Reactive temperature and growth time effects on the morphology of PMN–PT nanorods by hydrothermal synthesis

Accepted Manuscript Reactive temperature and growth time effects on the morphology of PMN-PT nanorods by hydrothermal synthesis W.B. Luo, K. He, D. Xu, C. Li, X.Y. Bai, Y. Shuai, C.G. Wu, W.L. Zhang PII:

S0925-8388(15)31460-2

DOI:

10.1016/j.jallcom.2015.10.205

Reference:

JALCOM 35760

To appear in:

Journal of Alloys and Compounds

Received Date: 23 September 2015 Revised Date:

20 October 2015

Accepted Date: 22 October 2015

Please cite this article as: W.B. Luo, K. He, D. Xu, C. Li, X.Y. Bai, Y. Shuai, C.G. Wu, W.L. Zhang, Reactive temperature and growth time effects on the morphology of PMN-PT nanorods by hydrothermal synthesis, Journal of Alloys and Compounds (2015), doi: 10.1016/j.jallcom.2015.10.205. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

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Graphic abstract

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Reactive temperature and growth time effects on the morphology of PMN-PT nanorods by hydrothermal synthesis W.B. Luo1, K.He2, D. Xu1,2*, C. Li1, X.Y. Bai1, Y. Shuai1,3, C.G. Wu1,3, W.L. Zhang1,3

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1. State Key Laboratory of Electronic Thin Films and Integrated Devices, University

of Electronic Science and Technology of China, Chengdu 610054, People’s Republic of China.

2. School of Material Science and Engineering, Jiangsu University, Zhenjiang 212013,

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People’s Republic of China.

3. Collaboration Innovation Center of Electronic Materials and Devices, University

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of Electronic Science and Technology of China, Chengdu 610054, China

Abstract: Single crystalline nanorod (Nr) is considered to be a promising candidate in many nano-electric devices due to its excellent electric properties. Here we report a method to fabricate 0.65(Mg1/3Nb2/3)O3-0.35PbTiO3 (PMN-PT) single crystalline Nr

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by controlling the hydrothermal synthesis temperature and reactive time. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) have been employed to investigate the morphology and crystal characteristics of the PMN-PT

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Nrs. It was confirmed that single crystalline PMN-PT Nrs have been fabricated under optimal synthesis condition. Finally, the ferroelectric properties of PMN-PT Nrs were

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measured, and the coercive field, remnant polarization and spontaneous polarization of the nanorods are 2.78 kV/mm, 17.08 µC/cm2 and 31.25 µC/cm2 respectively.

Key words: PMN-PT, Nanorods, Hydrothermal reaction, hysteresis. Corresponding author: Tel: +86-2883202140, Fax: +86-2883202569, E-mail address: [email protected]; [email protected]

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Introduction Functional materials like PZT[1, 2], BaTiO3[3, 4], ZnO[5-7], PMN-PT[8-10] et al. have

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attracted much attention in the field of military industry, civilian industry and daily life due to their remarkable ferroelectric, piezoelectric properties etc. In the application of energy harvesting, solid solutions (1-x)PbMg1/3Nb2/3O3-xPbTiO3

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(PMN-PT) with perovskite structure exhibit great ferroelectric/relaxor and piezoelectric/electrostrictive properties.[11] When “x” is in the range 0.32-0.36, the

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PMN-PT with formation of monoclinic Pm to tetragonal P4mm phase so called Morphotropic region exhibits excellent ferroelectric/piezoelectric properties.

[12]

For

example, it has been proved that the piezoelectric charge constant d33 of PMN-PT could arrive the range from 2000 to 2500 pC/N

[13]

, which is almost 4 times higher

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than that of PZT, and 90 times higher than that of ZnO[14, 15]. And, it is also reported that the recoverable energy-storage density W of the PMN-PT thin films could be as high as 11.8 J/cm3 [16]which indicated that PMN-PT possessed good energy storage

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ability. Therefore, the superior properties of solid solution PMN-PT make them useful for capacitors and energy electric generators.

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With the advance of the nanotechnology, the scientist found that even in the same

compound, the material with different morphology exhibit widely difference. Sun el al [17]

numerically estimates the potential output power and the energy conversion

efficiency of the different piezoelectric nanostructures of the PMN-PT. The analysis showed that PMN-PT Nrs would be superior candidates than the bulk in mechanical energy harvesting. Afterwards, Xu et al.

[18, 19]

prepared the PMN-PT Nrs by the

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hydrothermal process in 2012. They proved that the piezoelectric constant d33 of single PMN-PT Nr is much higher than other piezoelectric materials exactly.

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Therefore, the PMN-PT Nrs should be a promising material for various electrical devices application.

In this paper, the 0.65Pb(Mg1/3Nb2/3)O3-0.35PbTiO3 Nrs were prepared by the 21]

The effects of the hydrothermal temperature and the

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hydrothermal progress.[20,

progress time on the morphology of the PMN-PT Nrs were investigated. When the

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hydrothermal temperature is 235 oC, reacting time is 27 h, massive well-distributed pure PMN-PT Nrs could be obtained. The recoverable energy-storage density W (18.70 J/cm3) of the Nr was also estimated based on the remnant polarization Pr

Experiment

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(17.08 µc/cm2) and maximum polarization Pmax. (31.25 µc/cm2)

Hydrothermal method was carried to synthesize the as-wanted PMN-PT Nrs.

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Chemical grade, stoichiometric amounts of lead acetate trihydate, magnesium 2,4-pentanedionante

dehydrate,

niobium

ethoxide,

titanium

dissopropoxide

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bis(acetylacetonate) and 1, 1, 1-tri (hydroxymethyl) ethane were mixed with poly (ethylene glycol)-200 and methanol mixture under stirring condition. The volume ratio of the poly (ethylene glycol)-200 and methanol is 1:2. The concentration of resulting sol-gel was 0.1 M. Then, 50 ml PMN-PT sol-gel was dispersed into 600ml distilled water under strong stirring. 0.5 g polyacrylic acid (PAA) and 20 g KOH were added into yellow solution. After stirring ample time, the pellucid solution was

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introduced into a commercial autoclave with Polytetrafluoroethylene inner tank, sealed and kept in an oven for different temperature and time. For investigating the

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effects of temperature on the morphology of the PMN-PT Nrs, the reaction time was settled 27 h, and the hydrothermal temperature were settled 195, 215, 235 and 250 oC for sample PB1, PB2, PB3 and PB4 respectively. For investigating the effects of

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reaction time on the morphology of the PMN-PT Nrs, the hydrothermal temperature

was settled at 235 oC, the reaction time were settled as 12, 18, 23, 27 and 30 h. The

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detail parameters are show in table 1. After cooling, the yellow suspension was washed with DI water and ethanol six times to remove unwanted composites and dried at 80 oC in an electric hot plate. A green powder consisted of PMN-PT Nrs were obtained as the final product. For measuring the hysteresis loop of the single Nr, the

introduced later.

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Al electrodes were deposited on the two sides of the Nr, the detailed method will be

The morphology characteristics of PMN-PT Nrs were investigated by Scanning

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Electron Microscope (JSM-7500F, Japan). Transmission electron microscope (TEM) images and selected area electron diffraction (SAED) were obtained by Tecnai G2

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F20 S-TWIN. The ferroelectric hysteresis loop were measured by the RT 60 (The US)

Results and Discussions SEM images of the PMN-PT Nrs synthesized at different hydrothermal

temperatures are displayed in Fig. 1. It could be clearly seen from Fig. 1(a) that nearly no Nr was produced at 195 oC. The hydrothermal products are mainly consisted of

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nano powder as displayed in Fig. 1(b). As the hydrothermal temperature further increased, more and more Nrs appear in the SEM images. When the hydrothermal

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temperature increased to the 235 oC, the products consist of the massive and well distributed Nrs with the average length of 5 µm. But, with the temperature further

arose, the ratio of Nrs decrease, and plenty of the layer like structure emerge as

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indicated in Fig. 1(d). These results demonstrate that the reaction temperature has

great influence on the crystal growth. The grain core will begin to grow in a satisfied

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condition. In the Nr growth process, the crystal face would growth along on direction in the function of PAA. The PAA here severs as a restrictor of the radial direction growth[22]. If the temperature did not satisfy the PMN-PT crystal growth, the crystal nucleuses will not formally formed, as show in Fig. 1(a) and (b). When the

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temperature increases gradually, a small quantity of the crystal nucleuses will growth along the singleton direction in the function of the PAA as show in Fig. 1(c). It seems that the 235 oC may be the optimum growth temperature for the PMN-PT Nr growth.

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In this temperature, the hydrothermal products are mainly made up of Nrs. But with continue increase of the temperature, crystal nucleuses has higher growth rate and the

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surface would obtain higher energy. The effects of reactive time on the morphology of PMN-PT Nr was also studied

by SEM. Fig. 2 shows the SEM images of the PMN-PT Nrs prepared in 235 oC with

different reacting time. From Fig. 2, Nrs can be observed in all samples. The PMN-PT Nrs with small width and some flower structure could be observed in Fig. 2(a) at the shortest reactive time 12 h. The width of the Nr increases and the number of flower

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structure decreases as the react time increases. When the reacting time is 23 and 27 h, products with pure and massive Nrs could be obtained as show in Fig. 2(c) and (d).

the reacting time further increases according to Fig. 2(e).

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However, the number of Nrs decreases and some layer structure could be observed as

As mentioned previously, the optimum growth temperature of the PMN-PT Nrs

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may be 235 oC. It is worth to mention that the hydrothermal product with reaction

time 12 and 18 h contain many unwanted structures and the hydrothermal product

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with reaction time of 23 and 27 h nearly consist of pure Nrs. Thus, it is believed that the growth of the crystal nucleus is not coinstantaneous. When the reactive condition satisfies the limited growth kinetics condition, some crystal nucleus would growth preferentially, and the rest of the crystal nucleus growth latterly. With the adequate

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growth time nearly all crystal nucleus growth to the Nr as show in Fig. 2(c) and (d). Fig. 3 shows the TEM image of the PMN-PT Nr prepared by the hydrothermal in 235 o

C 27 h. Form Fig. 3(a), it could be easily estimate that the width of the Nr is 200nm.

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The high multiple images Fig. 3(b) shows the atoms arrangement of the Nr. The lattice parameter of the PMN-PT Nr is estimated 4.02 Å from Fig. 3(b). The insert part

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of the Fig. 4(b) is the electron diffraction image of the PMN-PT Nr, which suggests that the PMN-PT Nrs are single crystal PMN-PT. The ferroelectric hysteresis loop of the single PMN-PT Nr was measured. Fig.

4(a) shows the simple test method of the PMN-PT hysteresis measurement. The single PMN-PT Nr prepared in 235 oC 27 h were dispersed on a SiO2 coated Si substrate. The Al electron was deposited on the two sides of the Nr by the electron beam

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evaporation. Fig. 4(b) is the hysteresis loop of the single PMN-PT Nr. The coercive field, remnant polarization and spontaneous polarization of PMN-PT Nr are: 2.78

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kV/mm, 17.08 µC/cm2 and 31.25 µC/cm2 respectively. The ferroelectric parameters are silimar with other reported 0.65PMN-0.35PT ceramics(Pmax 31.5 µC/cm2, Pr 24.7 µC/cm2)[23]. Generally, the recoverable energy-storage density W of a capacitor could

formula expressed: W =∫

Pmax

Edp

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Pr

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be estimated from the polarization–electric field hysteresis (P–E) loops via the

where E is the applied electric field, P is the polarization, Pr is the remnant polarization and Pmax is the maximum polarization

[24, 25]

. According to the formula,

the area between the polarization axis and the discharge curve of the P–E loop

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represents the stored and recoverable energy. Based on this formula, the W values could be estimated according the P-E loops. In this case, the Newton-Cotes formula b

n

a

i =0

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( ∫ f ( x)dx ≈ (b − a )∑ Ci( n ) f ( xi ) ) was carried to solve the equation. The different parameter n from 1 to 6 was employed to the calculation. For n=1, 2, 3, 4, 5 and 6, the

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estimated W is 18.13, 18.84, 19.31, 18.46, 18.54 and 18.90 J/cm3 respectively. Thus, we could believe that the average energy-storage density W of this PMN-PT Nr is approximately 18.70 J/cm3 without the calculated value 18.13 and 19.31.

Conclusion The effects of the hydrothermal temperature and the reacting time on the morphology characteristics of the PMN-PT Nrs were investigated. Pure and massive

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PMN-PT nanorods have been synthesized by hydrothermal method at 235 oC for 27 h reactive. The coercive field, remnant polarization and spontaneous polarization of

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PMN-PT Nrs prepared at 235 oC and 27 h are: 2.78 kV/mm, 17.08µC/cm2 and 31.25

µC/cm2. The calculated recoverable energy-storage density W of the Nr is 18.70 J/cm3. which indicates the PMN-PT Nr has great potential application in the field of energy

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storing.

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Acknowledgments

This work was financially supported by National Natural Science Foundation of China (Grant No. 51572113), Cooperative Innovation Foundation of Jiangsu Province (BY2015064-04) and Jiangsu Government Scholarship for Overseas Studies

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Figure captions

Fig. 1 SEM images of the PMN-PT Nrs prepared by the hydrothermal reaction with different temperature in reaction time of 27 h. ((a), (b), (c) and (d) represent the

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images of the sample PB1, PB2, PB3 and PB4 respectively)

Fig. 2 SEM image of the PMN-PT Nrs prepared by the hydrothermal reaction in 235 o

C with different hydrothermal time 12, 18, 23, 27 and 30 h represented as (a),

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(b), (c), (d) and (e) respectively.

Fig. 3 TEM images of the PMN-PT Nr prepared in 235 oC 27h (PB4). ((a) is the low magnification of the PMN-PT Nr, (b) is the high magnification of the PMN-PT Nr, the insert part on the right of the (b) is the electron diffraction of the

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PMN-PT Nr)

Fig. 4(a) Diagrammatic sketch of the ferroelectric hysteresis loop measurement of the single PMN-PT Nr prepared at 235 oC 27 h. (b) Ferroelectric hysteresis loop of

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the single PMN-PT Nr prepared at 235 oC 27 h.

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Table 1 Detailed hydrothermal parameters of the PMN-PT preparation Reacting time (h) 27 27 27 27 12 18 23 27 30

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Hydrothermal temperature (oC) 195 215 235 250 235 235 235 235 235

Samples ID PB1 PB2 PB3 PB4 PC1 PC2 PC3 PC4 PC5

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Highlights

> 0.65(Mg1/3Nb2/3)O3-0.35PbTiO3 (PMN-PT) single crystalline nanorods were

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prepared by the hydrothermal method.

> The hydrothermal temperature has importance influence on the generation of the

crystal nucleus and the reaction time has great influence on the morphology of the

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PMN-PT Nanorods

> The coercive field, remnant polarization and spontaneous polarization of PMN-PT

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Nrs prepared at 235 oC and 27 h are: 2.78kV/mm, 17.08µc/cm2 and 31.25µc/cm2.