RU2509716C2 - Method of creation of composite ferroelectric nanostructure - Google Patents

Method of creation of composite ferroelectric nanostructure Download PDF

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RU2509716C2
RU2509716C2 RU2012124892/28A RU2012124892A RU2509716C2 RU 2509716 C2 RU2509716 C2 RU 2509716C2 RU 2012124892/28 A RU2012124892/28 A RU 2012124892/28A RU 2012124892 A RU2012124892 A RU 2012124892A RU 2509716 C2 RU2509716 C2 RU 2509716C2
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ferroelectric
matrix
material
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Александр Степанович Сидоркин
Надежда Геннадьевна Поправко
Ольга Владимировна Рогазинская
Светлана Дмитриевна Миловидова
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Александр Степанович Сидоркин
Надежда Геннадьевна Поправко
Ольга Владимировна Рогазинская
Светлана Дмитриевна Миловидова
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Abstract

FIELD: nanotechnology.
SUBSTANCE: invention relates to methods of synthesizing of new materials with predetermined electrophysical characteristics and can be used to create functional materials with the controlled characteristics for the needs of modern micro- and nanoelectronics. The method of creation of the composite ferroelectric nanostructure based on creation in the composite of effect of internal shifting field consists in embedding of the ferroelectric material, namely triglycine sulfate, to the porous dielectric matrix with the pore size of 10-100 nm. The embedding is carried out of a saturated aqueous solution (melt) of ferroelectric salt heated to temperatures close to the Curie temperature of the bulk ferroelectric material, and the size of the internal shifting field determining the degree of expansion of the temperature interval of existence of the ferroelectric phase is varied due to the difference in the lineal expansion coefficients of the ferroelectric material and the matrix material and also due to the total area of interaction of the of the ferroelectric material - matrix variable by selecting the size and topology of the matrix pores.
EFFECT: expansion of the temperature range of existence of the ferroelectric phase in the ferroelectric composite materials by tens of degrees.
4 cl, 2 dwg, 2 ex

Description

The invention relates to methods for synthesizing new materials with desired electrophysical characteristics and can be used to create functional materials with controlled characteristics for the needs of modern micro- and nanoelectronics.

A known method of producing ferroelectric structures based on their single crystals by introducing impurities into them, leading to the fixing of the polar state in certain areas of the crystal and, accordingly, to an increase in the phase transition temperature (Levanyuk A.R., Sigov AS Defects and Structural Phase Transitions. NY: Gordon and Breach, 1988). The formation of a defective structure in crystals upon the introduction of substitutional impurities in them promotes the fixation of spontaneous polarization in separate regions of the bulk sample, i.e., prevents the formation of a symmetric paraphase above the Curie temperature.

The disadvantage of this method is the impossibility of creating sufficiently high bias fields, allowing you to change the phase transition temperature by several degrees or more.

It is known that the effect of a substrate on a virtual strontium titanate ferroelectric turns it into a real ferroelectric with a sufficiently high phase transformation temperature (NAPertsev, AKTagantsev and N. Setter. Phase transitions and strain-induced ferroelectricity in SrTiO 3 epitaxial thin films, Phys. Rev. B 61 R825-R829, 2000).

However, this method relates to thin-film materials.

The closest is a method for producing ferroelectric thin films with an extended interval of existence of the ferroelectric phase with a decrease in thickness of less than several tens of nanometers (Bai F. Destruction of spin cycloid in (111) c- oriented BiFeO 3 thin films by epitiaxial constraint: Enhanced polarization and release of latent magnetization / F.Bai, J.Wang, M.Wutting, JFLi, N.Wang, A.Pyatakov, AKZvezdin, LECross, D.Viehland // Appl. Phys. Lett. - 2005. - V.86. - No. 3.- P.032511 (1-3)).

The presence of a limited contact area between the film and the substrate, as well as the specified geometry of the sample, prevents a significant expansion of the temperature range of the existence of the ferroelectric phase, since the ratio of the film thickness to the film-substrate interface limits the maximum internal bias fields that fix the polarized state of the material.

The objective of the invention is to obtain a functional ferroelectric material with predetermined electrical parameters, in particular the temperature of the ferroelectric phase transition.

The technical result is the expansion of the temperature range of the existence of the ferroelectric phase in ferroelectric composite materials by tens of degrees.

The technical result is achieved by the fact that in the method of creating a composite ferroelectric nanostructure based on creating an internal bias field effect in the composite, fixing the polarized state of the ferroelectric material and shifting the phase transition point, according to the invention, the ferroelectric material is embedded in a porous dielectric matrix with pore sizes of the order of 10-100 nm, the introduction is made from a saturated aqueous solution (melt) of ferroelectric salt, heated to ur, close to the Curie temperature of a bulk ferroelectric material, and the magnitude of the internal bias field, which determines the degree of expansion of the temperature range of the existence of the ferroelectric phase, varies due to the difference in the linear expansion coefficients of the ferroelectric and the matrix material, as well as due to the total interaction area of the ferroelectric - matrix, which is changed by selection of pore size and topology of the matrix.

Triglycine sulfate is used as a ferroelectric material.

Porous alumina with a system of symmetrically located isolated pores with an average diameter of about 40 nm and a pore density of about 10 7 per cm 2 or porous glass with an average pore diameter of 7 nm and a porosity of about 25%, the porous structure of which is three-dimensional system of arbitrarily located interconnected dendritic channels.

To obtain a temperature shift of the ferroelectric phase transition to lower temperatures, it is necessary to reduce the degree of interaction of the ferroelectric material with the matrix by selecting the matrix material with the coefficient of thermal expansion closest to the ferroelectric. In this case, the effect of the depolarizing field, which suppresses the ferroelectric properties, will prevail over the effect of the internal bias field.

The technical result obtained during the implementation of the invention, namely, the expansion of the temperature range of the existence of the ferroelectric phase in ferroelectric composite materials by tens of degrees, is achieved due to the fact that the ferroelectric material and the matrix material have different coefficients of thermal expansion, as a result of which heating occurs at the ferroelectric-matrix interface mismatch deformations generating an internal bias field. The indicated effect has a significant effect on the temperature of the ferroelectric phase transition at the sizes of ferroelectric particles of the order of 10-100 nm.

Figure 1 shows the surface of the matrix of porous alumina Al 2 O 3 with a system of symmetrically located isolated pores with an average diameter of about 40 nm. Figure 2 shows the surface of the matrix of porous glass with a system of interconnected dendritic channels with a diameter of 7 nm.

The method is implemented as a result of incorporation of a ferroelectric material into a porous dielectric matrix with an average pore diameter of up to 100 nm. The introduction is made from a saturated aqueous solution (melt) of a ferroelectric salt heated to temperatures close to the Curie temperature of a bulk ferroelectric material. When cooled to room temperature in a few days, the ferroelectric crystallizes in the pores of the matrix. As a result, a composite structure is formed, consisting of separate or interconnected ferroelectric particles (crystallites) in a dielectric medium. When heated, TGS crystallites interact with the surrounding matrix. The mismatch of the crystal lattices of the nanoparticles and the matrix leads to the appearance of mismatch strains and related stresses, which can be estimated by the formula σ = E one - ν T a n T a n T 0 ( a f - a s ) d T

Figure 00000001
where E is the Young's modulus of the ferroelectric, ν is its Poisson's ratio, a f and a s are the linear expansion coefficients of crystallites and matrices, respectively. The integral is taken from the crystallization temperature of the ferroelectric particles in the matrix to the measurement temperature. These voltages due to the piezoelectric effect generate an internal bias field, estimated as E = four π d σ ε
Figure 00000002
(here d is the piezoelectric module), which leads to a shift of the Curie point to the high-temperature region.

Example 1. The composite structure of TGS - Al 2 O 3 synthesized on the basis of a porous matrix of aluminum oxide with an average pore diameter of 40 nm and a distribution density of 10 7 per cm 2 . The porous structure of the matrix is a system of isolated cylindrical channels symmetrically arranged by type of honeycombs (Fig. 1). When triglycine sulfate is introduced into the pores, isolated nanocrystallites are formed, symmetrically located relative to each other in a dielectric medium. The phase transition temperature shift for this composite composition reaches 15 K above the Curie temperature of a bulk triglycine sulfate single crystal (49 ° C).

Example 2. The composite structure of TGS - SiO 2 synthesized based on a matrix of porous glass with an average pore diameter of 7 nm and a porosity of about 25%. The porous structure of the matrix is a three-dimensional system of arbitrarily located interconnected dendritic channels (figure 2). Thus, ferroelectric particles embedded in a matrix of this type can not only interact with each other, but also form cluster structures whose properties can differ significantly from the properties of isolated particles. The temperature shift of the ferroelectric phase transition according to the above mechanism in this composite reaches 50-70 K above the Curie temperature of the bulk TGS single crystal.

Claims (4)

1. A method of creating a composite ferroelectric nanostructure based on the creation of an internal bias field in the composite, fixing the polarized state of the ferroelectric material and shifting the phase transition point, characterized in that the ferroelectric material is embedded in a porous dielectric matrix with pore sizes of the order of 10-100 nm, implementation produced from a saturated aqueous solution (melt) of ferroelectric salt heated to temperatures close to the Curie temperature of bulk seg etoelektricheskogo material and the magnitude of the internal field offset, determining the degree of expansion of the temperature interval of existence of a ferroelectric phase is varied by the difference in the linear expansion coefficients of the ferroelectric and the matrix material, and also due to the total surface area of the ferroelectric - matrix variable by selecting the size and topology pore matrix.
2. The method according to claim 1, characterized in that triglycine sulfate is used as the ferroelectric material.
3. The method according to claim 1, characterized in that the porous alumina with a system of symmetrically located isolated pores with an average diameter of about 40 nm is used as a dielectric matrix.
4. The method according to claim 1, characterized in that as the dielectric matrix, porous glass with an average pore diameter of 7 nm is used, the porous structure of which is a three-dimensional system of arbitrarily located interconnected dendritic channels.
RU2012124892/28A 2012-06-18 2012-06-18 Method of creation of composite ferroelectric nanostructure RU2509716C2 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2599133C1 (en) * 2015-07-06 2016-10-10 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Воронежский государственный университет" (ФГБОУ ВПО "ВГУ") Ferroelectric nanocomposite material based on nanocrystalline cellulose and triglycine sulfate
RU2666857C1 (en) * 2017-11-08 2018-09-12 федеральное государственное бюджетное образовательное учреждение высшего образования "Воронежский государственный университет" (ФГБОУ ВО "ВГУ") Ferroelectric nanocomposite material based on nanocrystalline cellulose and rochelle salt

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CN1170705A (en) * 1997-04-04 1998-01-21 清华大学 Perovskite type oxide terroelectrics gold nanometer particle composite material and its preparing method
WO2004022637A2 (en) * 2002-09-05 2004-03-18 Nanosys, Inc. Nanocomposites
WO2005019324A1 (en) * 2003-08-19 2005-03-03 Advanced Sciences Company Limited Heterogenic materials
JP2006241195A (en) * 2005-02-28 2006-09-14 National Institute Of Advanced Industrial & Technology Ferroelectric film and method for producing the same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1170705A (en) * 1997-04-04 1998-01-21 清华大学 Perovskite type oxide terroelectrics gold nanometer particle composite material and its preparing method
WO2004022637A2 (en) * 2002-09-05 2004-03-18 Nanosys, Inc. Nanocomposites
WO2005019324A1 (en) * 2003-08-19 2005-03-03 Advanced Sciences Company Limited Heterogenic materials
RU2249277C1 (en) * 2003-08-19 2005-03-27 Займидорога Олег Антонович Heterogeneous substance (heteroelectric) for acting on electromagnetic fields
JP2006241195A (en) * 2005-02-28 2006-09-14 National Institute Of Advanced Industrial & Technology Ferroelectric film and method for producing the same

Non-Patent Citations (1)

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Title
Bai F., et. Al. Destruction of spin cycloid in (111)c-oriented BiFeO3 thin films by epitiaxial constraint: Enhanced polarization and release of latent magnetization. Appl. Phys. Lett., 2005, V. 86, p.032511. *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2599133C1 (en) * 2015-07-06 2016-10-10 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Воронежский государственный университет" (ФГБОУ ВПО "ВГУ") Ferroelectric nanocomposite material based on nanocrystalline cellulose and triglycine sulfate
RU2666857C1 (en) * 2017-11-08 2018-09-12 федеральное государственное бюджетное образовательное учреждение высшего образования "Воронежский государственный университет" (ФГБОУ ВО "ВГУ") Ferroelectric nanocomposite material based on nanocrystalline cellulose and rochelle salt

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