JPWO2018164068A1 - Complex oxide - Google Patents

Abstract

The present invention provides the following formula (I) or (II): Pb1-z / 2 ([ZrxSn1-x] 1-yTiy) 1-zM1zO3 (I); Pb1-w ([ZrxSn1-x] 1-yTiy) 1. -WM2wO3 (II) [where: x and y are points A1 (0.50, 0.07) and A2 (0.50, 0) on the triangular phase diagram drawn by the values of (x, y). .17), point A3 (0.65, 0.17), point A4 (0.75, 0.13), point A5 (0.75, 0.05), point A6 (0.70, 0.03) ) And a point A7 (0.60, 0.07) connected by a straight line (not including the boundary), z is 0.02 or more and 0.06 or less, and w is 0. Provided is a composite oxide of 0.02 or more and 0.06 or less.

Description

  TECHNICAL FIELD The present invention relates to a composite oxide, and more particularly to a composite oxide exhibiting an electrocaloric effect.

  In recent years, in small portable devices (smartphones, tablet PCs), and further in electronic devices such as data servers, the heat generated by the central processing unit (CPU), hard disk (HDD), etc. causes a decrease in device performance and a decrease in the life of electronic devices. Problems such as shortening of life and breakdown are becoming apparent. Thermal management in electronic devices is important for such problems. However, small electronic devices such as smartphones have a small power supply capacity and do not have a space for installing a large cooling device. Therefore, in such a small electronic device, at present, the only means for controlling the temperature is to radiate heat through the housing, and the heat source and the housing are thermally coupled by a thermal sheet or the like to release the heat. On the other hand, large electronic devices such as servers have sufficient power supply capacity and space, so that air conditioning equipment such as air conditioners, Peltier cooling devices, and the like are used.

As a material exhibiting the above-mentioned electrocaloric effect, for example, in Non-Patent Document 1, Pb _0.99 [(Zr _0.75 Sn _0.20 Ti _0.05 ) _0.98 Nb _0.02 ] O ₃ (Pb _0.99 Nb _0.02 [(Zr _0.789 Sn _0.211 ) _0.95 Ti _0.05 ] O ₃ equivalent) Niobium titanate lead zirconate stannate having a perovskite structure having the composition Ceramics are disclosed. In Non-Patent Document 1, the electrocaloric effect of this ceramic is evaluated by the Direct measurement method, and it is described that the electrocaloric effect of ΔT = 2.6K is exhibited when an electric field of 3 MV / m is applied at 161 ° C.

Non-Patent Document 2 discloses a commercial multilayer ceramic capacitor based on BaTiO ₃ . The electrocaloric effect of this ceramic capacitor is evaluated, and it is described that an electric field of 30 MV / m can be applied and that the electrocaloric effect of ΔT = 0.55K is exhibited.

B. A. Tuttle and D. A. Payne, Ferroelectrics, 37, 603-606 (1981) S Kar-Narayan and N D Mathur, J. Phys. D: Appl. Phys. 43 (2010) 032002 (4pp)

  In small electronic devices, there is a limit to heat dissipation through the housing as described above because the surface area of the housing is limited. Therefore, the temperature of each heat source is measured, and when the temperature exceeds a predetermined temperature, the performance of the CPU or the like is limited (the heat generation itself is suppressed). That is, an increase in the temperature of the housing may hinder the performance of the CPU or the like.

  Further, in a large-sized electronic device, although a sufficient cooling effect can be obtained by the air conditioning equipment as described above, there is a problem in that the power consumption is so large that the power cost is required for the heat management.

  Therefore, the present inventor has focused on the above-mentioned electrocaloric effect, and has come to the idea of using a composite oxide exhibiting this electrocaloric effect in a heat transfer device. A control voltage is required for this phenomenon, but since the above complex oxide is a ferroelectric insulator, it consumes very little power, has a low power cost, and is used in small portable devices with limited power capacity. It is possible.

  When using the electrocaloric effect in a high temperature environment such as server cooling, the problem is the amount of heat that can be handled and the insulating properties of the elements. In order to further increase the amount of heat that can be handled by a single element using the electrocaloric effect, it is necessary to use a material having a large electrocaloric effect for the dielectric layer of the element. Further, as for the electrocaloric effect, the amount of heat that can be handled increases as the electric field that can be applied increases. However, in general, dielectric ceramics have low insulating properties at high temperatures, and Joule heat is generated due to leakage current flowing when a voltage is applied.

The ceramic disclosed in Non-Patent Document 1 has a problem that it is difficult to apply a high electric field. Further, since the ceramic disclosed in Non-Patent Document 2 uses a ferroelectric material based on BaTiO ₃ which has a small electrocaloric effect, there is a problem that ΔT is small.

  Therefore, an object of the present invention is to provide a composite oxide exhibiting a large electrocaloric effect and having a high insulating property.

  As a result of intensive studies, the present inventors have found that a Pb (Zr, Sn, Ti) composite oxide is doped with Nb, Ta, W, or Mo, and the proportion thereof is set within a predetermined range to obtain a large value. The inventors have found that an electrocaloric effect and high insulation can be achieved, and have completed the present invention.

According to the first aspect of the present invention, the following formula (I) or (II):
_{Pb 1-z / 2 ([} Zr x Sn 1-x] 1-y Ti y) 1-z M 1 z O 3 (I)
_{Pb 1-w ([Zr x} Sn 1-x] 1-y Ti y) 1-w M 2 w O 3 (II)
[In the formula:
M ¹ is Nb or Ta,
M ² is W or Mo,
x and y are points A1 (0.50, 0.07) on the triangular phase diagram drawn by the value of (x, y),
Point A2 (0.50, 0.17),
Point A3 (0.65, 0.17),
Point A4 (0.75, 0.13),
Point A5 (0.75,0.05),
Point A6 (0.70,0.03) and point A7 (0.60,0.07)
It is in the range surrounded by the area connecting straight lines (but not including the boundary),
z is 0.02 or more and 0.06 or less,
w is 0.02 or more and 0.06 or less. ]
A complex oxide represented by:

According to the second aspect of the present invention,
Formula (I) or (II) below:
_{Pb 1-z / 2 ([} Zr x Sn 1-x] 1-y Ti y) 1-z M 1 z O 3 (I)
_{Pb 1-w ([Zr x} Sn 1-x] 1-y Ti y) 1-w M 2 w O 3 (II)
[In the formula:
M ¹ is Nb or Ta,
M ² is W or Mo,
x and y are points A11 (0.55, 0.15) on the triangular phase diagram drawn by the value of (x, y),
Point A12 (0.70, 0.15),
Point A13 (0.75, 0.13),
Point A14 (0.75,0.05),
Point A15 (0.70,0.05),
Point A16 (0.65, 0.08),
Point A17 (0.60,0.09) and point A18 (0.55,0.09)
It is in the range surrounded by the area that connects
z is 0.02 or more and 0.06 or less,
w is 0.02 or more and 0.06 or less. ]
A composite oxide represented by formula (I) or (II) is provided.

According to the third aspect of the present invention,
A composite oxide containing Pb, Zr, Sn, Ti and M ¹ or M ² ,
M ¹ is Nb or Ta,
M ² is W or Mo,
The molar part of Zr contained in 100 molar parts of Zr and Sn is p molar part,
The molar portion of Ti contained in 100 molar portions of Zr, Sn and Ti is q molar portion,
The content molar part of M ¹ in the total 100 molar parts of Zr, Sn, Ti and M ¹ is r molar part,
In 100 mol parts in total of Zr, Sn, Ti and M ² , the contained mol part of M ² is s mol part,
p and q are points C1 (50, 7) on the trigonometric diagram drawn by the value of (p, q),
Point C2 (50,17),
Point C3 (65, 17),
Point C4 (75,13),
Point C5 (75,5),
Point C6 (70,3) and point C7 (60,7)
It is in the range surrounded by the area connecting straight lines (but not including the boundary),
r is 2 or more and 6 or less,
s is 2 or more and 6 or less,
A composite oxide is provided.

According to the fourth aspect of the present invention,
A composite oxide containing Pb, Zr, Sn, Ti and M ¹ or M ² ,
M ¹ is Nb or Ta,
M ² is W or Mo,
The molar part of Zr contained in 100 molar parts of Zr and Sn is p molar part,
The molar portion of Ti contained in 100 molar portions of Zr, Sn and Ti is q molar portion,
The content molar part of M ¹ in the total 100 molar parts of Zr, Sn, Ti and M ¹ is r molar part,
In 100 mol parts in total of Zr, Sn, Ti and M ² , the contained mol part of M ² is s mol part,
p and q are points C11 (55, 15) on the triangular phase diagram drawn by the value of (p, q),
Point C12 (70,15),
Point C13 (75,13),
Point C14 (75,5),
Point C15 (70,5),
Point C16 (65,8),
Point C17 (60,9) and point C18 (55,9)
It is in the range surrounded by the area that connects
r is 2 or more and 6 or less,
s is 2 or more and 6 or less,
A composite oxide is provided.

  According to a fifth aspect of the present invention, there is provided an endothermic device comprising a laminated body having a plurality of electrode layers and a plurality of dielectric layers located between the electrode layers, the dielectric body comprising: There is provided an endothermic heating element whose layer is composed of the above complex oxide.

  According to a sixth aspect of the present invention, there is provided an electronic device including the heat absorbing / heating element.

According to the seventh aspect of the present invention,
A method for producing a composite oxide containing Pb, Zr, Sn, Ti and M ¹ (M ¹ is Nb or Ta) or M ² (M ² is W or Mo), comprising:
Pb, Zr, Sn, Ti and an oxide or salt of M ¹ or M ² ,
The molar part of Zr contained in 100 molar parts of Zr and Sn is p molar part,
The molar portion of Ti contained in 100 molar portions of Zr, Sn and Ti is q molar portion,
The content molar part of M ¹ in the total 100 molar parts of Zr, Sn, Ti and M ¹ is r molar part,
In 100 mol parts in total of Zr, Sn, Ti and M ² , the contained mol part of M ² is s mol part,
p and q are points C1 (50, 7) on the trigonometric diagram drawn by the value of (p, q),
Point C2 (50,17),
Point C3 (65, 17),
Point C4 (75,13),
Point C5 (75,5),
Point C6 (70,3) and point C7 (60,7)
It is in the range surrounded by the area connecting straight lines (but not including the boundary),
r is 2 or more and 6 or less,
s is 2 or more and 6 or less,
When M ¹ is included, the content of Pb based on 100 parts by mole of Zr, Sn, Ti and M ¹ is (100− (r / 2)), or when M ² is included, Zr, Sn, The content of Pb contained in 100 parts by mole of Ti and M ² is (100-s) parts by mole,
A manufacturing method is provided by mixing the above components in a proportion such that the above content is obtained and then firing in a lead atmosphere such that the above content is obtained.

According to the eighth aspect of the present invention,
A method for producing a composite oxide containing Pb, Zr, Sn, Ti and M ¹ (M ¹ is Nb or Ta) or M ² (M ² is W or Mo), comprising:
Pb, Zr, Sn, Ti and an oxide or salt of M ¹ or M ² ,
The molar part of Zr contained in 100 molar parts of Zr and Sn is p molar part,
The molar portion of Ti contained in 100 molar portions of Zr, Sn and Ti is q molar portion,
The content molar part of M ¹ in the total 100 molar parts of Zr, Sn, Ti and M ¹ is r molar part,
In 100 mol parts in total of Zr, Sn, Ti and M ² , the contained mol part of M ² is s mol part,
p and q are points C11 (55, 15) on the triangular phase diagram drawn by the value of (p, q),
Point C12 (70,15),
Point C13 (75,13),
Point C14 (75,5),
Point C15 (70,5),
Point C16 (65,8),
Point C17 (60,9) and point C18 (55,9)
It is in the range surrounded by the area that connects
r is 2 or more and 6 or less,
s is 2 or more and 6 or less,
When M ¹ is included, the content of Pb based on 100 parts by mole of Zr, Sn, Ti and M ¹ is (100− (r / 2)), or when M ² is included, Zr, Sn, The content of Pb contained in 100 parts by mole of Ti and M ² is (100-s) parts by mole,
A manufacturing method is provided by mixing the above components in a proportion such that the above content is obtained and then firing in a lead atmosphere such that the above content is obtained.

  According to the present invention, a composite oxide having a large electrocaloric effect and a high insulating property can be provided.

FIG. 1 is a schematic cross-sectional view of an endothermic heat generating element used in the present invention. FIG. 2 is a schematic cross-sectional view of another heat absorbing / heating element used in the present invention. FIG. 3 is a compositional triangular phase diagram of Zr, Sn, and Ti with respect to the sample of z = 0.02 (Sample Nos. 1 to 27) in the example. FIG. 4 is a graph showing the electric field dependence of ΔT for sample number 22. FIG. 5 is a graph showing the temperature dependence of ΔT when an electric field is applied, for sample number 22.

The material exhibiting the electrocaloric effect of the present invention is a Pb (Zr, Sn, Ti) complex oxide doped with M ¹ or M ² .

In one embodiment, the composite oxide of the present invention has the following formula (I) or (II):
_{Pb 1-z / 2 ([} Zr x Sn 1-x] 1-y Ti y) 1-z M 1 z O 3 (I)
_{Pb 1-w ([Zr x} Sn 1-x] 1-y Ti y) 1-w M 2 w O 3 (II)
[In the formula:
M ¹ is Nb or Ta,
M ² is W or Mo,
x is 0.55 or more and 0.75 or less, preferably 0.55 or more and 0.70 or less,
y is 0.05 or more and 0.15 or less,
z is 0.02 or more and 0.06 or less,
w is 0.02 or more and 0.06 or less. ]
Is a complex oxide represented by.

  In the above formula, x is 0.55 or more and 0.75 or less, preferably 0.55 or more and 0.70 or less, more preferably more than 0.60 and 0.70 or less, for example, more than 0.60 and 0. It may be 65 or less or 0.65 or more and 0.70 or less.

  In the above formula, y is 0.05 or more and 0.15 or less, preferably 0.05 or more and 0.10 or less, more preferably 0.05 or more and less than 0.08, for example, 0.05, 0.06 or 0. It can be 07. In another aspect, y may be preferably 0.07 or more and 0.10 or less, more preferably 0.09 or more and 0.10 or less.

  By setting x and y within the above ranges, the composite oxide of the present invention can exhibit a large electrocaloric effect. In particular, the composite oxide of the present invention can exhibit a large electrocaloric effect even in the temperature range of 80 ° C. or higher and 160 ° C. or lower. Furthermore, the composite oxide of the present invention can have high withstand voltage and the like. In particular, the composite oxide of the present invention can have high withstand voltage even in the temperature range of 80 ° C. or higher and 160 ° C. or lower.

  In the above formula, z may be 0.02 or more and 0.06 or less, for example 0.03 or more and 0.06 or less, or 0.03 or more and 0.05 or less.

  In the above formula, w may be 0.02 or more and 0.06 or less, for example 0.03 or more and 0.06 or less, or 0.03 or more and 0.05 or less.

  By setting z and w in the above ranges, the composite oxide of the present invention can have high insulating properties over a wide temperature range.

In one aspect, the complex oxide of the present invention is
x and y are points A1 (0.50, 0.07) on the triangular phase diagram drawn by the value of (x, y),
Point A2 (0.50, 0.17),
Point A3 (0.65, 0.17),
Point A4 (0.75, 0.13),
Point A5 (0.75,0.05),
Point A6 (0.70,0.03) and point A7 (0.60,0.07)
In a range surrounded by a straight line (that is, a region in which A1-A2-A3-A4-A5-A6-A7-A1 are sequentially connected) (however, the boundary is not included),
z is 0.02 or more and 0.06 or less,
It may be a composite oxide represented by the above formula (I) or (II), in which w is 0.02 or more and 0.06 or less.

In another aspect, the complex oxide of the present invention is
x and y are points A1 (0.50, 0.07) on the triangular phase diagram drawn by the value of (x, y),
Point A2 (0.50, 0.17),
Point A3 (0.65, 0.17),
Point A4 (0.75, 0.13),
Point A5 (0.75,0.05),
Point A6 (0.70,0.03) and point A8 (0.65,0.07)
Is in a range surrounded by a straight line (that is, a region in which A1-A2-A3-A4-A5-A6-A8-A1 are sequentially connected) (however, the boundary is not included),
z is 0.02 or more and 0.06 or less,
It may be a composite oxide represented by the above formula (I) or (II), in which w is 0.02 or more and 0.06 or less.

In a preferred embodiment, the composite oxide of the present invention is
x and y are points A11 (0.55, 0.15) on the triangular phase diagram drawn by the value of (x, y),
Point A12 (0.70, 0.15),
Point A13 (0.75, 0.13),
Point A14 (0.75,0.05),
Point A15 (0.70,0.05),
Point A16 (0.65, 0.08),
Point A17 (0.60,0.09) and point A18 (0.55,0.09)
In a region connected by a straight line (that is, a region in which A11-A12-A13-A14-A15-A16-A17-A18-A11 are sequentially connected),
z is 0.02 or more and 0.06 or less,
It may be a composite oxide represented by the above formula (I) or (II), in which w is 0.02 or more and 0.06 or less.

In a preferred embodiment, the composite oxide of the present invention is
x and y are points B1 (0.55, 0.15) on the triangular phase diagram drawn by the value of (x, y),
Point B2 (0.60, 0.15),
Point B3 (0.65, 0.15),
Point B4 (0.70, 0.13),
Point B5 (0.70,0.09),
Point B6 (0.70,0.05),
Point B7 (0.65, 0.07),
Point B8 (0.60,0.09) and point B9 (0.55,0.09)
In a region surrounded by a straight line (that is, a region in which B1-B2-B3-B4-B5-B6-B7-B8-B9-B1 are sequentially connected),
z is 0.02 or more and 0.06 or less,
It may be a composite oxide represented by the above formula (I) or (II), in which w is 0.02 or more and 0.06 or less.

In another preferred embodiment, the composite oxide of the present invention is
x and y are points B1 (0.55, 0.15) on the triangular phase diagram drawn by the value of (x, y),
Point B2 (0.60, 0.15),
Point B3 (0.65, 0.15),
Point B4 (0.70, 0.13),
Point B5 (0.70,0.09),
Point B6 (0.70,0.05),
Point B7 '(0.65, 0.08),
Point B8 (0.60,0.09) and point B9 (0.55,0.09)
In a region surrounded by a straight line (that is, a region in which B1-B2-B3-B4-B5-B6-B7'-B8-B9-B1 are sequentially connected),
z is 0.02 or more and 0.06 or less,
It may be a composite oxide represented by the above formula (I) or (II), in which w is 0.02 or more and 0.06 or less.

In a more preferred embodiment, the composite oxide of the present invention is
x and y are points B11 (0.60, 0.13) on the triangular phase diagram drawn by the value of (x, y),
Point B12 (0.70, 0.13) and point B13 (0.70, 0.09)
In a region surrounded by a straight line (that is, a region in which B11-B12-B13-B11 are sequentially connected),
z is 0.02 or more and 0.06 or less,
It may be a composite oxide represented by the above formula (I) or (II), in which w is 0.02 or more and 0.06 or less.

  By setting it as the said range, the composite oxide of this invention can have a larger electrocaloric effect, higher withstand voltage, etc.

In one aspect, the complex oxide of the present invention is
A composite oxide containing Pb, Zr, Sn, Ti and M ¹ or M ² ,
M ¹ is Nb or Ta,
M ² is W or Mo,
The molar part of Zr contained in 100 molar parts of Zr and Sn is p molar part,
The molar portion of Ti contained in 100 molar portions of Zr, Sn and Ti is q molar portion,
The content molar part of M ¹ in the total 100 molar parts of Zr, Sn, Ti and M ¹ is r molar part,
In 100 mol parts in total of Zr, Sn, Ti and M ² , the contained mol part of M ² is s mol part,
p is 55 or more and 75 or less, preferably 55 or more and 70 or less,
q is 5 or more and 15 or less,
r is 2 or more and 6 or less,
s is 2 or more and 6 or less,
It can be a complex oxide.

  The above p may be 55 or more and 75 or less, preferably 55 or more and 70 or less, more preferably more than 60 and 70 or less, for example, more than 60 and 65 or less, or 65 or more and 70 or less.

  The q may be 5 or more and 15 or less, preferably 5 or more and 10 or less, more preferably 5 or more and less than 8, such as 5, 6 or 7. In another aspect, q may be preferably 7 or more and 10 or less, more preferably 9 or more and 10 or less.

  By setting p and q within the above ranges, the composite oxide of the present invention can exhibit a large electrocaloric effect. In particular, the composite oxide of the present invention can exhibit a large electrocaloric effect even in the temperature range of 80 ° C. or higher and 160 ° C. or lower. Furthermore, the composite oxide of the present invention can have high withstand voltage and the like. In particular, the composite oxide of the present invention can have high withstand voltage even in the temperature range of 80 ° C. or higher and 160 ° C. or lower.

  The r may be 2 or more and 6 or less, for example 3 or more and 6 or less, or 3 or more and 5 or less.

  The s can be 2 or more and 6 or less, for example 3 or more and 6 or less, or 3 or more and 5 or less.

  By setting r and s in the above ranges, the composite oxide of the present invention can have high insulating properties over a wide temperature range.

In one aspect, the complex oxide of the present invention is
p and q are points C1 (50, 7) on the triangular phase diagram drawn by the value of (p, q),
Point C2 (50,17),
Point C3 (65, 17),
Point C4 (75,13),
Point C5 (75,5),
Point C6 (70,3) and point C7 (60,7)
Is in a range surrounded by a straight line (that is, a region in which C1-C2-C3-C4-C5-C6-C7-C1 are sequentially connected) (however, the boundary is not included),
r is 2 or more and 6 or less,
It may be the above composite oxide in which s is 2 or more and 6 or less.

In another aspect, the complex oxide of the present invention is
p and q are points C1 (50, 7) on the triangular phase diagram drawn by the value of (p, q),
Point C2 (50,17),
Point C3 (65, 17),
Point C4 (75,13),
Point C5 (75,5),
Point C6 (70,3) and point C8 (65,7)
In a range surrounded by a straight line (that is, a region in which C1-C2-C3-C4-C5-C6-C8-C1 are sequentially connected) (however, the boundary is not included),
r is 2 or more and 6 or less,
It may be the above composite oxide in which s is 2 or more and 6 or less.

In a preferred embodiment, the composite oxide of the present invention is
p and q are points C11 (55, 15) on the triangular phase diagram drawn by the value of (p, q),
Point C12 (70,15),
Point C13 (75,13),
Point C14 (75,5),
Point C15 (70,5),
Point C16 (65,8),
Point C17 (60,9) and point C18 (55,9)
In a region connected by a straight line (that is, a region in which C11-C12-C13-C14-C15-C16-C17-C18-C11 are sequentially connected),
r is 2 or more and 6 or less,
It may be the above composite oxide in which s is 2 or more and 6 or less.

In a preferred embodiment, the composite oxide of the present invention is
p and q are points D1 (55, 15) on the triangular phase diagram drawn by the value of (p, q),
Point D2 (60,15),
Point D3 (65,15),
Point D4 (70,13),
Point D5 (70,9),
Point D6 (70,5),
Point D7 (65,7),
Point D8 (60,9) and point D9 (55,9)
In a range surrounded by a straight line (that is, a region in which D1-D2-D3-D4-D5-D6-D7-D8-D9-D1 are sequentially connected), r is 2 or more and 6 or less, It may be the above composite oxide in which s is 2 or more and 6 or less.

In another preferred embodiment, the composite oxide of the present invention is
p and q are points D1 (55, 15) on the triangular phase diagram drawn by the value of (p, q),
Point D2 (60,15),
Point D3 (65,15),
Point D4 (70,13),
Point D5 (70,9),
Point D6 (70,5),
Point D7 '(65,8),
Point D8 (60,9) and point D9 (55,9)
In a range surrounded by a straight line (that is, a region in which D1-D2-D3-D4-D5-D6-D7-D8-D9-D1 are sequentially connected), r is 2 or more and 6 or less, It may be the above composite oxide in which s is 2 or more and 6 or less.

In a more preferred embodiment, the composite oxide of the present invention is
p and q are points D11 (60, 13) on the triangular phase diagram drawn by the value of (p, q),
Point D12 (70,13) and point D13 (70,9)
Is in a range surrounded by a region in which a straight line is connected (that is, a region in which D11-D12-D13-D11 are sequentially connected), r is 2 or more and 6 or less, and s is 2 or more and 6 or less. It can be an oxide.

  By setting it as the said range, the composite oxide of this invention can have a larger electrocaloric effect, higher withstand voltage, etc.

In one aspect,
When M ¹ is included, the content of Pb contained in Zr, Sn, Ti, and M ¹ is 100 ((r / 2)).
When M ² is included, the content of Pb in 100 parts by mole of Zr, Sn, Ti and M ² is (100-s).

  The composite oxide of the present invention may have a perovskite structure.

  The complex oxide of the present invention can exert a large electrocaloric effect in the temperature range of 80 ° C. or higher and 160 ° C. or lower required for cooling servers and electronic components. Although the present invention is not bound by any theory, the composite oxide of the present invention utilizes a composition region in which the three phase transition points of the parent phase, ferroelectric, antiferroelectric and paraelectric, are gathered at one point. As a result, the number of states under a non-electric field increases and it is possible to cause a large entropy change even in a low electric field. As a result, an unprecedentedly large ΔT can be achieved. Further, the composite oxide of the present invention has a high insulating property by adding a donor element such as Nb, Ta, W, or Mo to a high temperature region, for example, in a temperature region of 80 ° C. or higher and 160 ° C. or lower, The reduction of the electric field is suppressed. In addition, Joule heat generation due to a leak current that leads to thermal destruction of the element is suppressed.

  As described above, the composite oxide of the present invention exhibits a large electrocaloric effect in the temperature range of 80 ° C or higher and 160 ° C or lower. Specifically, the composite oxide of the present invention is 2.0 K or more, preferably 2.5 K or more, more preferably when an electric field of 10 MV / m is applied in a temperature range of 80 ° C. or higher and 160 ° C. or lower. A ΔT of 3.0 K or more is shown.

  Here, ΔT means a temperature change of the sample caused by application and removal of an electric field to the sample. ΔT can be obtained by directly attaching an ultrafine thermocouple to the sample and measuring the temperature change during the application and removal of the electric field. As for the method of measuring ΔT, a platinum resistance temperature detector or a thermistor element may be directly attached as long as the temperature of the sample can be measured, or an IR camera (infrared camera / thermoviewer) may be used without contact. Good.

  Moreover, the complex oxide of the present invention can have high insulating properties over a wide temperature range.

The complex oxide of the present invention has, for example, 1 × 10 ⁸ Ω · cm or more and 1 × 10 ¹⁴ Ω · cm or less, preferably 1 × 10 ⁹ Ω · cm or more, in a temperature range of 80 ° C. or higher and 160 ° C. or lower. It has a specific resistance of 1 × 10 ¹² Ω · cm or less, more preferably 1 × 10 ¹⁰ Ω · cm or more and 1 × 10 ¹² Ω · cm or less.

  Further, the composite oxide of the present invention can have high withstand voltage characteristics over a wide temperature range.

  The composite oxide of the present invention exhibits a withstand voltage of 10 MV / m or more, preferably 20 MV / m or more, more preferably 30 MV / m in the temperature range of 80 ° C. or more and 160 ° C. or less.

  Further, the complex oxide of the present invention can undergo a phase transition even if the electric field is relatively low, that is, it can exhibit a large electrocaloric effect. Therefore, the complex oxide of the present invention can exhibit a high electrocaloric effect even in a shape having a relatively large thickness in which it is difficult to apply a strong electric field.

The composite oxide of the present invention can be obtained by, for example, mixing Pb, Zr, Sn, Ti and an oxide or salt of M ¹ or M ² and firing the mixture. By mixing Pb, Zr, Sn, Ti and M ¹ or M ² in a predetermined ratio and firing in a lead atmosphere, lead volatilization from the obtained composite oxide can be suppressed.

That is, the present invention is
A method for producing a composite oxide containing Pb, Zr, Sn, Ti and M ¹ (M ¹ is Nb or Ta) or M ² (M ² is W or Mo), comprising:
Pb, Zr, Sn, Ti and an oxide or salt of M ¹ or M ² ,
The molar part of Zr contained in 100 molar parts of Zr and Sn is p molar part,
The molar portion of Ti contained in 100 molar portions of Zr, Sn and Ti is q molar portion,
The content molar part of M ¹ in the total 100 molar parts of Zr, Sn, Ti and M ¹ is r molar part,
In 100 mol parts in total of Zr, Sn, Ti and M ² , the contained mol part of M ² is s mol part,
p is 55 or more and 75 or less, preferably 55 or more and 70 or less,
q is 5 or more and 15 or less,
r is 2 or more and 6 or less,
s is 2 or more and 6 or less,
Mix in the ratio
When M ¹ is included, the content of Pb based on 100 parts by mole of Zr, Sn, Ti and M ¹ is (100− (r / 2)), or when M ² is included, Zr, Sn, The content of Pb contained in 100 parts by mole of Ti and M ² is (100-s) parts by mole,
A manufacturing method is provided by firing in a lead atmosphere such that

In one aspect, the present invention provides a composite oxide comprising Pb, Zr, Sn, Ti and M ¹ (M ¹ is Nb or Ta) or M ² (M ² is W or Mo). A manufacturing method,
Pb, Zr, Sn, Ti and an oxide or salt of M ¹ or M ² ,
The molar part of Zr contained in 100 molar parts of Zr and Sn is p molar part,
The molar portion of Ti contained in 100 molar portions of Zr, Sn and Ti is q molar portion,
The content molar part of M ¹ in the total 100 molar parts of Zr, Sn, Ti and M ¹ is r molar part,
In 100 mol parts in total of Zr, Sn, Ti and M ² , the contained mol part of M ² is s mol part,
p and q are points C1 (50, 7) on the trigonometric diagram drawn by the value of (p, q),
Point C2 (50,17),
Point C3 (65, 17),
Point C4 (75,13),
Point C5 (75,5),
Point C6 (70,3) and point C7 (60,7)
It is in the range surrounded by the area connecting straight lines (but not including the boundary),
r is 2 or more and 6 or less,
s is 2 or more and 6 or less,
When M ¹ is included, the content of Pb based on 100 parts by mole of Zr, Sn, Ti and M ¹ is (100− (r / 2)), or when M ² is included, Zr, Sn, The content of Pb contained in 100 parts by mole of Ti and M ² is (100-s) parts by mole,
There is provided a manufacturing method by mixing in the following ratio and baking after baking in a lead atmosphere such that the above ratio is obtained.

In another aspect, the present invention provides a composite oxide comprising Pb, Zr, Sn, Ti and M ¹ (M ¹ is Nb or Ta) or M ² (M ² is W or Mo). A manufacturing method,
Pb, Zr, Sn, Ti and an oxide or salt of M ¹ or M ² ,
The molar part of Zr contained in 100 molar parts of Zr and Sn is p molar part,
The molar portion of Ti contained in 100 molar portions of Zr, Sn and Ti is q molar portion,
The content molar part of M ¹ in the total 100 molar parts of Zr, Sn, Ti and M ¹ is r molar part,
In 100 mol parts in total of Zr, Sn, Ti and M ² , the contained mol part of M ² is s mol part,
p and q are points C1 (50, 7) on the trigonometric diagram drawn by the value of (p, q),
Point C2 (50,17),
Point C3 (65, 17),
Point C4 (75,13),
Point C5 (75,5),
Point C6 (70,3) and point C8 (65,7)
It is in the range surrounded by the area connecting straight lines (but not including the boundary),
r is 2 or more and 6 or less,
s is 2 or more and 6 or less,
When M ¹ is included, the content of Pb based on 100 parts by mole of Zr, Sn, Ti and M ¹ is (100− (r / 2)), or when M ² is included, Zr, Sn, The content of Pb contained in 100 parts by mole of Ti and M ² is (100-s) parts by mole,
There is provided a manufacturing method by mixing in the following ratio, and baking after baking in a lead atmosphere such that the above ratio is obtained.

In one aspect, the present invention provides a composite oxide comprising Pb, Zr, Sn, Ti and M ¹ (M ¹ is Nb or Ta) or M ² (M ² is W or Mo). A manufacturing method,
Pb, Zr, Sn, Ti and an oxide or salt of M ¹ or M ² ,
The molar part of Zr contained in 100 molar parts of Zr and Sn is p molar part,
The molar portion of Ti contained in 100 molar portions of Zr, Sn and Ti is q molar portion,
The content molar part of M ¹ in the total 100 molar parts of Zr, Sn, Ti and M ¹ is r molar part,
In 100 mol parts in total of Zr, Sn, Ti and M ² , the contained mol part of M ² is s mol part,
p and q are points C11 (55, 15) on the triangular phase diagram drawn by the value of (p, q),
Point C12 (70,15),
Point C13 (75,13),
Point C14 (75,5),
Point C15 (70,5),
Point C16 (65,8),
Point C17 (60,9) and point C18 (55,9)
It is in the range surrounded by the area that connects
r is 2 or more and 6 or less,
s is 2 or more and 6 or less,
When M ¹ is included, the content of Pb based on 100 parts by mole of Zr, Sn, Ti and M ¹ is (100− (r / 2)), or when M ² is included, Zr, Sn, The content of Pb contained in 100 parts by mole of Ti and M ² is (100-s) parts by mole,
There is provided a manufacturing method by mixing in the following ratio and baking after baking in a lead atmosphere such that the above ratio is obtained.

Preferably, in the mixing step of the above production method,
When M ¹ is included, the content of Pb is 100 ((r / 2)), or when M ² is included, the content of Pb based on 100 parts of Zr, Sn, Ti and M ¹ is 100. The total molar content of Pb based on 100 molar parts of Zr, Sn, Ti and M ² is (100-s) molar part,
Mix Pb, Zr, Sn, Ti and an oxide or salt of M ¹ or M ² , preferably an oxide.

  Since the complex oxide of the present invention exhibits an excellent electrocaloric effect, it can be used as a material for an endothermic element.

  Hereinafter, the heat absorbing / heating element of the present invention will be described with reference to the drawings. However, the shapes and arrangements of the heat absorption and heat generation elements and the constituent elements of the embodiments described below are not limited to the illustrated examples.

  As shown in FIG. 1, a heat-absorbing element 1a according to a first embodiment of the present invention is a dielectric composed of a pair of electrodes 2 and 4 and a complex oxide of the present invention located between the pair of electrodes. And a body portion 6. When a voltage is applied between the electrodes 2 and 4, an electric field is applied to the dielectric part 6. As a result, the dielectric part 6 generates heat. When the voltage between the electrodes 2 and 4 is removed, the electric field applied to the dielectric part 6 disappears. As a result, the dielectric part 6 absorbs heat.

  The shape of the dielectric part 6 is not particularly limited, and can be formed into various shapes such as a sheet shape, a block shape and the like. The molding method is not particularly limited, and compression, sintering or the like can be used. Moreover, you may mix and shape with binders, such as resin or glass.

  The material forming the electrodes 2 and 4 is not particularly limited, but examples thereof include Ag, Cu, Pt, Ni, Al, Pd, Au, and alloys thereof (for example, Ag—Pd). Among them, Pt, Ag, Pd or Ag-Pd is preferable.

  The electrodes 2 and 4 may have a function of transporting the amount of heat of the dielectric part in addition to the function of applying an electric field to the dielectric part. Therefore, from the viewpoint of heat transfer, the material forming the electrode is preferably a material having high thermal conductivity, for example, Ag.

  The shapes of the electrodes 2 and 4 are not particularly limited, but from the viewpoint of heat transfer, a shape that covers the entire one surface of the dielectric portion 6 is preferable.

  INDUSTRIAL APPLICABILITY Since the heat absorbing / heating element of the present invention exhibits an excellent electrocaloric effect, it can be used as a heat management element, particularly as a cooling element.

  The heat absorbing / heating element of the present invention uses the dielectric part made of a material that exhibits a large electrocaloric effect in the temperature range of 80 ° C. or higher and 160 ° C. or lower. Therefore, the heat absorbing / heating element of the present invention can be preferably used especially in applications such as servers under a relatively high temperature environment.

  In a preferred embodiment, the heat sinking / heating element of the present invention may include a laminate of a plurality of electrodes and a plurality of dielectric layers. That is, the present invention is an endothermic device comprising a laminated body having a plurality of electrode layers and a plurality of dielectric layers located between the electrode layers, wherein the dielectric layer is the present invention. Provided is an endothermic element which is composed of the complex oxide of.

  For example, the heat absorbing / heating element 1b as shown in FIG. 2 can be used. In the heat absorbing / heating element 1b of the second embodiment of the present invention, the plurality of internal electrodes 12a and 12b and the plurality of dielectric portions 14 are alternately laminated. The internal electrodes 12a and 12b are electrically connected to the external electrodes 16a and 16b, respectively, which are arranged on the end faces of the heat absorbing / heating element 1b. When a voltage is applied from the outer electrodes 16a and 16b, an electric field is formed between the inner electrodes 12a and 12b. The electric field causes the dielectric part 14 to generate heat. When the voltage is removed, the electric field disappears, and as a result, the dielectric portion 14 absorbs heat.

  In one aspect, the dielectric portions 14 to be laminated may all have the same composition, or one or more dielectric portions having different compositions may be laminated.

  With such a structure, it becomes possible to apply a stronger electric field to the dielectric portion 14, and a larger ΔT can be obtained. Further, since the internal electrode also functions as a heat propagation path into the inside of the dielectric portion, efficient heat management is possible.

  In the heat absorbing / heating elements 1a and 1b described above, the electrodes and the dielectric part are in contact with each other over substantially the entire surface, but the present invention is not limited to such a structure, and an electric field can be applied to the dielectric part. Any structure will do. Further, although the heat absorbing / heating elements 1a and 1b have a rectangular parallelepiped block shape, the shape of the heat absorbing / heating element of the present invention is not limited to this, and may be, for example, a cylindrical shape or a sheet shape, and further, the unevenness or the through holes. Etc. may be included.

  The heat-absorbing element of the present invention absorbs the heat generated by the heat source mainly when the electric field is released and heat is absorbed, or when the temperature of the heat-absorbing element is lowered by this heat absorption. Further, the heat absorbing / heating element of the present invention releases the absorbed heat to the outside mainly when an electric field is applied to radiate the heat. Therefore, the heat absorbing / heating element of the present invention can be used as a cooling device.

  Although the endothermic and exothermic element of the present invention has been described above, the present invention is not limited to the above-described embodiment, and various modifications can be made.

  The present invention also provides an electronic component including the heat absorbing / heating element of the present invention, and an electronic device including the heat absorbing / heating element or the electronic component of the present invention.

  The electronic components are not particularly limited, but include, for example, a central processing unit (CPU), a hard disk (HDD), a power management IC (PMIC), a power amplifier (PA), a transceiver IC, a voltage regulator (VR), and the like. Integrated circuits (ICs), light emitting diodes (LEDs), incandescent light bulbs, light emitting devices such as semiconductor lasers, parts that can be a heat source such as field effect transistors (FETs), and other parts such as lithium ion batteries, substrates, heat sinks Components generally used for electronic devices such as housings can be cited.

  The electronic device is not particularly limited, but examples thereof include a mobile phone, a smartphone, a personal computer (PC), a tablet terminal, a hard disk drive, and a data server.

In Preparation of endothermic and exothermic elements _{Pb 1-z / 2 ([} Zr x Sn 1-x] 1-y Ti y) 1-z Nb z O 3, Pb 3 O 4, ZrO 2, SnO, TiO 2 and Nb ₂ O ₅ was prepared, weighed so as to have the composition shown in Table 1 (sample numbers 1 to 39), and then pulverized and mixed by a ball mill. The obtained mixture was calcined in the air at 850 ° C. to prepare a calcined powder having a perovskite structure.

  A polyvinyl butyral binder, a plasticizer and ethanol were added to this calcined powder and wet mixed by a ball mill to prepare a ceramic slurry. This ceramic slurry was formed into a green sheet by a doctor blade method so that the thickness of the dielectric layer after firing would be 40 μm. Next, Pt paste was screen-printed on the ceramic green sheet to form internal electrodes.

Next, a plurality of ceramic green sheets on which the internal electrodes were formed were laminated so that the drawn-out sides of the internal electrodes were staggered to obtain a laminated green chip. This laminated body was degreased under an atmosphere of N ₂ : atmosphere = 1: 1 at 450 to 550 ° C., 10 g of PbZrO ₃ powder and 1 to ₂ g of green chips were enclosed in an alumina closed sheath, and the mixture was baked at 1300 ° C. for 4 hours. A ceramic laminate was obtained. Finally, Ag paste was applied as an external electrode and baked to prepare a laminated heat-absorbing element.

The external dimensions of the laminated heat generating and heating element obtained as described above are 7.2 mm in width, 10 mm in length, and 0.92 mm in thickness, and the thickness of the dielectric layer interposed between the internal electrodes is 40 μm and the internal electrodes are 40 μm. The thickness was 1.5 μm. The total number of effective dielectric layers was 20, and the counter electrode area per layer was 40.2 mm ² .

(Evaluation)
-Elemental analysis When the laminated endothermic heating element obtained above was dissolved and subjected to ICP (Inductively Coupled Plasma) analysis, Zr, Sn, [ZrSn], Ti, [ZrSnTi], except for Pt as an internal electrode component, It was confirmed that each composition of Nb was as shown in Table 1.

-XRD structural analysis When the laminated endothermic heat generating element obtained above was analyzed by XRD (X-ray diffraction) structural analysis, it was confirmed that the main component had a perovskite structure.

・ Measurement of electrocaloric effect (ΔT measurement)
With respect to the electrocaloric effect characteristics of the laminated endothermic heat generating element obtained above, an ultrafine thermocouple of φ = 0.5 mm was directly attached to the element, and the temperature change ΔT when an electric field was applied was measured at 80 ° C. to 200 ° C., The temperature dependence of ΔT was evaluated. The results are shown in Table 2.

  A sample that causes dielectric breakdown when an electric field of 10 MV / m is applied in a temperature range of 80 ° C. to 200 ° C. is disadvantageous in being used as a cooling device for small electronic devices, and thus was rejected. Further, a sample whose ΔT peak top temperature is not in the temperature range of 80 ° C. to 200 ° C. and a sample whose ΔT at the peak top temperature is less than 2K were also regarded as NG for the same reason. A sample having a ΔT peak top temperature in the temperature range of 80 ° C. to 200 ° C. and a ΔT at the peak top temperature of 2K or higher was designated as G, and a sample having a ΔT at the peak top temperature of 3K or higher was designated as G *. FIG. 3 shows a compositional triangular phase diagram of Zr, Sn and Ti for the sample of z = 0.02 (Sample Nos. 1-27). In FIG. 3, ● indicates G *, ○ indicates G, and × indicates NG. Further, FIG. 4 shows the electric field dependence of ΔT of Sample No. 22 and FIG. 5 shows the temperature dependence of ΔT when the electric field is applied.

  In addition, in the above-described embodiment, an example in which Nb or Ta is added to the lead zirconate titanate stannate antiferroelectric ceramics is shown, but the additive element is not limited to this. When the average ionic radius of the additive element is smaller than the average ionic radius of the matrix ceramic that acts as a donor in the matrix ceramic and has a composition ratio of B site elements (Zr, Sn, Ti) of the matrix ceramic having a perovskite structure. It is considered good. Elements that satisfy this include Mo and W, and it is considered that similar effects can be obtained even when these elements are added.

  The composite oxide of the present invention can be preferably used as a material for an endothermic heating element because it exhibits a high electrocaloric effect. INDUSTRIAL APPLICABILITY The heat absorbing / heating element of the present invention can be used as a heat management element in a refrigerator or a freezer, and is also used as a cooling device for various electronic devices, for example, small electronic devices such as mobile phones in which the heat countermeasure problem has become remarkable. Can be used.

1a, 1b ... Heat absorbing / heating element 2, 4 ... Electrode 6 ... Dielectric part 12a, 12b ... Internal electrode 14 ... Dielectric layer 16a, 16b ... External electrode

Claims (15)

Formula (I) or (II) below:
_{Pb 1-z / 2 ([} Zr x Sn 1-x] 1-y Ti y) 1-z M 1 z O 3 (I)
_{Pb 1-w ([Zr x} Sn 1-x] 1-y Ti y) 1-w M 2 w O 3 (II)
[In the formula:
M ¹ is Nb or Ta,
M ² is W or Mo,
x and y are points A1 (0.50, 0.07) on the triangular phase diagram drawn by the value of (x, y),
Point A2 (0.50, 0.17),
Point A3 (0.65, 0.17),
Point A4 (0.75, 0.13),
Point A5 (0.75,0.05),
Point A6 (0.70,0.03) and point A7 (0.60,0.07)
It is in the range surrounded by the area connecting straight lines (but not including the boundary),
z is 0.02 or more and 0.06 or less,
w is 0.02 or more and 0.06 or less. ]
A composite oxide represented by formula (I) or (II). Formula (I) or (II) below:
_{Pb 1-z / 2 ([} Zr x Sn 1-x] 1-y Ti y) 1-z M 1 z O 3 (I)
_{Pb 1-w ([Zr x} Sn 1-x] 1-y Ti y) 1-w M 2 w O 3 (II)
[In the formula:
M ¹ is Nb or Ta,
M ² is W or Mo,
x and y are points A11 (0.55, 0.15) on the triangular phase diagram drawn by the value of (x, y),
Point A12 (0.70, 0.15),
Point A13 (0.75, 0.13),
Point A14 (0.75,0.05),
Point A15 (0.70,0.05),
Point A16 (0.65, 0.08),
Point A17 (0.60,0.09) and point A18 (0.55,0.09)
It is in the range surrounded by the area that connects
z is 0.02 or more and 0.06 or less,
w is 0.02 or more and 0.06 or less. ]
A composite oxide represented by formula (I) or (II). x and y are points B1 (0.55, 0.15) on the triangular phase diagram drawn by the value of (x, y),
Point B2 (0.60, 0.15),
Point B3 (0.65, 0.15),
Point B4 (0.70, 0.13),
Point B5 (0.70,0.09),
Point B6 (0.70,0.05),
Point B7 (0.65, 0.07),
Point B8 (0.60,0.09) and point B9 (0.55,0.09)
It is in the range surrounded by the area that connects
The composite oxide represented by the formula (I) or (II) according to claim 1 or 2. x and y are points B11 (0.60, 0.13) on the triangular phase diagram drawn by the value of (x, y),
Point B12 (0.70, 0.13) and point B13 (0.70, 0.09)
It is in the range surrounded by the area that connects
The composite oxide represented by the formula (I) or (II) according to claim 1 or 2. A composite oxide containing Pb, Zr, Sn, Ti and M ¹ or M ² ,
M ¹ is Nb or Ta,
M ² is W or Mo,
The molar part of Zr contained in 100 molar parts of Zr and Sn is p molar part,
The molar portion of Ti contained in 100 molar portions of Zr, Sn and Ti is q molar portion,
The content molar part of M ¹ in the total 100 molar parts of Zr, Sn, Ti and M ¹ is r molar part,
In 100 mol parts in total of Zr, Sn, Ti and M ² , the contained mol part of M ² is s mol part,
p and q are points C1 (50, 7) on the trigonometric diagram drawn by the value of (p, q),
Point C2 (50,17),
Point C3 (65, 17),
Point C4 (75,13),
Point C5 (75,5),
Point C6 (70,3) and point C7 (60,7)
It is in the range surrounded by the area connecting straight lines (but not including the boundary),
r is 2 or more and 6 or less,
s is 2 or more and 6 or less,
Complex oxide. A composite oxide containing Pb, Zr, Sn, Ti and M ¹ or M ² ,
M ¹ is Nb or Ta,
M ² is W or Mo,
The molar part of Zr contained in 100 molar parts of Zr and Sn is p molar part,
The molar portion of Ti contained in 100 molar portions of Zr, Sn and Ti is q molar portion,
The content molar part of M ¹ in the total 100 molar parts of Zr, Sn, Ti and M ¹ is r molar part,
In 100 mol parts in total of Zr, Sn, Ti and M ² , the contained mol part of M ² is s mol part,
p and q are points C11 (55, 15) on the triangular phase diagram drawn by the value of (p, q),
Point C12 (70,15),
Point C13 (75,13),
Point C14 (75,5),
Point C15 (70,5),
Point C16 (65,8),
Point C17 (60,9) and point C18 (55,9)
It is in the range surrounded by the area that connects
r is 2 or more and 6 or less,
s is 2 or more and 6 or less,
Complex oxide. p and q are points D1 (55, 15) on the triangular phase diagram drawn by the value of (p, q),
Point D2 (60,15),
Point D3 (65,15),
Point D4 (70,13),
Point D5 (70,9),
Point D6 (70,5),
Point D7 (65,7),
Point D8 (60,9) and point D9 (55,9)
7. The complex oxide according to claim 5 or 6, which is in a range surrounded by a region in which is connected by a straight line. p and q are points D11 (60, 13) on the triangular phase diagram drawn by the value of (p, q),
Point D12 (70,13) and point D13 (70,9)
7. The complex oxide according to claim 5 or 6, which is in a range surrounded by a region in which is connected by a straight line. When M ¹ is included, the content of Pb contained in Zr, Sn, Ti, and M ¹ is 100 ((r / 2)).
The complex oxidation according to any one of claims 5 to 8, wherein when M ² is contained, the content mole part of Pb with respect to 100 mole parts in total of Zr, Sn, Ti and M ² is (100-s) mole part. object.   The composite oxide according to claim 1, wherein the main component of the composite oxide has a perovskite structure.   A heat-absorbing element comprising a laminate having a plurality of electrode layers and a plurality of dielectric layers located between the electrode layers, wherein the dielectric layer is any one of claims 1 to 10. An endothermic heat generating element comprising the complex oxide according to 1.   An electronic device comprising the heat absorbing / heating element according to claim 11. A method for producing a composite oxide containing Pb, Zr, Sn, Ti and M ¹ (M ¹ is Nb or Ta) or M ² (M ² is W or Mo), comprising:
Pb, Zr, Sn, Ti and an oxide or salt of M ¹ or M ² ,
The molar part of Zr contained in 100 molar parts of Zr and Sn is p molar part,
The molar portion of Ti contained in 100 molar portions of Zr, Sn and Ti is q molar portion,
The content molar part of M ¹ in the total 100 molar parts of Zr, Sn, Ti and M ¹ is r molar part,
In 100 mol parts in total of Zr, Sn, Ti and M ² , the contained mol part of M ² is s mol part,
p and q are points C1 (50, 7) on the trigonometric diagram drawn by the value of (p, q),
Point C2 (50,17),
Point C3 (65, 17),
Point C4 (75,13),
Point C5 (75,5),
Point C6 (70,3) and point C7 (60,7)
It is in the range surrounded by the area connecting straight lines (but not including the boundary),
r is 2 or more and 6 or less,
s is 2 or more and 6 or less,
When M ¹ is included, the content of Pb based on 100 parts by mole of Zr, Sn, Ti and M ¹ is (100− (r / 2)), or when M ² is included, Zr, Sn, The content of Pb contained in 100 parts by mole of Ti and M ² is (100-s) parts by mole,
And a firing method under firing in a lead atmosphere such that the firing rate is the same. A method for producing a composite oxide containing Pb, Zr, Sn, Ti and M ¹ (M ¹ is Nb or Ta) or M ² (M ² is W or Mo), comprising:
Pb, Zr, Sn, Ti and an oxide or salt of M ¹ or M ² ,
The molar part of Zr contained in 100 molar parts of Zr and Sn is p molar part,
The molar portion of Ti contained in 100 molar portions of Zr, Sn and Ti is q molar portion,
The content molar part of M ¹ in the total 100 molar parts of Zr, Sn, Ti and M ¹ is r molar part,
In 100 mol parts in total of Zr, Sn, Ti and M ² , the contained mol part of M ² is s mol part,
p and q are points C11 (55, 15) on the triangular phase diagram drawn by the value of (p, q),
Point C12 (70,15),
Point C13 (75,13),
Point C14 (75,5),
Point C15 (70,5),
Point C16 (65,8),
Point C17 (60,9) and point C18 (55,9)
It is in the range surrounded by the area that connects
r is 2 or more and 6 or less,
s is 2 or more and 6 or less,
When M ¹ is included, the content of Pb based on 100 parts by mole of Zr, Sn, Ti and M ¹ is (100− (r / 2)), or when M ² is included, Zr, Sn, The content of Pb contained in 100 parts by mole of Ti and M ² is (100-s) parts by mole,
And a firing method under firing in a lead atmosphere such that the firing rate is the same.   The method for producing a composite oxide according to claim 13 or 14, wherein the main component of the composite oxide has a perovskite structure.

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