Учебное пособие 800637

tg	tg (T)		.	,	-
25	1	.			-
					tg .
tg .	1	7 ° /
			1-	[1],	-
		tg			-
,		.
200		tg
≈ 79 ° .	200
(	≈ 113 ° ),				.
ё	.				ln (1/T)
		≈ 1,6	,
.		[2].			-

1.Gridnev S.A. // Ferroelectrics. 2002. V. 266. P. 171–209.

2.Kang B.S., Choi S.K. // J. Appl. Phys. 2003. V. 94. P. 1904–1911.

537.226

,

:

. .	1, . .				2,	. .	3, . .		4, . .	5
1	. .	.,	-	.-	.	, [e-mail]
2	. .,	-		.-	.	, [e-mail]
3	. .	.,	-	.-	.	, [e-mail]
	4		,	-	.-	.	, [e-mail]
5			,	-	.-	.	, [e-mail]
1,2,3				-				. . .
4,5	-
		«		»	.	. .	(	)
,
(PZT)										-
	:					Pb, Zr	Ti.		,
		,						,
-
.
				-			Pb(Zr,Ti)O3		(PZT)
			PZT,					.
(	),									-
			.						PZT	-
										,

100

	,	-
,		.
	,	-
		[1].
80% Ar + 20% O2	.	~ 800 ,
PZT,
	– 600 .
	EVO-40 (Zeiss),	-

INCA.

								,														-
																				2-8 Pa (		1
. 1, ).	2 Pa														7%							-
	PZT ,			8 Pa																		-
21%.				(		. 2,		).							Ti/Zr					≈ 2,5%,		-
				.
)	1,2							1			)	0,47
Pb/(Zr+Ti)	1,1							2				0,46
											Ti/(Zr+Ti)
												0,45
	1,0											0,44
	2	3	4	5	6	7		8				0,43
														2	3	4	5		6	7	8
			Pressure, Pa													Pressure, Pa
	. 1.												Pb/(Zr+Ti) ( )					Ti/(Ti+Zr) (				)
															PZT.				1		. 1,
															(		)				,	2
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											.
				6,8x10-3
				6,4x10-3
				6,0x10-3
			a. u.	5,6x10-3
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				4,8x10-3					Zr
									Ti
						0	1	2	3		4	5		6	7	8
										Pressure, Pa

. 2.

Pb, Zr Ti

101

1.-

:	. . .	[	.] //	. - 2016. -
. 42(14). -	. 87 – 93.

UDC 537.226

EVOLUTION OF DIELECTRIC PROPERTIES IN THE (1-x)NaNbO3 - xGd1/3NbO3 SOLID SOLUTION SYSTEM

I.P. Raevski1, S.P. Kubrin2, V.A. Shuvaeva3, S.I. Raevskaya4, M.A. Malitskaya5, V.A. Iorshin6, I.N.

Zakharchenko7, V.V. Titov8, J.-L. Dellis9, G. R. Li10 1Dr. phys-mat.sci., professor, [e-mail]

2PhD, senior research associate, [e-mail]

3Dr. phys-mat.sci., leading research associate, [e-mail] 4PhD, associate professor, [e-mail]

5PhD, senior research associate, [e-mail]

6Student , [e-mail]

7PhD, senior research associate, [e-mail]

8PhD, research associate, [e-mail]

9 PhD, professor, [e-mail]

10 PhD, head of laboratory, [e-mail]

1-8Southern Federal University

9Université de Picardie Jules Verne

10Shanghai Institute of Ceramics, Chinese Academy of Sciences

Dielectric studies of (1-x)NaNbO3 - xGd1/3NbO3 solid solution compositions prepared using solid phase reactions route have been carried out in the temperature range 12-700 K. The permittivity– temperature dependences of the compositions studied were found to change, as x grows, from relatively sharp maxima typical of usual antiferroelectrics to the diffused but frequency-independent maxima typical of ferroelectrics and antiferroelectrics with diffused phase transition and then to the smeared and frequency-dependent maxima typical of relaxors.

Keywords: antiferroelectric, diffused phase transition, NaNbO3, relaxor.

One of the main trends of modern materials science is the replacement of leadcontaining electronic materials with their lead-free analogues. Among the most prospective representatives of the new generation of lead-free functional materials are sodium niobate NaNbO3 -based solid solutions. Previously the main attention was paid to the ferroelectric NaNbO3 - KNbO3 and NaNbO3 - LiNbO3 solid solutions prospective for piezoelectric applications [1, 2]. Nowadays a far more promising application of NaNbO3 and its derivatives is considered to be high energy storage capacitors, where the antiferroelectric nature of the material is utilized.[3].

Solid solutions of NaNbO3 may be divided into two groups [4]. In solid solutions of the group I ( e.g. NaNbO3 - KNbO3 and NaNbO3 - LiNbO3) high temperature ferroelectric

(FE) phase appears at small (a few mol.%) content x of the second component, concentration dependence of the temperature Tm of dielectric permittivity maximum is rather smooth and the (T) maxima are sharp. In solid solutions of the group II the antiferroelectric (AFE) phase

remains stable up to a comparatively high threshold x=x0 value (x0 is usually about 10-15 mol.% [5]) while in compositions with x>x0 the phase, usually referred to as FE or ferrielec-

tric becomes stable, which is accompanied by an abrupt drop in Tm values and dramatic smearing of the (T) maxima. Solid solutions of the group II are most prospective for high

energy storage applications [3]. Though at room temperature NaNbO3 is an AFE, a sufficiently strong electric field induces in NaNbO3 an othorhombic (space group Pmc21) FE phase Q which remains stable after removing the field and it is destroyed only by heating up to high temperatures [3]. Recently stabilized antiferroelectricity and superior energy storage properties were reported for the compositions of the NaNbO3 -based lead-free ceramics with A-site

102

vacancies obtained via a Bi2O3 substitution -solid solution system [5]. The scope of the present work was the study of evolution of dielectric properties in the similar solid solution system with A-site vacancies (1-x)NaNbO3 - xGd1/3NbO3 .

Ceramic samples of (1-x)NaNbO3 - xGd1/3NbO3 compositions with x=0, 0.05, 0.10,

0.15 and 0.20 were prepared using solid phase reactions route. All the investigated compositions were single-phase and have a structure of the perovskite type. Dielectric studies carried

out in the 12 K-700 K temperature range have shown that the Tm(x) dependence has an abrupt drop at x = x0 ≈ 0.1. While Tm values of compositions with x<x0 do not depend on frequency, compositions with x>x0 exhibit a frequency dispersion of (T) and a frequency shift of Tm, i.e.

the increase of Tm with frequency. The frequency shift of Tm for the compositions with x>x0 is well described by the Vogel-Fulcher relation typical of relaxors. Diffusion of the (T) maxi- mum increases as x grows and the (T) maxima for compositions with x>x0 exhibiting relax-

or-like properties appear to be very smeared.

Acknowledgment. This study is supported by the Russian Science Foundation (project 19-12-00205).

References

1. Rödel J. Transferring lead-free piezoelectric ceramics into application / K.G. Webber, R. Dittmer, W. Jo, M. Kimura, D. Damjanovic // J. Eur. Ceram. Soc. – 2015. – V.35. – № 6. – P. 1659

–1681.

2.Wei H. An overview of lead-free piezoelectric materials and devices / H. Wei, H. Wang, Y. Xia, et al. // Mater. Chem. C. – 2018. – V. 6. – P. 12446-12467.

3.Liu Z. Antiferroelectrics for energy storage applications: a review / Z. Liu, T. Lu, J. Ye, G. Wang, X. Dong, R. Withers, Y. Liu // Adv. Mater. – 2018. – V. 3. – № 90. – P. 1800111.

4.Raevski I.P. NaNbO3-based relaxor / I. P. Raevski, L. A. Reznitchenko, M. A. Malitskaya, et al. // Ferroelectrics – 2004. – V. 299. – № 1. – P. 95 – 101.

5.Zhou M. Superior energy storage properties and excellent stability of novel NaNbO3-based

lead-free ceramics with A-site vacancy obtained via a Bi2O3 substitution strategy / M. Zhou, R. Liang, Z. Zhou, X. Dong // J. Mater. Chem. A. – 2018. – V. 6. – P. 17896 – 17904.

538.95

		. .		1, . .	2, . .	3, . .	4
				1	, [e-mail]
			2		, [e-mail]
3	.	.-	.	,		, [e-mail]
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12.5425.2017/8.9,

1. Rybianets A.N. New "damped by scattering" ceramic piezocomposites with extremally low QM values / A.N. Rybianets // Ferroelectrics. - 2007. - V. 360. - Issue 1. - P. 84-89.

104

2.Rybianets A. Impedance spectroscopy characterization of highly attenuating piezocomposites / A. Rybianets, Y. Eshel, R. Tasker // Proceedings of the 9th European Conference on NonDestructive Testing (ECNDT 2006). - 2006. - Paper 129. - P. 1-9.

3.Rybyanets A.N. Ceramic Piezocomposites: Modeling, Technology, and Characterization /

A.N. Rybyanets // Nova Science Publishers Inc. - 2010. - hapter 3. - P. 113-174.

: 538.95

-

. .

1

4 -

.-

.

[5].

,

,

,

	1, . .	2, . .	3, . .	4
		, [e-mail]
	2	, [e-mail]
	3	, [e-mail]
.	,		, [e-mail]
	«		»
	.		.		,
:		.	,	,	,

			-
	,	[1].	-
.	IEEE	,
,	,		-
	IEEE [2].	[3, 4]	-
			-
		.	-
	(PRAP)		-
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		(STEP) [6],
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12.5425.2017/8.9,

).

1.Rybyanets A. Ceramic Piezocomposites: Modeling, Technology, and Characterization / Andrey Rybyanets, Anastasia Rybyanets // IEEE Trans. UFFC. - 2011. - V. 58. - N. 9. - P. 1757-1774.

2.IEEE Standard on Piezoelectricity. ANSI/IEEE Std. 1987, 176 p.

3.Pardo, L.; Alemany, C.; Ricote, J.; Moure, A.; Poyato, R.; Alguero, M. Proc. Intern. Conf. Material Technology and Design of Integrated Piezoelectric Devices. Couurmayeur, Italy. 2004, 145.

4.Rybianets A.N. Automatic iterative evaluation of complex material constants of highly attenuating piezocomposites / A.N. Rybianets, R. Tasker // Ferroelectrics. - 2007. - V. 360. - P. 90-95.

5.PRAP (Piezoelectric Resonance Analysis Programme). TASl Technical Software Inc. (www.tasitechnical.com).

6.STEP (Electromechanical Response Characterisation Program). TASI Technical Software Inc. (www.tasitechnical.com).

537.226.4

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	2	.	.-	.	,	. . ., [e-mail]
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1.Whatmore R.W. Ferroelectrics, microsystems and nanotechnology / R.W.Whatmore // Ferroelectrics. - 1999. - V. 225. - P. 179-192.

2.Kholkin A.L. Self-polarization effect in Pb(Zr,Ti)O3 thin films / A.L. Kholkin, K.G. Brooks, D.V. Taylor, S. Hiboux, N. Setter // Integr. Ferroelectrics. - 1998. - V. 22. - P. 525533.

:538.956

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			1				,		, [e-mail]
						2		, [e-mail].
			3	.		-	,	.	, [e-mail]
			4	.		-		,	, [e-mail]
				5 -	.	.-	.	, . .	., [e-mail]
			6			.-	.	, . . ., [e-mail]
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	. .		. – 2012. –				. 54. –	. 5. –	. 947-949.
										109