phase materials. Herein, the La1-xSrxMnO3 (LSMO, x=0.1, 0.2, 0.3, 0.4, 0.5) ceramics

with different Sr mole ratio (x) were prepared by combining the sol-gel process with

auto-combustion, followed by cold-pressing and sintering. The dielectric properties of LSMO

were studied at frequency ranges from 104 Hz to 108 Hz. The negative permittivity was realized,

and the permittivity and ac conductivity were drastically tuned by the Sr-doping effect.

Experimental results and theoretical simulation results indicate that the negative permittivity is

attributed to the Lorentz resonance (x=0.1) and the plasma oscillation (x>0.1), respectively. It is

further found that the doping elements tune the permittivity by adjusting the concentration of the

effective electrons, which is further supported by the frequency dependences of the conductivity

(σ'ac~ f ).

KEYWORDS: Double negative materials; Negative permittivity; Perovskite Manganite;

Metamaterial;

1
1. Introduction

In recent years, many unique electromagnetic properties, such as negative refraction effects are

desirable to use in various application fields, such as cloaking, novel cavity resonators,

microwave attenuation and microstrip antenna, etc [1-3]. Therefore, the negative index materials

(NIM), also called double negative materials (DNMs) with double negative parameters of

permittivity (ε<0) and permeability (μ<0), are receiving an increasing level of attention [4-5].

According to our previous works on cermets, DNMs have been obtained by adjusting the

microstructures of the composites, due to the plasma oscillation when the metal appropriately

diluted in insulating ceramics to achieve the moderate electron concentration and the magnetic

resonances of the magnetic inclusions in composites [6-7]. Interestingly, the La1-xSrxMnO3

(LSMO, x<0.17) are ferromagnetic conductors with Curie point above the room temperature [8].

Thereby, it is reasonable that LSMO could be an alternative to cermets to realize double negative

properties [9-11], due to its moderate electron concentration as well as its ferromagnetism [12].

The strontium-doped lanthanum manganites (La1-xSrxMnO3, LSMO) have attracted much

attention and are most commonly used as cathode in solid oxide fuel cells (SOFC), giant

magnetoresistance (GMR) films in magnetic field sensors or non-volatile magnetic random

access memories due to their excellent electrical and magnetic properties which could be tunable

with different Sr contents for the double-exchange effect [13-15]. Such interesting effect suggest

that LSMO can be used as microwave absorbing materials, and thus the microwave

characteristics, such as the effective complex relative permittivity εr=εr -j εr and permeability

µ r=µ r -j µ r of LSMO-epoxy composites were investigated in the frequency range of 2-18

GHz, to determine the reflection and attenuation characteristics of microwave absorbing [16].

Unfortunately, few works reported the dielectric or magnetic spectrum of pure LSMO at room

2
temperatures in air, such as the previous studies on the effects of domain wall motions and

domain rotations on the magnetic spectrum [17-18]. In particular, researches on the radio

frequency electrical properties, e.g. permittivity and electrical conductivity are lacking,

suggesting that further investigations are necessary to investigate the polarization and conduction

mechanism in LSMO.

In this work, we synthesize La1-xSrxMnO3 (x=0.1, 0.2, 0.3, 0.4, 0.5) by combining the ordinary

sol-gel process with auto- combustion at low temperature, wherein the Sr-doping effect on the

complex permittivity is investigated by using the Impedance/Material Analyzer. The negative

permittivity of LSMO is realized by tuning the effective concentration of conduction electrons

through the Sr-doping.

2. Experimental Methods

2.1 Samples Preparation

The sol-gel technology followed by cold-pressing and sintering was used to prepare

La1-xSrxMnO3 (LSMO, x=0.1, 0.2, 0.3, 0.4, 0.5) ceramics. The process of sol preparation is

described in detail in reference [19]. And then the sol was ignited to burn, followed by

calcinations to yield LSMO polycrystalline oxide powder, and then the powder was pressed into

discs with dimensions of 16 mm in diameter and 2 mm thickness, and the discs were sintered at

1350 °C for 2 hours.

2.2 Measurements

An X-ray diffractometer XRD (Rigaku D/Max - r B type) and field emission scanning electron

microscopy (FESEM, SU-70) were used to characterize the microstructure and morphology of

the sintered ceramics.

3
 The electrical properties were investigated by using an Agilent 4294A impedance analyzer.

The permittivity and conductivity measurements were performed under 100 mV ac voltages at

room temperature in the frequency range from 10 kHz to 100 MHz. The parameters of complex

permittivity (εr', εr'') and the real part of ac conductivity (σ'ac) were determined by the following

formula,

Cd
ε r′ =
ε0 A (1)

d
ε r′′ =
RA2πfε 0 (2)

d
σ ac ' =
RA (3)

where d is the sample thickness, C the capacitance, A the electrode plate area, R is resistances

and ε0 the absolute permittivity of free space (8.85×10-12 F m-1).

3. Results and Discussion

The XRD patterns and SEM images for La1-xSrxMnO3 (LSMO, x=0.1, 0.2, 0.3, 0.4, 0.5)

ceramics are shown in Figure 1. For all samples sintered at 1350 °C for 2 h, the perovskite-type

LSMO phase was identified from XRD patterns (Figure 1a), which revealed good crystallinity

with no detectable secondary phase within the sensitivity limits of the experiment. The XRD

patterns also indicate that the symmetry of crystal structure is improved with the increased

amount of Sr doping, for the bimodal diffraction peaks show a general tendency to be unimodal

peak with the increased amount of Sr doping. For example, (202) diffraction peak in XRD

patterns is present for samples with the Sr content of x≤0.3, and then (202) peak is absent for the

Sr contents of x≥0.4. It is attributed to the role of Sr, which has a larger ionic radius than that of

La3+ (rLa3+=0.106 nm, rSr2+=0.112 nm), to increase the average ionic radius <rA> (where, <rA>

4
= (1 − x ) rLa 3+ + xrSr 2+ = ( rSr 2+ − rLa 3+ ) x + rLa 3+ ); Meanwhile, the role of Sr-doping can change the

valence state of Mn ionic (Mn3+→Mn4+) to keep electrically neutral, and then the average ionic

radius <rB> (where, <rB> = (1 − x)rMn 3+ + xrMn 4+ = (rMn 4+ − rMn 3+ ) x + rMn 3+ ) is decreased.

Consequently, the "tolerance factor" t = ( rA +rO ) 2 ( rB + rO )

defined by Goldschmidt [20], is enlarged, and the crystal structure of the samples is changed by

the Jahn-Teller effect from rhombohedral to tetragonal crystal structure [21], i.e., the crystal

distortion diminishes and the symmetry of crystal structure is improves. Therefore, the

conduction band is enlarged, and the double exchange effect is then enhanced for the double

exchange interaction in direct proportion to the bandwidth of the eg electron, enhancing the

electromagnetic properties.

The SEM images for fractured surfaces in Figure 1(b)-(f) indicate that the particle sizes of

the LSMO samples are estimated to 2.5 μm (x= 0.1), 1.3 μm (x= 0.2), 2.8 μm (x= 0.3), 0.9 μm

(x= 0.4) and 0.8 μm (x=0.5), respectively.

As shown in Figure 2, the dielectric spectra for the LSMO samples with different Sr

contents were presented. For sample with x=0.1, the real part of permittivity εr' is negative when

the strong resonance appears (insert of Figure 2a). As the imaginary part (εr'') shown in Figure

2(b), the resonance frequency is about 8 MHz, and the dielectric dispersion displays a classical

Lorentz model [22]. Then the increase of the strontium content results in the appearance of

negative permittivity in the overall frequency range of our investigation (10 kHz -100 MHz).

From the above discussion, it is evident that the permittivity was drastically tuned by the

Sr-doping effect. And for the imaginary part (εr''), the εr''-f curves show a good linear relation

with frequency, especially in high frequency band (insert of Figure 2b).

5
 As the dielectric constant is defined in terms of the electric field E and the polarization P,

the displacement D=ε0E+P=εrε0E, thus the relative permittivity εr=1+P/E. As is known, the

equation for electronic motion expressing the interaction of the electromagnetic wave (EM wave)

with matter is written as [23-24]:

d 2x dx
m 2
+ mωτ + mω02 x = eE0 e −iωt
dt dt (4)

Where, m is the mass of the electron, ωτ takes into account damping effects, ω0=2πf0 is the

characteristic frequency, E0 is the amplitude and ω= 2πf is the angular frequency of the incident

EM wave, e is the electron charge (1.6×10-19 C). The solution of x to this equation is the electron

displacement, and then the displacement is given by

eE0 e − iωt
x=
m(ω02 − ω 2 + iωωτ ) (5)

If now we suppose that N is the total number of electrons, thus P=Nex, therefore the complex,

frequency dependent relative permittivity εr=1+P/E=1+ Nex/E becomes:

neff e 2 ω p2
εr = 1+ = 1 +
ε 0 meff (ω02 − ω 2 + iωωτ ) ω02 − ω 2 + iωωτ
(6)

where ωp = 2πfp= ( n eff e 2 / meff ε 0 )1/2 is the plasma frequency, neff is the effective concentration of

conduction electrons, meff is the effective mass of the electron. The equation (6) is called Lorentz

model and each electron participating in the interaction of the EM wave leads to such a mode.

The plasma oscillation model can be obtained from the Lorentz model when the item of restoring

6
force ( mω 02 x ) in equation (4) are negligibly small by setting ω0=0 [25]. Hence, the plasma

oscillation model frequency dependence of permittivity can be simplified to

ω p2
ε r = 1− (7)
ω 2 - iωωτ

The εr' - f curve of La1-xSrxMnO3 (x= 0.1) fitted using the Lorentz model by equation (6) (solid

line in Figure 2a) and La1-xSrxMnO3 with different Sr content (x = 0.2, 0.3, 0.4, and 0.5) fitted by

the plasma oscillation model (dotted and dash line in Figure 2a) agree well with the

experimental results, suggesting the effective fp of 7.9 MHz(x= 0.1), 28.0 MHz (x= 0.2), 45.2

MHz (x= 0.3), 44.3 MHz (x= 0.4) and 42.5MHz (x= 0.5), respectively.

The anomalous dispersion phenomena of the above results can be explained by the

double-exchange model due to the Sr-doping effect. As a function of Sr doping, the valence state

of Mn3+ ionic will be changed to Mn4+, causing the 3d eg electrons to ′cruise′ between these two

ions through an oxygen atom, and the eg electrons called itinerant electron is similar to the

conduction electrons. With increasing Sr doping, the concentration of the eg electrons is adjusted,

which is further supported by the frequency dependences of the conductivity (σ'ac) (Figure 3).

For sample with x=0.1, the σ'ac is almost frequency independent at low frequencies; while at high

frequencies, σ'ac increases with the frequency, and the frequency dispersion behavior represents

the Jonscher power law in the form of σ'ac(f) ∝ (2πf)n, and the fitting result of n is 0.91 (shown in

Table 1), which indicates that the conductive mechanism is hopping conduction due to the fact

that the majority of electrons were localized [26]. The σ'ac(f) exhibits a characteristic of plateau

in the low-frequency regime and a frequency dispersion in the high-frequency regime with an

onset frequency that is a function of the materials [27]. The same phenomenon of that the

frequency as marking the onset of ac conduction was also noted in Co/ZnO nanocomposites [28].

7
For samples with x = 0.2, 0.3, 0.4, 0.5, the σ'ac decreases with increasing frequency due to the

skin effect of conduction electrons in LSMO, which is similar to the free electron conduction,

showing different conductive mechanism from the sample with x = 0.1. The reason is that the eg

electron concentration is increased for the increasing of Mn4+ ions as Sr-doping effect.

Furthermore, the frequency dependence of σac for sample with Sr content of x=0.2, 0.3, 0.4 and

0.5 follows the Drude model [29]:

σ dcωτ2
σ ac ' =
ω 2 + ωτ2 (8)

where σdc=Ne2τ/m =ωp2τ/4π is the DC limit of the conductivity, ωτ=1/τ is the relaxation rate, and

ωp is the plasma frequency. The fitting results for the samples with Sr content of x=0.2, 0.3, 0.4

and 0.5 according to Eq. (8) are shown in Figure 3 as dotted lines, and the fitting results are

shown in Table 1. The fitting results of σdc suggest that the electron concentration was adjusted.

4. Conclusions

In summary, the dielectric properties of the LSMO ceramics with different Sr contents were

studied at wide frequency ranges from 104 Hz to 108 Hz. The concentration of the eg electrons is

adjusted by the Sr-doping content, therefore, the permittivity and ac conductivity were tuned and

the negative permittivity is realized. The results could be explained by Lorentz resonance (x=0.1)

and the plasma oscillation (x> 0.1), respectively. Furthermore, the doping elements tune the

electronic properties by tuning the effective concentration of free electrons, which is further

proved by the frequency dependences of the conductivity (σ'ac).

8
ACKNOWLEDGMENTS

The authors acknowledge the supports of National Natural Science Foundation of China

(50772061, 51172131).

AUTHOR INFORMATION

Corresponding Author

*R. H. Fan, Key Laboratory for Liquid-Solid Structural Evolution and Processing of Materials

(Ministry of Education), Shandong University, Jinan 250061, China

E-mail: [email protected]

Author Contributions

The manuscript was written through contributions of all authors. All authors have given approval

to the final version of the manuscript.

Notes

The authors declare no competing financial interest.

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Figure lists

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FIG. 1 The XRD patterns (a) and SEM images (b-f) of the La1-xSrxMnO3 (x =0.1, 0.2, 0.3, 0.4,

0.5) ceramics sintered at 1350 °C for 2 h.

FIG. 2 Dielectric spectra of La1-xSrxMnO3 (x =0.1, 0.2, 0.3, 0.4, 0.5) ceramics; the real (a) and

imaginary (b) parts of the complex permittivity for ceramics with different Sr mole ratios (x). For

x=0.1, the frequency dependence described by Lorentz model (solid red curves) and for x =0.2,

0.3, 0.4, 0.5, the dielectric dispersion can be fitted by plasma oscillation model.

FIG. 3 Frequency dependence of ac conductivity σ'ac for La1-xSrxMnO3 (x =0.1, 0.2, 0.3, 0.4, 0.5)

ceramics. The red solid line is σ'ac of sample with x=0.1 fitted by the Jonscher power law in the

form of σ'ac(f) ∝ (2πf)n, characterizing hopping conduction behavior. For samples with x =0.2, 0.3,

0.4, 0.5, the σ'ac decreases with increasing frequency, showing different conductive mechanism.

Table Captions:

Table 1. The fitting parameters obtained upon fitting conductivity behavior.

12
FIG. 1 The XRD patterns (a) and SEM images (b-f) of the La1-xSrxMnO3 (x =0.1, 0.2, 0.3, 0.4,

0.5) ceramics sintered at 1350 °C for 2 h.

13
FIG. 2 Dielectric spectra of La1-xSrxMnO3 (x =0.1, 0.2, 0.3, 0.4, 0.5) ceramics; the real (a) and

imaginary (b) parts of the complex permittivity for ceramics with different Sr mole ratios (x). For

14
x=0.1, the frequency dependence described by Lorentz model (solid red curves) and for x =0.2,

0.3, 0.4, 0.5, the dielectric dispersion can be fitted by plasma oscillation model.

FIG. 3 Frequency dependence of ac conductivity σ'ac for La1-xSrxMnO3 (x =0.1, 0.2, 0.3, 0.4, 0.5)

ceramics. The red solid line is σ'ac of sample with x=0.1 fitted by the Jonscher power law in the

form of σ'ac(f) ∝ (2πf)n, characterizing hopping conduction behavior. For samples with x =0.2,

0.3, 0.4, 0.5, the σ'ac decreases with increasing frequency, showing different conductive

mechanism.

15
Table 1. Fitting parameters for La1-xSrxMnO3 (x=0.1, 0.2, 0.3, 0.4, 0.5)

Fitting parameters
x error
n dc (S/cm)

0.1 0.91 - 1.75%

0.2 - 0.06 0.21%

0.3 - 0.19 0.72%

0.4 - 0.05 0.64%

0.5 - 0.04 0.22%

16